Volcanic Fumaroles Research Articles

The Yadovitaya fumarole, Tolbachik volcano: A comprehensive mineralogical and geochemical study and driving factors for mineral diversity

Active volcanic fumaroles are one of the most spectacular natural objects in terms of mineral diversity. The Great Tolbachik Fissure Eruption (GTFE) (Kamchatka) fumaroles are renowned for its exceptional number of mineral species. The total number of minerals that have been reliably identified from this particular locality exceeds 400, which is approximately 6.5 % of all known minerals to date. In this study, we employ a comprehensive approach (bulk chemistry, microprobe analysis, powder X-ray diffraction, HR X-ray computed tomography, and 34S, 18O, and 65Cu isotope measurements) to study the distribution of primary exhalation and secondary mineral assemblages and to reveal the driving factors responsible for the unique mineral diversity in the Yadovitaya fumarole. High oxygen fugacity, the interaction of minerals with atmospheric oxygen and water from seasonal precipitation (leading to abundant hydrated mineral associations), temperature conditions controlling the spatial distribution of mineral-forming components, gas-rock interactions, and basaltic scoria morphology perfect for the crystallization of various minerals are some of the factors revealed. The combination of these factors caused a stepwise mineralization resulting in 12 zones of the Yadovitaya fumarole with characteristic mineral assemblages. The described mineralogy of the Yadovitaya fumarole demonstrates a consistent spatial evolution of fumarolic mineral assemblages that vary in complexity, chemistry, and interaction patterns with the surrounding environment. The examination of mineralogical and geochemical data yields novel insights into the active volcanic systems that are associated with the formation of distinct oxidation-type fumaroles.

Polyoxometalates from gases: Mineral-inspired synthesis and characterization of novel compounds containing [M⊂Cu12O8(AsO4)8]q- polyoxocuprate clusters (M = Ti(IV), Bi(III))

A novel type of polyoxocuprate (POCu) clusters, [M⊂Cu12O8(AsO4)8]q- (M = Ti(IV), Bi(III)), with a cubooctahedral arrangement of Cu2+ cations, have been prepared by chemical vapor transport reactions (CVT) using the methodology inspired by mineralogical discoveries at volcanic fumaroles of the Tolbachik volcano (Kamchatka peninsula, Russia). Three new compounds, Na21Cl6F[TiF6][TiCu12O8(AsO4)8] (1), Na18Cl6[TiCu12O8(AsO4)8] (2), and Na18Cl5[BiCu12O8(AsO4)8] (3), prepared under low-vacuum conditions, contain the {[M⊂Cu12O8](AsO4)8} (M = Ti4+, Fe3+) clusters with a Keggin-ion-like cubooctahedral arrangement of Cu2+ cations encapsulating Mn+ cations strikingly similar to the {[Pd13O8]L8]q- polyoxoanions observed in polyoxopalladates. The packing modes of clusters in different structures are different, with the structures of 1 and 3 based upon cubic-close-packing and hexagonal-close-packing arrangements, respectively. The packing of clusters in 2 is rather complex that results in its extreme structural complexity with the amount of Shannon structural information per unit cell exceeding 3000 bits. In the title compounds, the POCu clusters are embedded into salt matrices and therefore can be considered as an inverse analogue of salt-inclusion compounds, i.e., as inclusion-in-salt compounds. The successful synthesis of new types of POCu clusters using the CVT techniques opens up a new synthetic pathway for the exploration of polyoxocuprates with promising interesting structures and physical properties.

