Growth patterns and implications of complex dendrites in calcite travertines from Lýsuhóll, Snæfellsnes, Iceland

Calcite dendrite crystals are important but poorly understood components of calcite travertine that forms around many hot springs. The Lýsuhóll hot-spring deposits, located in western Iceland, are formed primarily of siliceous sinters that were precipitated around numerous springs that are now inactive. Calcite travertine formed around the vent and on the discharge apron of one of the springs at the northern edge of the area. The travertine is formed largely of two types (I and II) of complex calcite dendrite crystals, up to 1 cm high, that grew through the gradual addition of trilete sub-crystals. The morphology of the dendrite crystals was controlled by flow direction and the competition for growth space with neighbouring crystals. Densely crowded dendrites with limited branching characterize the rimstone dams whereas widely spaced dendrites with open branching are found in the pools. Many dendrite bushes in the pools nucleated around plant stems. Growth of the dendrite crystals was seasonal and incremental. Calcite precipitation was driven by rapid CO₂ degassing of CO₂-rich spring waters during the spring and summer. During winter, when snow covered the ground and temperatures were low, opal-A precipitated on the exposed surfaces of the dendrites. Segmentation of dendrite branches by discontinuities coated with opal-A and overgrowth development around sub-crystals resulted from this seasonal growth cycle. The calcite dendrite crystals in the Lýsuhóll travertine differ in morphology from those at other hot springs, such as those at Lake Bogoria, Kenya, and Waikite in New Zealand. Comparison with the calcite dendrite crystals found at those sites shows that dendrite morphology is site-specific and probably controlled by carbonate saturation levels that, in turn, are controlled by the rate of CO₂ degassing and location in the spring outflow system.     

Melt inclusion constraints on volatile systematics and degassing history of the 2014–2015 Holuhraun eruption,Iceland

The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H₂O, CO₂, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO₂, 0.13–0.16 wt% H₂O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures?≥?0.4 GPa (~?12 km depth) promoting deep degassing of CO₂. Prior to the onset of degassing, the melt CO₂ content may have reached 3000–4000 ppm, with the total magmatic CO₂ budget estimated at  23–55 Mt. SO₂ release commenced at 0.12 GPa (~?3.6 km depth), eventually leading to entrapment of SO₂ vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H₂O, 5.9–7.7 Mt CO₂, and 11.3 Mt of SO₂ over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H₂O, where field measurements may be heavily biased by the incorporation of meteoric water.     

Origin of pedogenic needle-fiber calcite revealed by micromorphology and stable isotope composition—a case study of a Quaternary paleosol from Hungary

Pedogenic needle-fiber calcite was studied regarding its morphology, texture and stable isotope composition from the paleosol of the Quaternary Várhegy travertine (Budapest, Hungary). The needle-fiber calcite is composed of 40–200 μm long monocrystals. Smooth rods as well as serrated-edged crystals with calcite overgrowths were identified by SEM. Needles have several textural varieties: randomly distributed crystals in vugs and pores with calcite hypocoatings, bundles of subparallel crystals forming coatings around grains and alveolar structure with bridging needles in vugs.The morphological study of needle-fiber calcite suggests that needles are calcified fungal sheaths and produced by fungal biomineralization, a common process in recent and fossil soils and calcretes. The stable isotope composition of needle-fiber calcite (average: δ¹⁸O=-7.1‰ and δ¹³C=-7.3‰ vs. V-PDB) indicates significant incorporation of organically derived CO₂ and probably biological influence on needle genesis. Dissolved host rock travertine and/or atmospheric CO₂ could also contribute some carbon to the acicular calcite.     

