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Geochemistry of Travertines and Calcareous Tufas

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A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Geochemistry and Geochronology".

Deadline for manuscript submissions: closed (30 April 2023) | Viewed by 17110

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Special Issue Editors

Dr. Francesca Giustini

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Guest Editor

Istituto di Geologia Ambientale e Geoingegneria, CNR, 00015 Rome, Italy
Interests: stable and radiogenic isotopes; environmental geochemistry

Dr. Mauro Brilli

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Guest Editor

Istituto di Geologia Ambientale e Geoingegneria, CNR, 00015 Rome, Italy
Interests: light, stable isotopes applied to earth-life sciences and cultural heritage

Special Issue Information

Dear Colleagues,

Travertine and calcareous tufa are lithological terms generally used to describe continental carbonates, forming in a subaerial environment by precipitation of calcite/aragonite from waters ranging in temperature from ambient to boiling, around groundwater seepages, springs, and along streams and rivers. These deposits exist across all continents, some of them are confined to small, local discharge aprons below spring emergences, whereas others cover extensive areas and form impressive structures (e.g., Tivoli in Italy, Pamukkale in Turkey, Mammoth Hot Springs in USA, Plitvice in Croatia). Travertine and calcareous tufa are complex systems, which are generally investigated using a multidisciplinary approach: geochemistry (elemental and isotope compositions, dating), meso- and macro-scale morphological observations, mineralogy, petrography, and sedimentology, analysis of biotic content, that aim to elucidate travertine and tufa formation processes, environments, depositional models, and their subsequent history (diagenesis). The active carbonates depositing systems are natural laboratories, where it is possible to study the geochemical characteristics of forming-travertine/tufa and their parent waters. Fossil deposits are important terrestrial archives that may record past climate, environmental changes, neotectonic activity, hydrological–hydrothermal circulations; and indicate possible locations of geothermal resources or contribute to define the carbon cycle.

For this Special Issue, we invite you to publish your contributions related to travertine, calcareous tufa and related sediments (e.g., lacustrine carbonates, calcrete), fossils, and/or active deposits, with special focus on their mineralogy, major and trace element compositions, stable isotopes (oxygen, carbon, strontium), and radioisotopes (radiocarbon, uranium series). Contributions related to geochemistry of waters from which carbonate precipitates are also welcome.

Dr. Francesca Giustini
Dr. Mauro Brilli
Guest Editors

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Keywords

continental carbonates
travertine
calcareous tufa
stable isotope
radioisotopes
dating
mineralogy
elemental composition
hydrochemistry

Published Papers (12 papers)

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Editorial

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4 pages, 167 KiB

Open AccessEditorial

Editorial for Special Issue “Geochemistry of Travertines and Calcareous Tufas”

by Francesca Giustini and Mauro Brilli

Minerals 2024, 14(5), 442; https://doi.org/10.3390/min14050442 - 24 Apr 2024

Abstract

Travertine and calcareous tufa are the lithological terms generally used to describe continental carbonates [...] Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

Research

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18 pages, 10950 KiB

Open AccessArticle

Age and Depositional Temperature of Quaternary Travertine Spring Mounds from Slovakia

by Daniella S. C. Vieira, Daniel Pivko, László Rinyu, László Palcsu, Gabriella I. Kiss, Hsun-Ming Hu, Chuan-Chou Shen and Sándor Kele