Effects of condensates from volcanic fumaroles and cigarette smoke extracts on airway epithelial cells

The impact of volcanic airborne products on airway epithelium homeostasis is largely unknown. This study assessed the effects of volcanic Fumarole Condensates (FC) alone or combined with Cigarette Smoke Extracts (CSE) on airway epithelial cells (16HBE and A549). Chemical composition of FC was analyzed by gas chromatography and HPLC. Cells were exposed to FC and IL-33 and IL-8 were assessed. The effects of FC and CSE on cell injury were evaluated assessing cell metabolism/cell viability, mitochondrial stress, cell apoptosis/cell necrosis, and cell proliferation. FC contained: water vapor (70–97%), CO2 (3–30%), acid gases (H2S, SO2, HCl, HF) around 1%. FC increased the intracellular IL-33 but differently modulated IL-33 and IL-8 gene expression and IL-8 release in the tested cell lines. FC without/with CSE: (a) increased cell metabolism/cell viability in 16HBE, while decreased it in A549; (b) increased mitochondrial stress in both cell types. FC with CSE increased cell necrosis in A549 in comparison to CSE alone. CSE reduced cell proliferation in 16HB,E while increased it in A549 and FC counteracted these effects in both cell types. Overall, FC induce a pro-inflammatory profile associated to a metabolic reprogramming without a relevant toxicity also in presence of CSE in airway epithelial cells.

Volcanic native sulphur pebbles excavated from the near-shore deposits of Hakata Bay, Kyushu, Japan: Their formation, preservation and archaeological significance

Several archives written in Japan, China and Korea during medieval times document markedly elevated demand for native sulphur which was an ingredient of gunpowder and a key resource during times of war in east Asia. According to historic documents, numerous macroscopic sulphur pebbles (up to about 20 mm in diameter) with distinct lemon-yellow color were excavated from the coastal deposits of Hakata Bay, northern Kyushu (Japan). Radiocarbon (14C) dating using high-resolution accelerator mass spectrometry of intercalated charcoal remains indicates deposition during the late 11th to early 12th century CE. The age of these deposits indicates the earliest industrial use of native sulphur in the world. The isotopic composition of the excavated sulphur pebbles is consistent with the values obtained for the native volcanic sulphur from the active geothermal regions within Kyushu. Often and very intimately associated opal-CT, cristobalite/tridymite and tridymite fragments were found with the sulphur pebbles, which reinforce the proposed provenance of high-temperature volcanic fumaroles. A possible mechanism for the long-term preservation of the sulphur pebbles within the sediments is discussed on the basis of the isotopic signatures of the easily oxdizable sulphide-sulphur in the matrix. The reduction of marine sulphates in the brackish pore-waters in association with the decay of organic debris, which act as electron donors for microbial reduction of marine sulphates provides a favorable environment for prolonged reducing conditions. Such conditions limited microbial oxidation of the native sulphur pebbles by sulphur-oxidizing bacteria and fungi. Spillage of the pebbles during cargo handling and their incorporation within the sediments and other debris drifting along the near-shore of Hakata Bay is the most plausible explanation for this unusual occurrence of sulphur pebbles.

Na2Cu+[Cu2+ 3O](AsO4)2Cl and Cu3[Cu3O]2(PO4)4Cl2: two new structure types based upon chains of oxocentered tetrahedra

Abstract Single crystals of Na2Cu+[Cu2+ 3O](AsO4)2Cl (1) and Cu3[Cu3O]2(PO4)4Cl2 (2) were prepared by chemical vapor transport reactions. Both crystal structures are based upon the same [O2Cu6]8+ chains formed by corner-sharing (OCu4)6+ tetrahedra and interconnected by (TO4)3− (T = P, As) tetrahedra into porous {[OCu3](TO4)2Cl}3− frameworks. The channels within the frameworks are occupied by Na+, Cu+ and Cl− ions in the crystal structure of 1, whereas the channels in the structure of 2 contain edge-sharing CuO4Cl tetragonal pyramids. Both compounds are structurally related to the previously described synthetic Na2Cu+[Cu2+ 3O](PO4)2Cl and NaCu2+[Cu2+ 3O](PO4)2Cl. The compound 2 is structurally and chemically related to yaroshevskite, Cu3[Cu3O]2(VO4)4Cl2, a mineral discovered in volcanic fumaroles, but the two structure types are drastically different. The crystal chemical analysis of the title and related compounds allows to recognize a family of at least four compounds based upon {[OCu3](TO4)2Cl}3− frameworks with channels occupied by different chemical constituents.

