Low-temperature Hydrothermal Environment Research Articles

Hydrothermal genesis and growth of the banded agates from the Allumiere-Tolfa volcanic district (Latium, Italy)

In this work, we studied the hydrothermal agates from the Neogene–Quaternary volcanic district of Allumiere-Tolfa, north-west of Rome (Latium, Italy) using a combination of micro-textural, spectroscopic, and geochemical data. The examined sample consists of (1) an outer cristobalite layer deposited during the early stages of growth, (2) a sequence of chalcedonic bands (including i.e., length-fast, zebraic, and minor length-slow chalcedony) with variable moganite content (up to ca. 48 wt%), (3) an inner layer of terminated hyaline quartz crystals. The textures of the various SiO2 phases and their trace element content (Al, Li, B, Ti, Ga, Ge, As), as well as the presence of mineral inclusions (i.e., Fe-oxides and sulfates), is the result of physicochemical fluctuations of SiO2-bearing fluids. Positive correlation between Al and Li, low Al/Li ratio, and low Ti in hyaline quartz points to low-temperature hydrothermal environment. Local enrichment of B and As in chalcedony-rich layers are attributed to pH fluctuations. Analysis of the FT-IR spectra in the principal OH-stretching region (2750–3750 cm−1) shows that the silanol and molecular water signals are directly proportional. Strikingly, combined Raman and FT-IR spectroscopy on the chalcedonic bands reveals an anticorrelation between the moganite content and total water (SiOH + molH2O) signal. The moganite content is compatible with magmatic-hydrothermal sulfate/alkaline fluids at a temperature of 100–200 °C, whereas the boron-rich chalcedony can be favored by neutral/acidic conditions. The final Bambauer quartz growth lamellae testifies diluted SiO2-bearing solutions at lower temperature. These findings suggest a genetic scenario dominated by pH fluctuations in the circulating hydrothermal fluid.

Clay mineral characteristics in volcanic tuffs of Dokdo, South Korea: implication on their genesis and evolution

Secondary alteration minerals like clays accompanied by volcanic activity can provide an important information on eruption cycle. Representative volcanic tuffs and seabed sediments were collected from the Dokdo volcanic island in East Sea, South Korea, to interpret eruption cycle based on clay mineral characteristics and other geochemical proxies (sulfur isotope composition, Si/Al, K/Al, among others). Tuffs are mainly composed of volcanic glass and hydrothermally altered phenocrysts. Secondary minerals such as clay mineral species in volcanic tuffs mostly were identified as smectite comprising dioctahedral sheets, based on expanding to 15.8 A after treatment with 1 M MgCl2 solution, and 060 reflections near at 1.48 A. Moreover, the results of infrared bands, based on (Al, Al)–OH (904–912 cm−1), (Al, Fe)–OH (865–877 cm−1), (Fe, Mg)–OH (778–798 cm−1) indicate the presence of dioctahedral sheets in clay mineral structure. Partially, occurrence of kaolinite and relatively low pH values and K/Al ratios at the Eolgulbawi tuff support chemical flexibility of clay mineral species. The δ34S value of Dongdo tuff (H2O–S: 15.3‰) is close to water leached sulfate, whereas Seodo tuff II including pyrite and native sulfur (− 5.5‰) shows a value of H2S-bearing volcanic gases. The similarity of chemical compositions between clay fractions and surrounding volcaniclastic rocks suggests that the smectite formed in low-temperature hydrothermal environments, where alkali elements were supplied under reducing conditions. Clay fractions separated from seabed sediments include diatom frustule with higher SiO2/Al2O3 ratios, and clay minerals contain mineral nitrogen originated from organic-rich seafloor sediments. Moreover, the δ34S values of seabed sediments (1.8‰, 8.4‰) indicate that the different origin of clay mineral species between tuffs and seabed sediments. It can be concluded that the alteration types and clay mineral characteristics are similar to the Surtseyan volcano, generally known as shallow-marine phreatomagmatic eruption and deposits. It further suggests that clay minerals sensitive to environmental change will be useful to interpret the volcanic environment characterized by explosive hydrovolcanic activities that occurred at the time of magma in contact with water before erupting into the atmosphere.