Fluid inclusions as microchemical systems: evidence and modelling of fluid–host interactions in plagioclase

Dense, CO₂‐rich fluid inclusions hosted by plagioclases, An₄₅ to An₅₄, of the O.‐v.‐Gruber‐ Anorthosite body, central Dronning Maud Land, East Antarctica, contain varying amounts of small calcite, paragonite and pyrophyllite crystals detected by Raman microspectroscopy. These crystals are reaction products that have formed during cooling of the host and the original CO₂‐rich H₂O‐bearing enclosed fluid. Variable amounts of these reaction products illustrates that the reaction did not take place uniformly in all fluid inclusions, possibly due to differences in kinetics as caused by differences in shape and size, or due to compositional variation in the originally trapped fluid. The reaction albite + 2anorthite + 2H₂O + 2CO₂ = pyrophyllite + paragonite + 2calcite was thermodynamically modelled with consideration of different original fluid compositions. Although free H₂O is not detectable in most fluid inclusions, the occurrence of OH‐bearing sheet silicates indicates that the original fluid was not pure CO₂, but contained significant amounts of H₂O. Compared to an actual fluid inclusion it is obvious, that volume estimations of solid phases can be used as a starting point to reverse the retrograde reaction and recalculate the compositional and volumetrical properties of the original fluid. Isochores for an unmodified inclusion can thus be reconstructed, leading to a more realistic estimation of P–T conditions during earlier metamorphic stages or fluid capturing.     

The analysis of the volatiles from fluid inclusions in hydrothermal fluorite

Volatiles from primary fluid inclusions in hydrothermal fluorite were studied. The gases released were analysed with a mass spectrometer using an internal standard; water-vapour pressure was measured manometrically.To extract the volatiles, both heating and grinding in vacuum were used. In the thermal treatment, volatiles from other sources besides the inclusions were also found: H₂ and hydrocarbons, as well as additional amounts of H₂O and CO₂. The vacuum grinding, on the other hand, leads to volatile deficiency, especially with respect to H₂O and CO₂, due to retention of these components on the ground material.The study of the dependence of amount of volatiles released upon heating, on the grain size of the mineral fractions, was used as additional information for evaluating the amounts of volatiles coming from a source other than inclusions.The thermal studies were supplemented by decrepitophonic measurements.It is concluded that the volatiles from inclusions are represented practically only by CO₂ and H₂O in a 1:100 molar ratio. Conclusions about the conditions of mineral formation are drawn.     

Ore Genesis of the Kalatongke Cu–Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu–Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt (CAOB). The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200–400°C, 400–900°C and 900–1200°C. The released volatiles from silicate mineral separates at 400–900°C and 900–1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O (av. ~92 mol%) with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values (from ?20.86‰ to ?12.85‰) of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantle-derived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200–400°C are dominated by H2O with minor CO2, N2+CO and SO2, with δ13CCO2 values (?25.66‰ to ?22.98‰) within the crustal ranges, and are considered to be related to secondary tectonic– hydrothermal activities.     

Calcite from the Quaternary spring waters at Tylicz, Krynica, Polish Carpathians

At Tylicz, near Krynica Spa (Polish Carpathians), spelean deposits fill fissures and caverns in Eocene flysch rocks. They occur as: (1) clastic cave sediments transformed into hard crusts due to cementation by finely crystalline low-Mg calcite, (2) drusy calcite that covers crust surfaces and fills voids in the crust and (3) colloform calcite. Two varieties of drusy calcite are distinguished: acicular and columnar. The acicular calcite is built up of crystallites forming spherulitic fans or cones. In places it is syntaxially covered with colloform calcite. The drusy calcite is low-Mg ferroan calcite with non-ferroan subzones, whereas the colloform calcite is a low-Mg non-ferroan variety. The columnar calcite crystals form fan-like bundles. Cross-sections cut perpendicular to the c-axes of columnar crystals are equilateral triangular in shape, although some have slightly curved edges. The columnar crystals have steep rhombic terminations and most have curved triangular faces, i.e. gothic-arch calcite. Saddle crystals have also been observed. The columnar crystals are composed of radially orientated crystallites whose long dimension is parallel to the c-axis. The curved crystal faces of such polycrystals are interpreted as a result of differential growth rates of the crystallites. The spelean calcites precipitated from CO₂-saturated water. The high rate of CaCO₃ precipitation is thought to be responsible for the formation of radial structures. Finely crystalline calcite formed within pore spaces of clastic sediments close to the water-air interface, drusy calcite crystallized beneath the water-air interface, and colloform calcite precipitated from thin films of water.     