An evolutionary system of mineralogy, Part VI: Earth’s earliest Hadean crust (>4370 Ma)

AbstractPart VI of the evolutionary system of mineralogy catalogs 262 kinds of minerals, formed by 18 different processes, that we suggest represent the earliest solid phases in Earth’s crust. All of these minerals likely formed during the first tens of millions of years following the global-scale disruption of the Moon-forming impact prior to ~4.4 Ga, though no samples of terrestrial minerals older than ~4.37 Ga are known to have survived on Earth today. Our catalog of the earliest Hadean species includes 80 primary phases associated with ultramafic and mafic igneous rocks, as well as more than 80 minerals deposited from immiscible S-rich fluids and late-stage Si-rich residual melts. Earth’s earliest crustal minerals also included more than 200 secondary phases of these primary minerals that were generated by thermal metamorphism, aqueous alteration, impacts, and other processes. In particular, secondary mineralization related to pervasive near-surface aqueous fluids may have included serpentinization of mafic and ultramafic rocks, hot springs and submarine volcanic vent mineralization, hydrothermal sulfide deposits, zeolite and associated mineral formation in basaltic cavities, marine authigenesis, and hydration of subaerial lithologies. Additional Hadean minerals may have formed by thermal metamorphism of lava xenoliths, sublimation at volcanic fumaroles, impact processes, and volcanic lightning. These minerals would have occurred along with more than 180 additional phases found in the variety of meteorites that continuously fell to Earth’s surface during the early Hadean Eon.

On the paragenetic modes of minerals: A mineral evolution perspective

AbstractA systematic survey of 57 different paragenetic modes distributed among 5659 mineral species reveals patterns in the diversity and distribution of minerals related to their evolving formational environments. The earliest minerals in stellar, nebular, asteroid, and primitive Earth contexts were dominated by relatively abundant chemical elements, notably H, C, O, Mg, Al, Si, S, Ca, Ti, Cr, and Fe. Significant mineral diversification subsequently occurred via two main processes, first through gradual selection and concentration of rarer elements by fluid-rock interactions (for example, in hydro-thermal metal deposits, complex granite pegmatites, and agpaitic rocks), and then through near-surface biologically mediated oxidation and weathering.We find that 3349 mineral species (59.2%) are known from only one paragenetic context, whereas another 1372 species (24.2%) are associated with two paragenetic modes. Among the most genetically varied minerals are pyrite, albite, hornblende, corundum, magnetite, calcite, hematite, rutile, and baryte, each with 15 or more known modes of formation.Among the most common paragenetic modes of minerals are near-surface weathering/oxidation (1998 species), subsurface hydrothermal deposition (859 species), and condensation at volcanic fumaroles (459 species). In addition, many species are associated with compositionally extreme environments of highly differentiated igneous lithologies, including agpaitic rocks (726 species), complex granite pegmatites (564 species), and carbonatites and related carbonate-bearing magmas (291 species). Biological processes lead to at least 2707 mineral species, primarily as a consequence of oxidative weathering but also through coal-related and other taphonomic minerals (597 species), as well as anthropogenic minerals, for example as byproducts of mining (603 minerals). However, contrary to previous estimates, we find that only ~34% of mineral species form exclusively as a consequence of biological processes. By far the most significant factor in enhancing Earth’s mineral diversity has been its dynamic hydrological cycle. At least 4583 minerals—81% of all species—arise through water-rock interactions.A timeline for mineral-forming events suggests that much of Earth’s mineral diversity was established within the first 250 million years. If life is rare in the universe, then this view of a mineralogically diverse early Earth provides many more plausible reactive pathways over a longer timespan than previous models. If, however, life is a cosmic imperative that emerges on any mineral- and water-rich world, then these findings support the hypothesis that life on Earth developed rapidly in the early stages of planetary evolution.