Hydrothermal Alteration of Etna Ash and Implications for Mars

Volcanic activity represents one of the main factors controlling the geological evolution of Mars, whose morphology has remarkable counterparts on Earth. Studies on the Martian surface revealed the widespread occurrences of newly formed minerals originated by the hydrothermal alteration of volcanic rocks. In this work, we carried out a series of experiments to test the reactions occurring during the hydrothermal alteration of basaltic ash from Etna (Italy) as a possible similar reaction fully grown on the Martian rock. The volcanic ash used for the hydrothermal alteration experiments was collected during the eruption of Etna in 2001, and its composition shares similarities with Martian bedrocks. Ash was altered under hydrothermal conditions at initial pH 5 at two temperatures (150 and 200 °C) and reaction times of 5, 10, and 31 days. After a number of runs, we attained analcime NaAlSi2O6·H2O. Our findings are in line with the hypothesis that zeolite on Mars probably originated from a low-temperature hydrothermal environment. The conclusions accord with the assumption that the analcime crystals recognized on Mars formed under the same conditions as those of our experimental setups.

Selenium Minerals: Structural and Chemical Diversity and Complexity

Chemical diversity of minerals containing selenium as an essential element has been analyzed in terms of the concept of mineral systems and the information-based structural and chemical complexity parameters. The study employs data for 123 Se mineral species approved by the International Mineralogical Association as of 25 May 2019. All known selenium minerals belong to seven mineral systems with the number of essential components ranging from one to seven. According to their chemical features, the minerals are subdivided into five groups: Native selenium, oxides, selenides, selenites, and selenates. Statistical analysis shows that there are strong and positive correlations between the chemical and structural complexities (measured as amounts of Shannon information per atom and per formula or unit cell) and the number of different chemical elements in a mineral. Analysis of relations between chemical and structural complexities provides strong evidence that there is an overall trend of increasing structural complexity with the increasing chemical complexity. The average structural complexity for Se minerals is equal to 2.4(1) bits per atom and 101(17) bits per unit cell. The chemical and structural complexities of O-free and O-bearing Se minerals are drastically different with the first group being simpler and the second group more complex. The O-free Se minerals (selenides and native Se) are primary minerals; their formation requires reducing conditions and is due to hydrothermal activity. The O-bearing Se minerals (oxides and oxysalts) form in near-surface environment, including oxidation zones of mineral deposits, evaporites and volcanic fumaroles. From the structural viewpoint, the five most complex Se minerals are marthozite, Cu(UO2)3(SeO3)2O2·8H2O (744.5 bits/cell); mandarinoite, Fe2(SeO3)3·6H2O (640.000 bits/cell); carlosruizite, K6Na4Na6Mg10(SeO4)12(IO3)12·12H2O (629.273 bits/cell); prewittite, KPb1.5ZnCu6O2(SeO3)2Cl10 (498.1 bits/cell); and nicksobolevite, Cu7(SeO3)2O2Cl6 (420.168 bits/cell). The mechanisms responsible for the high structural complexity of these minerals are high hydration states (marthozite and mandarinoite), high topological complexity (marthozite, mandarinoite, carlosruizite, nicksobolevite), high chemical complexity (prewittite and carlosruizite), and the presence of relatively large clusters of atoms (carlosruizite and nicksobolevite). In most cases, selenium itself does not play the crucial role in determining structural complexity (there are structural analogues or close species of marthozite, mandarinoite, and carlosruizite that do not contain Se), except for selenite chlorides, where stability of crystal structures is adjusted by the existence of attractive Se–Cl closed-shell interactions impossible for sulfates or phosphates. Most structurally complex Se minerals originate either from relatively low-temperature hydrothermal environments (as marthozite, mandarinoite, and carlosruizite) or from mild (500–700 °C) anhydrous gaseous environments of volcanic fumaroles (prewittite, nicksobolevite).

Comparative Analysis of Microbial Communities in Iron-Dominated Flocculent Mats in Deep-Sea Hydrothermal Environments.

It has been suggested that iron is one of the most important energy sources for photosynthesis-independent microbial ecosystems in the ocean crust. Iron-metabolizing chemolithoautotrophs play a key role as primary producers, but little is known about their distribution and diversity and their ecological role as submarine iron-metabolizing chemolithotrophs, particularly the iron oxidizers. In this study, we investigated the microbial communities in several iron-dominated flocculent mats found in deep-sea hydrothermal fields in the Mariana Volcanic Arc and Trough and the Okinawa Trough by culture-independent molecular techniques and X-ray mineralogical analyses. The abundance and composition of the 16S rRNA gene phylotypes demonstrated the ubiquity of zetaproteobacterial phylotypes in iron-dominated mat communities affected by hydrothermal fluid input. Electron microscopy with energy-dispersive X-ray microanalysis and X-ray absorption fine structure (XAFS) analysis revealed the chemical and mineralogical signatures of biogenic Fe-(oxy)hydroxide species and the potential contribution of Zetaproteobacteria to the in situ generation. These results suggest that putative iron-oxidizing chemolithoautotrophs play a significant ecological role in producing iron-dominated flocculent mats and that they are important for iron and carbon cycles in deep-sea low-temperature hydrothermal environments. We report novel aspects of microbiology from iron-dominated flocculent mats in various deep-sea environments. In this study, we examined the relationship between Zetaproteobacteria and iron oxides across several hydrothermally influenced sites in the deep sea. We analyzed iron-dominated mats using culture-independent molecular techniques and X-ray mineralogical analyses. The scanning electron microscopy-energy-dispersive X-ray spectroscopy SEM-EDS analysis and X-ray absorption fine structure (XAFS) analysis revealed chemical and mineralogical signatures of biogenic Fe-(oxy)hydroxide species as well as the potential contribution of the zetaproteobacterial population to the in situ production. These key findings provide important information for understanding the mechanisms of both geomicrobiological iron cycling and the formation of iron-dominated mats in deep-sea hydrothermal fields.