CO2 emission accompanying the fracture of calcite

Time resolved mass spectroscopy of the emissions accompanying the fracture of calcite (rhombohedral CaCO₃) show that the principle volatile product, CO₂, is released in bursts milliseconds after the fracture event. Similar measurements during the abrasion of calcite and during low temperature thermal decomposition of pulverized calcite show similar CO₂ bursts. We argue that the observed bursts reflect localized decomposition of the calcite during the relaxation of reversible plastic deformation created by fracture and abrasion. This implies that mechanical, non-thermal processes play an important role in producing the observed decomposition products.     

The melt inclusion record from the rhyolitic Kos Plateau Tuff (Aegean Arc)

The >60 km³ rhyolitic Kos Plateau Tuff provides an exceptional probe into the behavior of volatile components in highly evolved arc magmas: it is crystal-rich (30–40 vol% crystals), was rapidly quenched by the explosive eruptive process, and contains abundant homogeneous melt inclusions in large quartz crystals. Several methods for measuring major, trace and volatile element concentrations (SIMS, FTIR, Raman spectroscopy, electron microprobe, LA–ICPMS) were applied to these melt inclusions. We found a ~2 wt% range of H₂O contents (4.5–6.5 wt% H₂O, measured independently by SIMS, FTIR, and Raman spectroscopy) and relatively low CO₂ concentrations (15–140 ppm measured by FTIR, with most analyses <100 ppm). No obvious correlations between H₂O, CO₂, major and trace elements are observed. These observations require a complex, protracted magma evolution in the upper crust that included: (1) vapor-saturated crystallization in a chamber located between 1.5 and 2.5 kb pressure, (2) closed-system degassing (with up to 10 vol% exsolved gas) as melts percolated upwards through a vertically extensive mush zone (2–4 km thick), and (3) periodic gas fluxing from subjacent, more mafic and more CO₂-rich magma, which is preserved as andesite bands in pumices. These processes can account for the range of observed H₂O and CO₂ values and the lack of correlation between volatiles and trace elements in the melt inclusions.     

Experimental study of the aragonite to calcite transition in aqueous solution

The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 °C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca²⁺]:[CO₃²⁻] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy.Experiments using carbonate solutions prepared with water enriched in ¹⁸O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of ¹⁸O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the ¹⁸O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C¹⁶O₃²⁻]_aq and [H₂¹⁸O] and the time for oxygen isotope exchange in the fluid at 200 °C was estimated at ∼0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.     

Reaction kinetics of dolomite rim growth

Reaction rims of dolomite (CaMg[CO₃]₂) were produced by solid-state reactions at the contacts of oriented calcite (CaCO₃) and magnesite (MgCO₃) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO₃ interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO₃. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E _a (CaO) = 192 ± 54 kJ/mol and E _a (MgO) = 198 ± 44 kJ/mol, respectively.     

Carbonate cements in Miller field of the UK North Sea: a natural analog for mineral trapping in CO<Subscript>2</Subscript> geological storage

Miller field of the North Sea has had high concentrations of natural CO₂ for ~70 Ma. It is an ideal analog for the long-term fate of CO₂ during engineered storage, particularly for formation of carbonate minerals that permanently lock up CO₂ in solid form. The Brae Formation reservoir sandstone contains an unusually high quantity of calcite concretions; however, C and O stable isotopic signatures suggest that these are not related to the present-day CO₂ charge. Margins of the concretions are corroded, probably because of reduced pH due to CO₂ influx. Dispersed calcite cements are also present, some of which postdate the CO₂ charge and, therefore, are the products of mineral trapping. It is calculated that only a minority of the reservoired CO₂ in Miller (6–24%) has been sequestrated in carbonates, even after 70 Ma of CO₂ emplacement. Most of the CO₂ accumulation is dissolved in pore fluids. Therefore, in a reservoir similar to the Brae Formation, engineered CO₂ storage must rely on physical retention mechanisms because mineral trapping is both incomplete and slow.     