Thallium Isotope Fractionation During Magma Degassing: Evidence From Experiments and Kamchatka Arc Lavas

AbstractThallium (Tl) isotope ratios are an emerging tool that can be used to trace crustal recycling processes in arc lavas and ocean island basalts (OIBs). Thallium is a highly volatile metal that is enriched in volcanic fumaroles, but it is unknown whether degassing of Tl from subaerial lavas has a significant effect on their residual Tl isotope compositions. Here, we present Tl isotope and concentration data from degassing experiments that are best explained by Rayleigh kinetic isotope fractionation during Tl loss. Our data closely follow predicted isotope fractionation models in which TlCl is the primary degassed species and where Tl loss is controlled by diffusion and natural convection, consistent with the slow gas advection velocity utilized during our experiments. We calculate that degassing into air should be associated with a net Tl isotope fractionation factor of αnet = 0.99969 for diffusion and natural gas convection (low gas velocities) and αnet = 0.99955 for diffusion and forced gas convection (high gas velocities). We also show that lavas from three volcanoes in the Kamchatka arc exhibit Tl isotope and concentration patterns that plot in between the two different gas convection regimes, implying that degassing played an important role in controlling the observed Tl isotope compositions in these three volcanoes. Literature inspection of Tl isotope data for subaerial lavas reveals that the majority of these appear only minorly affected by degassing, although a few samples from both OIBs and arc volcanoes can be identified that likely experienced some Tl degassing.

Experimental Evidence of the Viability of Thermoelectric Generators to Power Volcanic Monitoring Stations.

Although there is an important lack of commercial thermoelectric applications mainly due to their low efficiency, there exist some cases in which thermoelectric generators are the best option thanks to their well-known advantages, such as reliability, lack of maintenance and scalability. In this sense, the present paper develops a novel thermoelectric application in order to supply power to volcanic monitoring stations, making them completely autonomous. These stations become indispensable in any volcano since they are able to predict eruptions. Nevertheless, they present energy supply difficulties due to the absence of power grid, the remote access, and the climatology. As a solution, this work has designed a new integral system composed of thermoelectric generators with high efficiency heat exchangers, and its associated electronics, developed thanks to Internet of Things (IoT) technologies. Thus, the heat emitted from volcanic fumaroles is transformed directly into electricity with thermoelectric generators with passive heat exchangers based on phase change, leading to a continuous generation without moving parts that powers different sensors, the information of which is emitted via LoRa. The viability of the solution has been demonstrated both at the laboratory and at a real volcano, Teide (Canary Islands, Spain), where a compact prototype has been installed in an 82 C fumarole. The results obtained during more than eight months of operation prove the robustness and durability of the developed generator, which has been in operation without maintenance and under several kinds of meteorological conditions, leading to an average generation of 0.49 W and a continuous emission over more than 14 km.

Polyoxometalate chemistry at volcanoes: discovery of a novel class of polyoxocuprate nanoclusters in fumarolic minerals

Polyoxometalate (POM) chemistry is an important avenue of comprehensive chemical research, due to the broad chemical, topological and structural variations of multinuclear polyoxoanions that result in advanced functionality of their derivatives. The majority of compounds in the polyoxometalate kingdom are synthesized under laboratory conditions. However, Nature has its own labs with the conditions often unconceivable to the mankind. The striking example of such a unique environment is volcanic fumaroles – the natural factories of gas-transport synthesis. We herein report on the discovery of a novel class of complex polyoxocuprates grown in the hot active fumaroles of the Tolbachik volcano at the Kamchatka Peninsula, Russia. The cuboctahedral nanoclusters {[MCu12O8](AsO4)8} are stabilized by the core Fe(III) or Ti(IV) cations residing in the unique cubic coordination. The nanoclusters are uniformly dispersed over the anion- and cation-deficient NaCl matrix. Our discovery might have promising implications for synthetic chemistry, indicating the possibility of preparation of complex polyoxocuprates by chemical vapor transport (CVT) techniques that emulate formation of minerals in high-temperature volcanic fumaroles.