Minerals 2023, 13(6), 794; https://doi.org/10.3390/min13060794 - 10 Jun 2023

Viewed by 1198

Abstract

Travertine spring mounds are common in Slovakia; however, their age and depositional temperature are still poorly known. Our study is the first multimethodological investigation involving stable carbon, oxygen, and clumped isotope (Δ₄₇) analyses and U-Th age determination of travertine mounds from different locations in Slovakia (Santovka, Dudince, Čerin, Bešeňová, Liptovský Ján, Liptovské Sliače, Vyšné Ružbachy, Gánovce, and Sivá Brada) to provide information about their age, origin, precipitation conditions, and temperature. The positive δ¹³C values imply that the parent water was charged with heavy CO₂ of deep origin. The δ¹⁸O values of spring waters range between −11.4‰ and −8.9‰, whereas the δ²H values vary from −80.5‰ to −58.3, indicating a meteoric origin for spring waters. Clumped isotope compositions (Δ₄₇) correspond to a deposition temperature between 4 °C and 32 °C. The U-Th age data of the studied travertines vary from 1.2 (Liptovské Sliače) to 301 ka (Dudince). Our results can serve as a basis for further detailed geochronological and geochemical studies to reconstruct the paleoclimate and paleoenvironment during travertine deposition periods in Slovakia since the mid-Pleistocene transition. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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16 pages, 2562 KiB

Open AccessArticle

Geochemical Stratigraphy of the Prima Porta Travertine Deposit (Roma, Italy)

by Mauro Brilli and Francesca Giustini

Minerals 2023, 13(6), 789; https://doi.org/10.3390/min13060789 - 08 Jun 2023

Cited by 1 | Viewed by 1011

Abstract

A stratigraphy of a buried travertine deposit was developed using stable isotope geochemistry, trace elements, and radiometric dating. The travertine was identified in a well at Prima Porta (north of Rome, Italy), located at the western boundary of the Tiber Valley, a morpho-tectonic depression of extensional origin. It deposited close to a spring that discharged groundwaters from the nearby volcanic aquifer and was associated with the rise of a deep-seated CO₂-rich fluid. The deposition occurred between 53.5 ± 10 ka to 24.2 ± 4.7 ka; its activation was probably coeval with the wettest climatic conditions occurring during Marine Isotope Stage 3, and the end coincided with the cold and arid phase of the last glacial maximum. The chronostratigraphy showed a strong variation in the accumulation rate along the depositional sequence, greater in the lower half and much slower in the upper part, with a sharp decrease in the accumulation rate occurring between 47 and 43 ka. Isotope and chemical stratigraphy described a temporal evolution of events that are correlated to the global climatic variability; palaeoclimatic changes, in fact, influenced the hydrological regime and indirectly the tectonic activity by modulating the emission of deep CO₂, the chemistry of the groundwater, and ultimately the precipitation of the travertine. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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21 pages, 3274 KiB

Open AccessArticle

Uranium Geochemistry of Italian Travertines and Calcareous Tufas: Exploring the Relationship between Carbonate Deposition, Groundwater Circulation and Subsurface Geology

by Francesca Giustini and Mauro Brilli

Minerals 2023, 13(6), 782; https://doi.org/10.3390/min13060782 - 08 Jun 2023

Viewed by 1000

Abstract

A database consisting of 163 data on the uranium content and ²³⁴U/²³⁸U initial activity ratio of 15 Italian travertine and calcareous tufa sites was created using data from the relevant literature. Using a graphical method, data were interpreted considering the U geochemistry in natural environments as well as the geological, hydrogeological and hydrogeochemical settings of each site. The U content and ²³⁴U/²³⁸U initial activity ratio in travertine and tufa appear to be affected by different factors, such as the availability of U in the aquifer rocks, the redox state of the waters, and the alpha-active radionuclide recoil phenomenon. The data allow the identification of four groups of travertines/tufas: (i) those precipitated from circulating groundwater, with a short/fast flow path, in volcanic rocks with a high radionuclide content; (ii) those precipitated from circulating groundwater, with a long, deep flow path in carbonate/evaporite formations with a relatively low radionuclide content; and (iii) those precipitated from cold waters associated with riverine systems, which are characterized by oxidizing conditions and fed by high-discharge springs recharged by carbonate aquifers. The fourth group represents the intermediate situations frequently occurring due to the mixing of waters from different aquifers. The results suggest an interpretative model that might contribute to the paleo-environmental reconstruction of fossil travertine and calcareous tufa depositing systems. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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37 pages, 17530 KiB

Open AccessArticle

Travertines of the South-Eastern Gorny Altai (Russia): Implications for Paleoseismology and Paleoenvironmental Conditions

by Evgeny V. Deev, Svetlana N. Kokh, Yuri Dublyansky, Ella V. Sokol, Denis Scholz, Gennady G. Rusanov and Vadim N. Reutsky