Evolution of metamorphic volatiles during exhumation of microdiamond-bearing granulites in the Western Gneiss Region, Norway

Fluid inclusions in garnet, kyanite and quartz from microdiamond-bearing granulites in the Western Gneiss Region, Norway, document a conspicuous fluid evolution as the rocks were exhumed following Caledonian high- and ultrahigh-pressure (HP–UHP) metamorphism. The most important of the various fluid mixtures and daughter minerals in these rocks are: (N₂ + CO₂ + magnesian calcite), (N₂ + CO₂ + CH₄ + graphite + magnesian calcite), (N₂ + CH₄), (N₂ + CH₄ + H₂O), (CO₂) and (H₂O + NaCl + CaCl₂ + nahcolite). Rutile also occurs in the N₂ + CO₂ inclusions as a product of titanium diffusion from the garnet host into the fluid inclusions. Volatiles composed of N₂ + CO₂ + magnesian calcite characterise the ambient metamorphic environment between HP–UHP (peak) and early retrograde metamorphism. During progressive decompression, the mole fraction of N₂ increased in the fluid mixtures; as amphibolite-facies conditions were reached, CH₄ and later, H₂O, appeared in the fluids, concomitant with the disappearance of CO₂ and magnesian calcite. Graphite is ubiquitous in the host lithologies and fluid inclusions. Thermodynamic modelling of the metamorphic volatiles in a graphite-buffered C-O-H system demonstrates that the observed metamorphic volatile evolution was attainable only if the f _O2 increased from c. −3.5 (±0.3) to −0.8 (±0.3) log units relative to the FMQ oxygen buffer. External introduction of oxidising aqueous solutions along a system of interconnected ductile shear zones adequately explains the dramatic increase in the f _O2. The oxidising fluids introduced during exhumation were likely derived from dehydration of oceanic crust and continental sediments previously subducted during an extended period of continental collision in conjunction with the Caledonian orogeny. Received: 15 December 1997 / Accepted: 25 May 1998     

Influences of air CO<Subscript>2</Subscript> on hydrochemistry of drip water and implications for paleoclimate study in a stream-developed cave,SW China

Cave air CO₂ is a vital part of the cave environment. Most studies about cave air CO₂ variations are performed in caves with no streams; there are few studies to date regarding the relationship of cave air CO₂ variations and drip water hydrochemistry in underground stream–developed caves. To study the relationship of underground stream, drip water, and cave air CO₂, monthly and daily monitoring of air CO₂ and of underground stream and drip water was performed in Xueyu Cave from 2012 to 2013. The results revealed that there was marked seasonal variation of air CO₂ and stream hydrochemistry in the cave. Daily variations of cave air CO₂, and of stream and drip water hydrochemistry, were notable during continuous monitoring. A dilution effect was observed by analyzing hydrochemical variations in underground stream and drip water after rainfall. High cave air CO₂ along with low pH and low δ¹³C_DIC in stream and drip water indicated that air CO₂ was one of the dominant factors controlling stream and drip water hydrochemistry on a daily scale. On a seasonal scale, stream flows may promote increased cave air CO₂ in summer; in turn, the higher cave air CO₂ could inhibit degassing of drip water and make calcite δ¹³C more negative. Variation of calcite δ¹³C (precipitated from drip water) was in reverse of monthly temperature, soil CO₂, and cave air CO₂. Therefore, calcite δ¹³C in Xueyu Cave could be used to determine monthly changes outside the cave. However, considering the different precipitation rate of sediment in different seasons, it was difficult to use stalagmites to reconstruct environmental change on a seasonal scale.     