Cu9O2(VO4)4Cl2, the First Copper Oxychloride Vanadate: Mineralogically Inspired Synthesis and Magnetic Behavior.

A new spin-1/2 frustrated antiferromagnet, Cu9O2(VO4)4Cl2, was synthesized via chemical vapor transport method that emulates mineral formation in volcanic fumaroles. Cu9O2(VO4)4Cl2 is the first copper oxychloride vanadate obtained in the ternary CuO-V2O5-CuCl2 anhydrous system. Copper ions constitute a three-dimensional complex framework with a topological structure novel for synthetic compounds but similar to that in the fumarolic mineral yaroshevskite. All of the oxygen atoms except for the O7 site are strongly bonded in the VO4 tetrahedra. The O7 site belongs to an additional oxygen atom (Oa) being tetrahedrally coordinated by four Cu atoms, thus forming the OCu4 tetrahedra. The structural formula can be represented as Cu3[Cu6O2](VO4)4Cl2 highlighting oxocentered units in the structure. IR spectra reveal several absorption bands at 526, 578, and 601 cm-1 interpreted as a characteristic feature of the OCu4 tetrahedra. Cu9O2(VO4)4Cl2 reveals ferrimagnetic behavior with the Curie temperature TC = 24 K and the uncompensated moment of Mr ∼ 1.9 μB/f.u.

Mapping metabolic activity at single cell resolution in intact volcanic fumarole sediment.

Interactions among microorganisms and their mineralogical substrates govern the structure, function and emergent properties of microbial communities. These interactions are predicated on spatial relationships, which dictate metabolite exchange and access to key substrates. To quantitatively assess links between spatial relationships and metabolic activity, this study presents a novel approach to map all organisms, the metabolically active subset and associated mineral grains, all while maintaining spatial integrity of an environmental microbiome. We applied this method at an outgassing fumarole of Vanuatu's Marum Crater, one of the largest point sources of several environmentally relevant gaseous compounds, including H2O, CO2 and SO2. With increasing distance from the sediment-air surface and from mineral grain outer boundaries, organism abundance decreased but the proportion of metabolically active organisms often increased. These protected niches may provide more stable conditions that promote consistent metabolic activity of a streamlined community. Conversely, exterior surfaces accumulate more organisms that may cover a wider range of preferred conditions, implying that only a subset of the community will be active under any particular environmental regime. More broadly, the approach presented here allows investigators to see microbial communities 'as they really are' and explore determinants of metabolic activity across a range of microbiomes.

Biosilica layer-by-layer modified with polyamines and carboxyarsenazo for REE preconcentration prior to ICP-MS determination in lignites and volcanic fumarole sediment.

Biosilica-based adsorbents prepared from rice husk, sequentially modified with polymeric polyamines and carboxyarsenazo were proposed for the preconcentration of 13 lanthanides, La, Sc, and Y. It is shown that the proposed adsorbent quantitatively extracted rare earth elements (REEs) from solutions with pH 3.5-6.5. Carrying out adsorption at pH 3.5-4.5 allows the quantitative separation of rare earth elements from accompanying ions of non-ferrous, alkaline and alkaline-earth metals. A procedure for solid-phase extraction followed by mass spectrometric determination (SPE-ICP-MS) of REEs has been developed, which includes passing of 100 mL of the analyzed solution (pH 4) through a column with the adsorbent at a flow rate of 1 mL min-1, elution of REEs with 5 mL 1 M HNO3 (a preconcentration factor of 20) and subsequent determination of elements in the eluate by inductively coupled plasma mass spectrometry (ICP-MS). The accuracy of the results was confirmed by the recovery test of spiked samples and by analysis of a Certified Reference Material. The limit of detection was 0.04-10.9 ng L-1. The procedure was used for determination of REEs in lignites from Krasnoyarsk Krai (Russia) and fumarole sediment from Kudryavy volcano of the Greater Kuril Chain (Sakhalin Oblast, Russia).