Origin and significance of the yellow cathodoluminescence (CL) of quartz

The origin of yellow cathodoluminescence (CL) in quartz has been investigated by a combination of CL microscopy and spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and spatially resolved trace-element analysis by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The study shows that the appearance of a ~570 nm (2.17 eV) emission band can be attributed to high oxygen deficiency and local structural disorder in quartz. A proposed luminescence center model implies self-trapped exciton (STE) emission from localized amorphized regions in quartz. Although the high-intensity emission at 570 nm is in general consistent with high concentrations of E ′1 defects detected by EPR spectroscopy, CL studies with different electron beam parameters and annealing experiments up to 600 °C show a temperature and irradiation dependence of the luminescence related defects excluding the role of E ′1 centers as direct luminescence activators for the 570 nm emission. The evaluation of geochemical data shows that quartz with yellow CL occurs in low-temperature hydrothermal environment (mostly <250 °C) and is related to fast crystallization in an environment with oxygen deficiency.

Low-Temperature Hydrothermal Alteration of Trachybasalt at Conical Seamount, Papua New Guinea: Formation of Smectite and Metastable Precursor Phases

AbstractThe conversion of volcanic glass to secondary alteration products is one of the most common mineralogical transformations during low-temperature hydrothermal alteration of submarine basalts. To better understand the mechanism and kinetics of this transformation, porphyritic and formerly glassy trachybasalt, recovered from Conical Seamount, Papua New Guinea, was studied in detail. Low-temperature interaction of trachybasalt with hydrothermal fluids at this submerged volcano occurred in response to the formation of submarine epithermal-style gold mineralization. Alteration of the coherent volcanic rocks is heterogeneous with pronounced differences in alteration intensity occurring between igneous minerals and the surrounding glassy groundmass. In comparison to the volcanic glass, the crystalline phases were less prone to hydrothermal alteration with the alteration susceptibility decreasing from clinopyroxene through biotite to feldspar. Low-temperature alteration of clinopyroxene resulted in the formation of abundant saponite-like smectite with no topotactic relationship being observed between the two phases. In contrast, the conversion of biotite to smectite involved structural inheritance as the orientation of common structural blocks was maintained during alteration. Transmission and analytical electron microscopy revealed that pervasive alteration of interstitial glass in the groundmass of the trachybasalt resulted in the formation of montmorillonite- and saponite-like smectite whereby smectite composition is strongly influenced by the glass chemistry. The occurrence of poorly crystalline domains with a 0.3 to 0.4 nm layer spacing in the altered interstitial glass suggests that the transformation of glass to smectite involved the formation of a transitional alteration product. Comparison with the results of previous studies highlights the fact that the glass-to-smectite transformation can proceed through more than one reaction pathway. Reaction style and reaction progress are controlled by kinetic factors such as the mode of fluid transport triggering alteration in the low-temperature hydrothermal environment. Alteration of the trachybasalt at Conical Seamount is inferred to have taken place at a comparably low fluid-rock ratio as the low permeability and the absence of primary fractures and joints restricted fluid circulation through the coherent volcanic rocks.

Characterization of metalliferous sediment from a low-temperature hydrothermal environment on the Eastern Flank of the East Pacific Rise