Minerals 2023, 13(2), 259; https://doi.org/10.3390/min13020259 - 12 Feb 2023

Cited by 2 | Viewed by 1621

Abstract

The south-eastern Gorny Altai is one of the most hazardous seismogenic area in the north of Central Asia. We present a synthesis of field, ²³⁰Th-U geochronological, mineralogical and geochemical data collected on seven Quaternary travertines. All travertines occur within the zones of active faults that border the Chuya and Kurai intermontane basins. Travertine cement mainly comprises calcite (with minor amounts of aragonite), which cements alluvial, alluvial fan, and colluvial deposits. The results of ²³⁰Th-U dating suggest that deposition of the travertines was triggered by large paleoearthquakes in the last eight thousand years. Several stages of travertine formation with ages 9–11 ka BP correspond to the known period of strong paleoseismicity in the region (8–16 ka BP). The 123 ka BP travertine resulted from a slip triggered by the Middle Pleistocene deglaciation, while that of 400 ka BP represents seismic motions likely associated with the main Cenozoic orogenic phase. All travertine forming events fall within warm and wet climatic phases (interglacials). Large earthquakes activated faults and caused a rapid rise along them of ambient-temperature bicarbonate groundwater, which was previously sealed in deep-seated Upper Neoproterozoic–Paleozoic limestone-dolostone aquifers. Rapid CO₂ degassing of the spring water was the most important control of calcite or aragonite precipitation. Such travertines represent an important tool for paleoseismological research in seismically active regions. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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19 pages, 5798 KiB

Open AccessArticle

Geochemical Characterization of Laminated Crystalline Crust Travertines Formed by Ca²⁺-Deficient Hot Springs at Sobcha (China)

by Zhipeng Lu, Huaguo Wen, Lianchao Luo, Liang Li and Ying Nie

Minerals 2023, 13(2), 220; https://doi.org/10.3390/min13020220 - 02 Feb 2023

Viewed by 1550

Abstract

Travertines formed of crystalline crust have been widely reported, but there has not been focus on their geochemical characteristics. We therefore carefully conducted a series of geochemical investigations and U-Th dating on a travertine mound mainly composed of crystalline crust from Sobcha (southwest China) to determine their geochemical features and geological implications. The Sobcha travertines dominantly consist of granular crystals and fan crystals and show δ¹³C from 3.4‰ to 4.9‰ V-PDB, δ¹⁸O from −26.7‰ to −23.7‰ V-PDB, and ⁸⁷Sr/⁸⁶Sr from 0.712458 to 0.712951. When normalized to PASS, the Sobcha travertines exhibit MREE enrichment relative to HREE and LREE, HREE enrichment relative to LREE, and positive Eu anomalies. The δ¹³C signatures and mother CO₂ evaluation of the Sobcha travertines show that the Sobcha travertines were thermogene travertines largely receiving mother CO₂ from (upper) mantle (i.e., magmatic CO₂) or a mixture of soil-derived CO₂ and CO₂ related to carbonate decarbonation. The ⁸⁷Sr/⁸⁶Sr of the Sobcha travertines is out of the ⁸⁷Sr/⁸⁶Sr ranges of local deposits exposed at Sobcha and surrounding areas but is well matched with the mean ⁸⁷Sr/⁸⁶Sr of Nadi Kangri volcanic rocks which cropped out to the northeast of the studied travertines (over 20 km away). This might indicate the important role of the Nadi Kangri volcanic rocks in suppling Sr to the studied travertines, but more studies are required. The LREE depletion compared to MREE and HREE in the Sobcha travertines was interpreted to be caused by the difference in geochemical mobility between LREEs and HREEs during water–rock interaction at depth, while the MREE enrichment compared to HREE was considered to be most likely inherited from reservoir/aquifer rocks. The positive Eu anomalies of the Sobcha travertines may result from very high reservoir temperatures and/or preferential dissolution of Eu-rich minerals/rocks (especially plagioclase). The Sobcha travertine mounds displays no or very slight vertical variations in δ¹³C, ⁸⁷Sr/⁸⁶Sr, and REE patterns, indicating the compositional stability of mother CO₂ and paleo-fluids. However, a significant vertical increase in δ¹⁸O was observed and was explained as the result of gradual water temperature decrease related to climate cooling, self-closure of the vents, or mound vertical growth. The findings in this study might help us better understand the deposition of crystalline crust in Ca²⁺-deficient hot spring systems. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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18 pages, 6203 KiB