Cadwaladerite, Al2(H2O)(OH)4·n(Cl,OH–,H2O), from Cerros Pintados, Chile, defined as a valid mineral species and the discreditation of lesukite

Abstract Cadwaladerite, described in 1941 as Al(OH)2Cl·4H2O, and lesukite, described in 1997 as Al2(OH)5Cl·2H2O, are very closely related chemically and structurally, but are found in very different environments. Cadwaladerite was found at the edge of a salar in Chile. Lesukite has been described from a volcanic fumarole and from burning coal seams. Both materials have cubic symmetry with a = 19.788 to 19.859Å. The crystal structure, common to both, consists of a rigid three-dimensional framework of edge- and corner-sharing Al(OH,H2O)6 octahedra that contains large interconnected cavities where loosely held Cl, OH, and H2O are located. The fact that Cl is loosely held within the structure is demonstrated by a dramatic reduction in Cl content after washing the material in distilled water, while the structural integrity is maintained. Herein, cadwaladerite is confirmed as a valid mineral species and lesukite is discredited because the only difference between the two materials is the loosely held extra-framework Cl, OH, and H2O. Cadwaladerite, Al2(H2O)(OH)4·n(Cl,OH,H2O) (Z = 48) takes precedence over lesukite based on the date of description. Material similar to cadwaladerite is found as a corrosion product on some types of nuclear fuel elements and is also closely related to the molecular species used in antiperspirant and water filtration.

Characterizing the Mineral Assemblages of Hot Spring Environments and Applications to Mars Orbital Data.

Certain martian hydrated silica deposits have been hypothesized to represent ancient hot spring environments, but many environments can produce hydrated silica on Earth. This study compares the mineral assemblages produced in terrestrial hot springs to those observed in silica-producing volcanic fumarolic environments to determine which diagnostic features of hot springs could be remotely sensed on Mars. We find that hot spring environments are more likely to produce geochemically mature silica (i.e., opal-CT and microcrystalline quartz) in addition to opal-A, whereas volcanic fumarolic environments tend to produce only opal-A, potentially reflecting differences in water-to-rock ratios. Neutral/alkaline hot springs contain few accessory minerals (typically calcite and Fe/Mg clays), while acidic hot springs commonly contain accessory kaolinite. By comparison, mineral assemblages at volcanic fumaroles contain protolith igneous minerals and a diversity of alteration minerals indicative of acidic conditions. Based on these terrestrial observations, the presence of opal-CT and/or microcrystalline quartz could be more diagnostic of a hot spring origin rather than a fumarolic origin, and accessory mineralogy could provide information on formation pH. On Mars, we observe that most orbital opal detections in outcrop are opal-A, sometimes accompanied by Fe/Mg clays, suggestive of neutral/alkaline conditions. However, these observations do not uniquely distinguish between hot springs and fumarolic environments, as opal-A can occur in both environments. Many martian silica detections occur in regionally extensive units, and sometimes in association with fluvial landforms suggesting a detrital or lower temperature authigenic origin. Thus, only a few martian opal detections may be mineralogically, spatially, and morphologically consistent with a hot spring origin. However, although it is difficult to unambiguously identify martian hot spring environments from orbital data sets, the orbital data are still valuable for identifying siliceous sites that are consistent with higher biosignature preservation potential, that is, sites with opal-A (not opal-CT), for future in situ investigations.