Carbonation of alkaline paper mill waste to reduce CO2 greenhouse gas emissions into the atmosphere

The global warming of Earth’s near-surface, air and oceans in recent decades is a direct consequence of anthropogenic emission of greenhouse gases into the atmosphere such as CO₂, CH₄, N₂O and CFCs. The CO₂ emissions contribute approximately 60% to this climate change. This study investigates experimentally the aqueous carbonation mechanisms of an alkaline paper mill waste containing about 55 wt% portlandite (Ca(OH)₂) as a possible mineralogical CO₂ sequestration process. The overall carbonation reaction includes the following steps: (1) Ca release from portlandite dissolution, (2) CO₂ dissolution in water and (3) CaCO₃ precipitation. This CO₂ sequestration mechanism was supported by geochemical modelling of final solutions using PHREEQC software, and observations by scanning electron microscope and X-ray diffraction of final reaction products. According to the experimental protocol, the system proposed would favour the total capture of approx. 218 kg of CO₂ into stable calcite/ton of paper waste, independently of initial CO₂ pressure. The final product from the carbonation process is a calcite (ca. 100 wt%)-water dispersion. Indeed, the total captured CO₂ mineralized as calcite could be stored in degraded soils or even used for diverse industrial applications. This result demonstrates the possibility of using the alkaline liquid–solid waste for CO₂ mitigation and reduction of greenhouse effect gases into the atmosphere.     

Suitability of Existing Numerical Model Codes and Thermodynamic Databases for the Prognosis of Calcite Dissolution Processes in Near-Surface Sediments Due to a CO2 Leakage Investigated by Column Experiments

Among the risks of CO₂ storage is the potential of CO₂ leakage into overlaying formations and near-surface potable aquifers. Through a leakage, the CO₂ can intrude into protected groundwater resources, which can lead to groundwater acidification followed by potential mobilisation of heavy metals and other trace metals through mineral dissolution or ion exchange processes. The prediction of pH buffer reactions in the formations overlaying a CO₂ storage site is essential for assessing the impact of CO₂ leakages in terms of trace metal mobilisation. For buffering the pH-value, calcite dissolution is one of the most important mechanisms. Although calcite dissolution has been studied for decades, experiments conducted under elevated CO₂ partial pressures are rare. Here, the first study for column experiments is presented applying CO₂ partial pressures from 6 to 43 bars and realising a near-natural flow regime. Geochemical calculations of calcite dissolution kinetics were conducted using PHREEQC together with different thermodynamic databases. Applying calcite surface areas, which were previously acquired by N₂-BET or calculated based on grain diameters, respectively, to the rate laws according to Plummer et al. (Am J Sci 278:179–216, doi:10.2475/ajs.278.2.179, 1978) or Palandri and Kharaka (US Geol Surv Open file Rep 2004–1068:71, 2004) in the numerical simulations led to an overestimation of the calcite dissolution rate by up to three orders of magnitude compared to the results of the column experiments. Only reduction of the calcite surface area in the simulations as a fitting procedure allowed reproducing the experimental results. A reason may be that the diffusion boundary layer (DBL), which depends on the groundwater flow velocity and develops at the calcite grain surface separating it from the bulk of the solution, has to be regarded: The DBL leads to a decrease in the calcite dissolution rate under natural laminar flow conditions compared to turbulent mixing in traditional batch experiments. However, varying the rate constants by three orders of magnitudes in a field scale PHREEQC model simulating a CO₂ leakage produced minor variations in the pH buffering through calcite dissolution. This justifies the use of equilibrium models when calculating the calcite dissolution in CO₂ leakage scenarios for porous aquifers and slow or moderate groundwater flow velocities. However, the selection of the thermodynamic database has an impact on the dissolved calcium concentration, leading to an uncertainty in the simulation results. The resulting uncertainty, which applies also to the calculated propagation of an aquifer zone depleted in calcite through dissolution, seems negligible for shallow aquifers of approximately 60 m depth, but amounts to 35 % of the calcium concentration for aquifers at a depth of approximately 400 m.     

In-situ Growth of Calcite at Devils Hole, Nevada: Comparison of Field and Laboratory Rates to a 500,000 Year Record of Near-Equilibrium Calcite Growth

Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO₃ solutions at 34 °C, CO₂ partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of P_{CO 2}, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.     