Open AccessArticle

Insights into Alpine-Karst-Type Tufa Deposits in Geological Environmental Records: A Case Study of the Calcareous Tufa Profile of the Jiuzhaigou Natural Reserve on the Eastern Margin of the Tibetan Plateau

by Congcong Lv, Xueqin Zhao, Yaoxi Jiang, Heyan Zhu, Hongmin Zhang, Fudong Wang, Qiongfang Li and Keli Hou

Minerals 2023, 13(1), 120; https://doi.org/10.3390/min13010120 - 13 Jan 2023

Cited by 2 | Viewed by 1433

Abstract

To study the geological environmental records of alpine-karst-type tufa deposits in the eastern margin of the Tibetan Plateau, the calcareous tufa profile exposed by the “8.8” Jiuzhaigou earthquake was taken as the research object and combined with a field geological investigation. Further, the petrography, sedimentology, chronology, and elemental geochemistry of the calcareous tufa were studied and analyzed. The results show the following. (1) The Sparkling Lake calcareous tufa profile was deposited under the background of a warm and humid climate during the Holocene. The growth pattern follows a bottom-to-top deposition. (2) At 750 ± 30–300 ± 30 aB.P., the calcareous tufa layers were gray-black as a whole, and the changes in mineral composition and elemental geochemistry indicate a fluctuating upward trend for temperature and precipitation during this period. (3) The formation of two sets of black peat layers in the upper part of the tufa calcareous profile is due to the synergistic action of multiple factors caused by strong tectonic activity. In conclusion, the deposition mechanism of the calcareous tufa in Jiuzhaigou was controlled by paleoclimate hydrology and glaciation for a long time, while strong tectonic activity over a short period of time considerably changed the color, structure, element content, and mineral composition of the calcareous tufa. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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22 pages, 9486 KiB

Open AccessArticle

Stable Carbon and Oxygen Isotopic Features of Banded Travertines from the Xiagei Fissure Ridge System (Shangri-La, China)

by Yaxian You, Huaguo Wen, Lianchao Luo, Zhipeng Lu and Liang Li

Minerals 2023, 13(1), 76; https://doi.org/10.3390/min13010076 - 03 Jan 2023

Cited by 1 | Viewed by 1371

Abstract

Banded travertines are important parts of fissure ridge systems, but studies on geochemical characterization of banded travertines are limited. This study investigated the lithofacies and stable carbon and oxygen isotopic features of banded travertines from Xiagei (southwestern China) to examine their formation mechanisms. Petrographic analyses of the banded travertines revealed two lithotypes: thick-laminated palisade crystalline crust and thin-laminated composite crystalline crust. δ¹³C and δ¹⁸O of the Xiagei banded travertines range from 2.82‰ to 4.50‰ V-PDB, and from −25.86‰ to −20.90‰ V-PDB. Parent CO₂ evaluation shows that the Xiagei banded travertines mainly received CO₂ from the decarbonation of marine carbonates, but the contributions of magmatic CO₂ and the dissolution of marine carbonates are also unneglectable. Significantly, the magmatic-derived CO₂ might indicate that the delamination of the lithosphere along with the asthenosphere upwelling could be taking place in the eastern Tibetan plateau. Paleotemperature calculation shows that the Xiagei travertines were precipitated from moderate- to high-temperature hot springs (44.3 to 86.8 °C). Interestingly, the thick-laminated palisade crystalline crust and thin-laminated composite crystalline crust display calculated paleotemperature between 66.6 and 86.8 °C and between 56.6 and 77.7 °C, respectively, reflecting the great role of water temperature in controlling the lithofacies of banded travertines. A comparison between the banded travertines at Xiagei and other areas also shows temperature is a non-negligible factor controlling banded travertine precipitation. However, this does not mean that water temperature is the decisive controlling factor and more studies on banded travertines are still indispensable to disclose the potential factors controlling the factors/processes affecting banded travertine lithofacies. This study provides a good example for understanding the relationship between lithofacies and stable isotopic geochemical characteristics of travertine deposits. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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27 pages, 3289 KiB