Stable hydrogen and oxygen isotopic compositions of water vapor in volcanic plumes sampled in glass bottles using cavity ring-down spectroscopy

The isotopic compositions (δ2H and δ18O) of fumarolic H2O emitted during volcanic eruptions can distinguish the type of eruption (magmatic or phreatic), but direct sampling of fumarolic H2O in eruptive volcanoes is often neither practical nor safe. In this study, we developed a new analytical system to safely determine the isotopic compositions of fumarolic H2O from the volcanic plume samples taken in glass bottles. The system consisted of stainless steel gas introduction line and a cavity ring-down spectroscopic unit. In the 1 L glass sample bottles, analytical precision (1σ) was estimated to be better than 2‰ and 0.3‰, respectively, when >3400 ppmv of H2O was introduced, and better than 3‰ (δ2H) and 0.4‰ (δ18O) when >1800 ppmv of H2O was introduced. The H2O concentration accuracy was better than 5%. Using this in-situ collection method and the analytical system, we determined the isotopic compositions of H2O in volcanic plume samples taken at Iwo-yama in the Kirishima volcano group (Japan), and deduced the isotopic composition of fumarolic H2O from the volcanic plume. The reciprocal of the H2O concentration in the plume samples showed a good linear relationship with the isotopic composition. The isotopic composition of fumarolic H2O from Iwo-yama estimated from the plume samples directly corresponded to the determined fumarolic H2O. This method improves upon previous analyses to obtain the isotopic compositions of fumarolic H2O, particularly by reducing tedious, time consuming, and dangerous sampling of water vapor at volcanic fumaroles.

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).

How do metals escape from magmas to form porphyry-type ore deposits?

Many precious and base metals (Cu, Au, Ag, Mo, W, Sn) in porphyry-type deposits are extracted from a granitic to granodioritic silicate melt and transported by magmatic-hydrothermal fluids to the site of ore deposition. Metals abundance increases from some ppb in the melt to % in ore bodies. Assuming a unique magmatic source for metals, it implies an exceptional combination of enrichment process acting over up to 4 orders of magnitude. Previous models of magma differentiation and hydrothermal circulations omitted to consider the role of metal segregation during magma chamber evolution. Models for the formation and evolution of intrusions have recently shifted from the so-called melting-storage-assimilation-homogenization (MASH) paradigm, basically steady state, to the mantle-melting-segregation-ascent-emplacement (m(M-SAE)) paradigm, dynamic and discontinuous in time. Successive magma injections of variable compositions progressively build the magma chamber. This is supported by field relations (e.g. cross-cutting dykes and stocks), textures (e.g. partially resorbed enclaves, or mineral fabrics), geochemistry (e.g. hybridization signatures), and age dating aswell as istopic studies. As melt crystallizes and forms a mush (>50% crystals), volatiles also exsolve forming a magmatic volatile phase (MVP) while melt motion slows down. Metals partition between the three phases: melt; crystals; and MVP. They generally prefer the MVP owing to more favorable partition coefficients. This is indicated by metal content in coeval melt and fluid inclusions with homogenization temperatures above 600 °C, or in volcanic fumaroles. Here, by simulating the physical interactions between the three phases we suggest a model of fluid sparging, during which metals segregate towards the MVP by diffusion and are further transported by advection as metal complexes. The model also provides estimates of metal enrichment. An undimensional Péclet number rules the competition between diffusion and advection, basically scaling with respect to the inverse of the product of melt viscosity (η) by metal diffusivity (D). The threshold value of the Péclet number between diffusion and advection is roughly 10−9. Fast diffusive metals (Au, Cu, Ag, W) readily diffuse from silicate melt and towards bubbles of the MVP. To escape the mush through tubular structures, the MVP must overcome a critical gas saturation level (about 20% vol.) usually reached after several magma injections. Advection then takes over and transports the metal-enriched MVP towards the top of the magma chamber. This leads to nearly coeval (1) separation between a high salinity-liquid phase and a low-salinity vapor phase, (2) fluid-rock interactions resulting in potassic, advanced argillic and phyllic alterations and (3) metal deposition. The metal enrichment scales as the ratio between partition coefficient (i.e. related to the gradient in chemical potential), diffusivity (i.e. related to the gradient of concentration), and melt viscosity (i.e. related to the gradient of momentum). The rates at which all such gradients relax determe metals enrichment, inducing chemical and physical instabilities, leading to a cyclic process. The whole cycle also encompasses the case of a partial, non-completed, full enrichment yielding to barren intrusions. A tentative model generalizes the sparging fluid model to other metal deposits linked to an intrusion. Such generalization should be interpreted as predicting metal enrichment by 3–4 orders of magnitude, rather than predicting an exact value.