Generation of CO2-rich melts during basalt magma ascent and degassing

To test mechanisms of basaltic magma degassing, continuous decompressions of volatile-bearing (2.7–3.8 wt% H₂O, 600–1,300 ppm CO₂) Stromboli melts were performed from 250–200 to 50–25 MPa at 1,180–1,140 °C. Ascent rates were varied from 0.25 to ~1.5 m/s. Glasses after decompression show a wide range of textures, from totally bubble-free to bubble-rich, the latter with bubble number densities from 10⁴ to 10⁶ cm^?3, similar to Stromboli pumices. Vesicularities range from 0 to ~20 vol%. Final melt H₂O concentrations are homogeneous and always close to solubilities. In contrast, the rate of vesiculation controls the final melt CO₂ concentration. High vesicularity charges have glass CO₂ concentrations that follow theoretical equilibrium degassing paths, whereas glasses from low vesicularity charges show marked deviations from equilibrium, with CO₂ concentrations up to one order of magnitude higher than solubilities. FTIR profiles and maps reveal glass CO₂ concentration gradients near the gas–melt interface. Our results stress the importance of bubble nucleation and growth, and of volatile diffusivities, for basaltic melt degassing. Two characteristic distances, the gas interface distance (distance either between bubbles or to gas–melt interfaces) and the volatile diffusion distance, control the degassing process. Melts containing numerous and large bubbles have gas interface distances shorter than volatile diffusion distances, and degassing proceeds by equilibrium partitioning of CO₂ and H₂O between melt and gas bubbles. For melts where either bubble nucleation is inhibited or bubble growth is limited, gas interface distances are longer than volatile diffusion distances. Degassing proceeds by diffusive volatile transfer at the gas–melt interface and is kinetically limited by the diffusivities of volatiles in the melt. Our experiments show that CO₂-oversaturated melts can be generated as a result of magma decompression. They provide a new explanation for the occurrence of CO₂-rich natural basaltic glasses and open new perspectives for understanding explosive basaltic volcanism.     

Experimental investigation of the mechanism of the reaction: 1 tremolite+11 dolomite ⇌ 8 forsterite+13 calcite+9 CO2+1H2O

Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO₂-H₂O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO₂ produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO₂ concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO₂-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO₂-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:

1. Dissolution of the reactants tremolite and dolomite.
2. Diffusion of the dissolved constituents in the fluid.
3. Heterogeneous nucleation of the product minerals.
4. Growth of forsterite and calcite from the fluid.

Two possible explanations are discussed for the development of the amoured texture at \(X_{{\text{CO}}_{\text{2}} }\) above 0.4. The first is based upon the assumption that dolomite has a lower rate of dissolution than tremolite at high \(X_{{\text{CO}}_{\text{2}} }\) values resulting in preferential calcite and forsterite nucleation and growth on the dolomite surface. An alternative explanation is the formation of a raised CO₂ concentration around the dolomite grains at high \(X_{{\text{CO}}_{\text{2}} }\) values, leading to product precipitation on the dolomite crystals.     

Volatile content and degassing processes in the AD 79 magma chamber at Vesuvius (Italy)

The evolution of volatiles in the AD 79 magma chamber at Vesuvius (Italy) was investigated through the study of melt inclusions (MI) in crystals of different origins. FTIR spectroscopy and EMPA were used to measure H₂O, CO₂, S and Cl of the different melts. This allowed us to define the volatile content of the most evolved, phonolitic portion of the magma chamber and of the mafic melts feeding the chamber. MI in sanidine from phonolitic and tephri-phonolitic pumices show systematic differences in composition and volatile content, which can be explained by resorption of the host mineral during syn-eruptive mixing. The pre-eruption content of phonolitic magma appears to have been dominated by H₂O and Cl (respectively 6.0 to 6.5 wt% and 6700 ppm), while magma chamber refilling occurred through the repeated injection of H₂O, CO₂ and S-rich tephritic magmas (respectively 3%, 1500 ppm and 1400 ppm). Strong CO₂ degassing probably occurred during the decompressional path of mafic batches towards the magma chamber, while sulphur was probably released by the magma following crystallization and mixing processes. Water and chlorine strongly accumulated in the magma and reached their solubility limits only during the eruption. Chlorine solubility appears to have been strongly compositionally controlled, and Cl release was inhibited by groundmass crystallization of leucite, which shifted the composition of the residual liquid towards higher Cl solubilities. Received: 28 October 1999 / Accepted: 21 April 2000