Open AccessArticle

Controls on Mg/Ca Ratios in Recent Stromatolites: Insights from Fluvial Systems in the Iberian Range (Spain)

by Luis F. Auqué, M. Cinta Osácar, Concha Arenas, Neven Cukrov, Sonja Lojen and Carlos Sancho

Minerals 2023, 13(1), 57; https://doi.org/10.3390/min13010057 - 29 Dec 2022

Viewed by 1405

Abstract

The utility of the Mg/Ca elemental ratio of calcite ((Mg/Ca)_calcite) as a temperature indicator in continental carbonate deposits is a matter of debate due to the different results obtained by diverse authors. In this study, we aimed to test the reliability of the (Mg/Ca)_calcite in fluvial carbonates. We selected the recent tufa stromatolite records of four rivers on the Iberian Peninsula for the trace element analysis based on six-monthly sampling. Previous sedimentary and hydrological studies on these fluvial basins provided the information for this work. The water temperature estimates for the stromatolite (Mg/Ca)_calcite substantially differed from the measured water temperatures in most of the studied cases. We thus assessed other factors that participate in the control of the Mg partitioning between water and calcite. The correction of the detrital Mg content yielded water temperatures that matched the measured ones in one of the rivers. The (Mg/Ca)_water, water discharge and calcite precipitation rates may also occasionally influence the (Mg/Ca)_calcite. The six-month behaviour of some of these parameters could interfere with the relationship between the (Mg/Ca)_calcite and water temperature. According to these results, and their comparison with other non-marine carbonates, the wide variety of parameters that are involved in the (Mg/Ca)_calcite limit it as a geochemical thermometer in continental sedimentary environments. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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20 pages, 4116 KiB

Open AccessArticle

Non-Linear Clumped Isotopes from DIC Endmember Mixing and Kinetic Isotope Fractionation in High pH Anthropogenic Tufa

by Chris Holdsworth, John MacDonald and Cedric John

Minerals 2022, 12(12), 1611; https://doi.org/10.3390/min12121611 - 14 Dec 2022

Cited by 3 | Viewed by 1628

Abstract

Clumped isotope values (Δ₄₇) of carbonates forming in high pH conditions do not correspond to mineral precipitation temperatures due to certain effects including kinetic isotope fractionation and dissolved inorganic carbon (DIC) endmember mixing. Field-based archives of these carbonate environments are needed to evaluate and quantify these effects accurately. In this study, we measure the clumped isotope values of anthropogenic carbonates for the first time. Tufa layers were analyzed from samples precipitating in a high pH (>10) stream that drains a major slag heap in north east England. Δ₄₇ values are 0.044‰–0.183‰ higher than expected equilibrium values. Non-linear distribution of clumped isotope data is diagnostic of DIC endmember mixing, rather than partial equilibration of DIC. Episodic dilution of hydroxide-rich stream waters by equilibrated rainfall surface runoff provides the mechanism by which mixing occurs. Δ₄₇ values are ~0.010‰–0.145‰ higher than linear clumped isotope mixing profiles, suggesting that the majority of Δ₄₇ increase results from a combination of endmember non-linear mixing effects and an atmosphere-hydroxide sourcing of DIC. The diagnostic trends and variation in clumped isotope values present in these results demonstrates the potential of anthropogenic carbonate systems as a useful archive for studying and quantifying kinetic effects in clumped isotopes. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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15 pages, 5088 KiB