Metalliferous deposits are described from the eastern flank of the East Pacific Rise (EPR) offshore Costa Rica, close to a basaltic seamount called “Dorado high”. Based on heat-flow data and porewater profiles, the site is an area of active low-temperature hydrothermal discharge. We focus on the mineralogical and chemical analysis from a 124 cm long gravity core (GC50), located on the northwestern slope of the 100 m high Dorado. In this core, the sediments consist of detrital clay minerals as well as authigenic minerals such as zeolites, apatites, and Fe/Mn-rich oxyhydroxides. In contrast, the reference sediments from adjacent areas without hydrothermal activity are olive gray hemipelagic muds composed of volcanic glass particles, clay minerals, siliceous microfossils, and some detrital quartz and feldspar. Bulk sediment chemistry and chemical enrichment factors calculated with respect to the reference sediment indicate that the most important chemical changes occurred at the base of the core from 100 to 124 cm bsf, with strong enrichments in MnO, CaO, P 2O 5, and Fe 2O 3. These enrichments are correlated with the occurrence of authigenic Fe-oxyhydroxide (goethite) and Mn oxide (todorokite and vernadite, at 100 cm bsf), and hydrothermal apatite (110–124 cm bsf). In the upper section of the core from 12 to 70 cm, the sediment is composed of abundant smectite and authigenic phillipsite, and only minor chemical changes can be observed with respect to the reference sediments. The ubiquitous presence of phillipsite suggests that the entire sedimentary column of core GC50 was first affected by diagenesis. However, below 70 cm bsf, these phillipsites are partially dissolved and Fe oxides occur from 110 to 124 cm, followed upward by Mn oxides at 100 cm. This transition from Fe to Mn-rich sediments can be interpreted in terms of an upward increasing redox potential. PAAS-normalized REY patterns of GC50 sediments present clearly negative Ce and positive Y anomalies inherited from seawater at the base of core GC50. These anomalies decrease upward, which we interpret together with the transition from Fe to Mn-rich sediments by an upward migrating low-temperature hydrothermal fluid. Thus, after a first stage of diagenesis, the discharge of a low-temperature hydrothermal fluid occurred through the sedimentary column, leading to the precipitation of hydrothermal compounds that are lacking towards the surface.

Structure and chemistry of phosphate minerals

AbstractFor complex rocks in which the structure of minerals, rather than their chemical composition, changes with progressive evolution of the system, it makes sense to try and monitor such an evolving system through the progressive change in the crystal structures of the constituent phases. In effect, the paragenetic sequences of minerals in such complex environments should be related to the crystal structures of the constituent minerals. In order to consider variations in structure topology, we need to organize crystal structures into hierarchical schemes, using the hypothesis that structures may be hierarchically ordered according to the polymerization of the coordination polyhedra with higher bondstrengths. Structural units are organized according to the mode of polymerization: unconnected polyhedra, clusters, chains, sheets and frameworks.The bond-valence structure of (OH) and (H2O) shows that on one side, (OH) and H2O are strong Lewis bases; on the other side, they are weak Lewis acids. As a result, a very important role of both (OH) and (H2O) is to prevent polymerization of the structural unit in specific directions. Thus, the dimensionality of the structural unit is controlled primarily by the amount and role of hydrogen in the structure. The way in which we have formulated these ideas also allows development of a predictive framework within which specific aspects of the chemistry and structure of phosphates can be considered.This approach to mineral structure, applied via the idea of a structural unit, can play a major role in developing structural hierarchies in order to bring about some sort of order to the plethora of hydroxyhydrated-phosphate structures. Furthermore, by combining the idea of binary structural representation with bond-valence theory, we see the eventual possibility of predicting stoichiometry and structural characteristics of these minerals, particularly those in complex low-temperature hydrothermal environments

Sepiolite asbestos from franklin, new jersey: A case study in medical geology

Asbestiform sepiolite has been found in a zinc deposit at Franklin, New Jersey. The host rock is Precambrian Franklin marble. Pseudomorphous foliated texture and cross-cutting relationships indicate replacement of talc by sepiolite. Sepiolite is manganoan, while talc contains little manganese, suggesting differences in manganese substitution in these minerals and providing evidence against solid-state replacement. Sepiolite from Franklin is of moderate crystallinity and consists of soft, flexible mass-fiber. Comparison with other sepiolite samples suggests that increased crystallinity among sepiolites parallels increased fiber length, while disorder appears to be associated with flexibility. Length and aspect ratio (length/width) distributions support toxicological equation of asbestiform sepiolite with the regulated asbestos minerals. The data presented here suggest that talc can be unstable in a low-temperature hydrothermal environment, altering under certain conditions to form sepiolite. In a wider context, sepiolite may be expected to precipitate at the end-stages of hydrothermal mineralization in some talc deposits and in carbonate and calc-silicate rocks. Many occurrences of sepiolite in these rocks may have been overlooked due to similarities with other minerals. The fact that sepiolite has been previously unrecognized and misidentified at Franklin is a case in point. Since there is evidence suggesting that sepiolite is fibrogenic and carcinogenic, its potential occurrence in consumer talcs and crushed-stone products has environmental health implications. Similarities in composition and other analytical parameters may cause sepiolite to be mistaken for fibrous talc or chrysotile in environmental samples.