CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

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Experimental palagonitization of basaltic glasses of varied composition

The rate of palagonitization of three chemically different types of basaltic glasses has been determined experimentally as a function of temperature (20–90 ° C) and time (3.5–14 months) in both fresh and saline water. Between ca. 40 ° C and 70 ° C there is a marked increase in the rate of transformation of the glasses, especially those of alkali basalt composition. The alteration process also accelerates after ca. 10 months at temperature higher than 70 ° C. These phenomena are possibly related to stepwise losses of the major elements, and minimum activation temperatures for the oxide/ion—water metasomatism.     

Formation of iron-containing colloids by the weathering of phyllite

The formation of colloids during the weathering of phyllite was investigated by exposing ground phyllite to Milli-Q water. Secondary mineral colloids of 10¹–10² nm were detected in significant concentrations. At pH of about 8.5, the solution concentration of these colloids reached up to 10 mg/L (however, acidification to pH 4.0 prevented the formation of the colloids). The mineralogical composition of the secondary mineral colloids is assumed to be a mixture of ferrihydrite, manganese oxyhydroxides, aluminosilicates, amorphous Al(OH)₃ and gibbsite with possible additions of iron silicates and␣iron-alumino silicates. The colloids were stable over longer periods of time (at least several weeks), even in the presence of suspended ground rock. Direct formation of iron-containing secondary mineral colloids at the rock–water interface by the weathering of rock material is an alternative to the well-known mechanism of iron colloid formation in the bulk of water bodies by mixing of different waters or by aeration of anoxic waters. This direct mechanism is of relevance for colloid production during the weathering of freshly crushed rock in the unsaturated zone as for instance crushed rock in mine waste rock piles. Colloids produced by this mechanism, too, can influence the transport of contaminants such as actinides because these colloids have a large specific surface area and a high sorption affinity.     

Chronology of Quaternary terrace deposits at the locality Hohle Gasse (Pratteln,NW Switzerland)

The Quaternary stratigraphy of the Alpine Foreland consists of distinct terrace levels, which have been assigned to four morphostratigraphic units: Höhere (Higher) Deckenschotter, Tiefere (Lower) Deckenschotter, Hochterrasse (High Terrace) and Niederterrasse (Lower Terrace). Here, we focus on the terrace gravels at Hohle Gasse, SSE of Pratteln near Basel, which are mapped as Tiefere Deckenschotter. Petrographic and morphometric data established from clasts allowed to infer the transport mechanisms and sources of the gravels. Sedimentological analyses indicate that the gravels were transported by a braided river and deposited in a distal glaciofluvial setting. In addition, it can be shown that the majority of the clasts display multiple reworking and only a minority maintained a distinct glaciofluvial shape. Cosmogenic multi-isotope dating using ¹⁰Be and ³⁶Cl allowed direct dating of the sediments at the study site. A depth-profile age of \(2 70_{ - 1 90}^{ + 8 30}\) ka for ¹⁰Be was achieved for the deposits at Hohle Gasse. Unfortunately, no age could be modelled from the ³⁶Cl concentrations as the blank correction was too high. Furthermore, this age proves that the studied terrace level should be assigned to the morphostratigraphic unit Hochterrasse.     

The last erosional stage of the Molasse Basin and the Alps

We present a synoptic overview of the Miocene-present development of the northern Alpine foreland basin (Molasse Basin), with special attention to the pattern of surface erosion and sediment discharge in the Alps. Erosion of the Molasse Basin started at the same time that the rivers originating in the Central Alps were deflected toward the Bresse Graben, which formed part of the European Cenozoic rift system. This change in the drainage direction decreased the distance to the marine base level by approximately 1,000 km, which in turn decreased the average topographic elevation in the Molasse Basin by at least 200 m. Isostatic adjustment to erosional unloading required ca. 1,000 m of erosion to account for this inferred topographic lowering. A further inference is that the resulting increase in the sediment discharge at the Miocene–Pliocene boundary reflects the recycling of Molasse units. We consider that erosion of the Molasse Basin occurred in response to a shift in the drainage direction rather than because of a change in paleoclimate. Climate left an imprint on the Alpine landscape, but presumably not before the beginning of glaciation at the Pliocene–Pleistocene boundary. Similar to the northern Alpine foreland, we do not see a strong climatic fingerprint on the pattern or rates of exhumation of the External Massifs. In particular, the initiation and acceleration of imbrication and antiformal stacking of the foreland crust can be considered solely as a response to the convergence of Adria and Europe, irrespective of erosion rates. However, the recycling of the Molasse deposits since 5 Ma and the associated reduction of the loads in the foreland could have activated basement thrusts beneath the Molasse Basin in order to restore a critical wedge. In conclusion, we see the need for a more careful consideration of both tectonic and climatic forcing on the development of the Alps and the adjacent Molasse Basin.     

Determination of line averages of sensible heat flux using an optical method

An optical method is discussed for the determination of the line average of the vertical temperature gradient, which is subsequently used for the calculation of the scaling temperature and of the sensible heat flux. The method requires conventional surveying instrumentation only, and the measurements are carried out easily. The attainable accuracy is estimated as 10% or better. Observations are also possible during night or light-wind conditions. In a field experiment, results from this optical method were compared with measurements taken with a conventional covariance eddy-flux instrument. Excellent agreement between both methods was found.     

Bearing of rare earth patterns of apatites from igneous and metamorphic rocks

Twelve apatite samples from igneous and metamorphic rocks from the Black Forest and igneous rocks from the Kaiserstuhl were analysed for their REE content. The ΣREE range from 0.116 to 1.69 wt.%; the lowest values were found in the metamorphic rocks. All apatites from the various parent rocks show a general enrichment of the lighter rare earths over the heavier and their chondrite-normalized rare earth patterns exhibit a more or less pronounced negative Ce anomaly. This Ce depletion is accompanied by relatively low La and Pr values. In addition, the apatites from igneous rocks from the Black Forest show a marked negative Eu anomaly. An explanation is offered for the simultaneous occurrence of a negative Ce and a negative Eu anomaly in one investigated rock system. The negative Ce anomaly is attributed to the occurrence of phases enriched in Ce (e.g., monazite, allanite) which crystallized prior to or simultaneously with apatite. The negative Eu anomaly in these magmatic apatites most probably is caused by discrimination of Eu²⁺ from the apatite lattice. The result of this discrimination is a selective Eu enrichment in the later crystallizing feldspars, plagioclase and orthoclase. At least in this case, the positive Eu anomaly in feldspars is not a reliable indicator of low oxygen fugacity during their crystallization; the Eu depletion of the earlier crystallized apatites is preferable for this purpose.