Open AccessArticle

Response of Travertine Dam to Precipitation over the Past 800 Years in Zabuye Salt Lake, Southwestern Tibetan Plateau

by Mingming Li, Mianping Zheng, Chuanyong Ye, Chenguang Wang, Xuefei Zhang, Xuefeng Wang, Yuanyi Zhao and Yanbo Zhang

Minerals 2022, 12(7), 916; https://doi.org/10.3390/min12070916 - 21 Jul 2022

Cited by 3 | Viewed by 1704

Abstract

The Tibetan Plateau is known as the core area of the third pole of the Earth and is a key area for global climate change research. This study uses the Zabuye Salt Lake travertine dam as the research object and U–Th dating as the chronological framework and proposes that the carbon and oxygen isotopes of travertine can be used as a precipitation index through the analysis of hydrogen and oxygen isotopes of spring water, and petrology, mineralogy, carbon and oxygen isotopes of travertine. The precipitation records of Zabuye Salt Lake over the last 800 years show a dry condition in 1191–1374 AD (Medieval Warm Period), a humid condition in 1374–1884 AD (Little Ice Age), and a dry condition in 1884–1982 AD (Current Warn Period), indicating a warm–dry/cold–moist climate pattern, which is consistent with precipitation records from many places on the Tibetan Plateau. We preliminarily point out that travertine can record the evolution of paleoprecipitation (paleomonsoon) at least on the decadal–centennial scale. The Indian summer monsoon has been the main factor influencing precipitation change in Zabuye Salt Lake over the past 800 years, and the change in evapotranspiration intensity caused by temperature change driven by solar radiation is also an important factor affecting dry–moist change. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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29 pages, 7267 KiB

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Mineralogy, Geochemistry, and Stable Isotopes (C, O, S) of Hot Spring Waters and Associated Travertines near Tamiahua Lagoon, Veracruz, Gulf of Mexico (Mexico)

by Israel Porras-Toribio, Teresa Pi-Puig, Ruth Esther Villanueva-Estrada, Marco Antonio Rubio-Ramos and Jesús Solé

Minerals 2022, 12(7), 822; https://doi.org/10.3390/min12070822 - 28 Jun 2022

Cited by 2 | Viewed by 1917

Abstract

Laminated travertine forms in and around an active hot spring on the west coast of Tamiahua Lagoon, north of the state of Veracruz, Mexico. Fluid chemistry is characterized by discharging slightly acidic pH hot water and gas at a constant flow rate. Moreover, finely interbedded mineralogical products from discharging waters at 70 °C host scattered hydrocarbons. The mineralogy and geochemistry of the travertine formations were characterized to determine their origin. Rock samples were collected and further studied by transmitted light petrography, X-ray diffraction, and EDS-coupled scanning electron microprobe. Identified mineralogy from outcrop samples includes aragonite, gypsum, anhydrite, and elemental sulfur as essential minerals, with calcite, celestine, barite, jarosite, opal, and fluorite as accessory minerals. Isotopic analyses for C and O were determined in carbonates, S isotope ratios on both elemental sulfur and sulfates, whereas measurements for trace elements and lanthanides were performed on carbonates. A suit of brines and condensates from gas samples was collected for H and O isotopic analyses and concentration determinations of the main ions and major and trace elements. Isotopic values of δ¹³C and δ¹⁸O of aragonite are in the range of +1.75‰ to +2.37‰ and −1.70‰ to −0.78‰, respectively. The δ³⁴S isotopic values of native sulfur and sulfates ranged from −4.0‰ to +1.2‰. The isotopic values of δ²H (−5.50‰) and δ¹⁸O (+7.77‰) of hot water samples collected in terraces where aragonite precipitates suggest a mixture between meteoric water and the Gulf of Mexico oil-field related waters. It was concluded that the aragonitic formations near Tamiahua Lagoon are hypogenic and were generated by CO₂ and H₂S emanations of deep origin and by oxidation-reduction reactions that can be linked to surficial bacterial activity. Full article

(This article belongs to the Special Issue Geochemistry of Travertines and Calcareous Tufas)

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