Copper minerals from volcanic exhalations – a unique family of natural compounds: crystal-chemical review

The crystal-chemical characterization of oxysalts (sulfates, arsenates, vanadates, selenites, silicates, molybdates and borates), chlorides and oxides with species-defining Cu2+ formed in volcanic fumaroles (96 minerals representing 80 structure types; 81 species are endemic to fumarolic formation) is given. Copper minerals are known only from oxidizing-type fumaroles. The most diverse copper mineralization occurs at the Tolbachik volcano (Kamchatka, Russia). Copper minerals from fumarolic systems are subdivided into two genetic groups: Group I are minerals formed in the hot zones of fumaroles (>473 K, mainly 673–973 K) and Group II are minerals formed in the moderately hot zones of fumaroles (<473 K, mainly at 343–423 K). Group I includes 81 mineral species. Their most defining chemical feature is that all of them are hydrogen-free, and many of them contain the additional anion O2−. In comparison with minerals from other geological environments, in minerals of Group I the Cu2+ cation exhibits the strongest affinity for four- and fivefold coordinations and the strongest distortion of Cu2+-centred octahedra. Group II consists of 15 chlorides and sulfates including 13 H-bearing species. In these minerals the Cu2+ cation shows affinity for octahedral coordination, with OH− and/or H2O0 as ligands. In terms of crystal chemistry these minerals are closer to supergene minerals rather than to high-temperature fumarolic species. Temperature is the major factor governing the crystal chemistry of Cu2+ oxysalts and chlorides in low-pressure systems. The defining feature of fumarolic copper mineralization over this whole temperature range is the important role of alkali cations. The available data on complexes of Cu2+-centred polyhedra in the structures of natural oxysalts and halides are summarized and reviewed. Isomorphism in copper minerals from volcanic exhalations is discussed. The structures of high-temperature Cu oxysalts with additional O2− anions (i.e. O atoms non-bonded to S6+, Mo6+, As5+, V5+, Se4+ or B3+) are also interpreted using an approach based on oxocentred tetrahedra.

Young, small-scale surface features in Meridiani Planum, Mars: A possible signature of recent transient liquid and gas emissions

Enigmatic small-scale (<1 m) depositional and erosional features found in basaltic sands partly covering bedrock exposures, imaged at several locations in the equatorial Meridiani Planum region by the Mars Exploration Rover Opportunity, may be evidence of previously unrecognized, geologically young (or even contemporary) Martian surface processes. Leveed fissures appear to have formed by venting from beneath; possible explanations include aeolian blowholes near crater margins, volcanic fumarole activity, or gas/vapour escape resulting from the decomposition of small pockets of ground ice, methane clathrates or hydrated sulphate minerals. Some leveed fissures cross-cut and are therefore younger than aeolian ripples thought to have last been active c. 50,000 years ago. Erosional gutters are sharply defined and fresh-looking, internally terraced, sometimes are deeper near one end, and in one case seem to give way to small depositional fans downslope; they have the appearance of having been formed by liquid flow rather than by wind erosion. There is evidence elsewhere that contemporary ground-ice thaw and consequent transient surface run-off may occur occasionally under present conditions at low, near-equatorial latitudes on Mars; short-lived (even for just a few minutes) meltwater emission and flow at the surface could form gutters before evaporating. Further possibilities are the decomposition of buried pockets of methane clathrates (which theoretical considerations suggest might be present and stable even in equatorial regions) giving rise to both methane gas venting and transient surface water, or the release of liquid brines by decomposition of hydrated magnesium sulphate minerals or deliquescence of perchlorates. Dry granular flow mechanisms proposed as explanations for Recurring Slope Lineae seem inadequate to explain the morphologies of leveed fissures and gutters.