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.     

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.     

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.     

Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

Developing country perspectives on ‘mitigation actions’, ‘NAMAs’, and ‘LCDS’

The MAPS programme, which seeks to deepen mitigation ambition in developing countries, is engaged in exploring the concepts of Nationally Appropriate Mitigation Actions (NAMAs) and Low Carbon Development Strategies (LCDS) from a developing country perspective. Here, climate mitigation practitioners in six developing countries were surveyed for their understanding of these concepts (anonymous, personal communications with climate mitigation practitioners in Argentina, Brazil, Chile, Colombia, India, and South Africa). It is found that there is much scope for clarity and conceptual elaboration in this policy space. NAMAs are largely interpreted as mitigation activities packaged for submission to the United Nations Framework Convention on Climate Change (UNFCCC) registry, but are not held to constitute the full set of mitigation activity in a developing country. New terminology may be needed to describe this broader set. A tighter interpretation of LCDS to distinguish between a strategic or coordinating policy action may be useful. Other themes arising include the way ‘national appropriateness’ is reflected in the concepts, and the role of international policy in deepening mitigation action in developing countries.     

Current approaches to MRV in South Africa: a scoping study

It is shown that there are MRV-related activities underway in South Africa, particularly focusing on measuring electricity consumption and monitoring GHG emissions. Yet currently many of these activities happen in parallel systems within multi-polar governance structures. A bottom-up perspective of MRV in South Africa, informed by interviews, workshops, desktop research, and stakeholder consultations, is provided and the systems, data, methodologies, and the institutional environment relevant to a South African MRV system are examined. The development of the local monitoring and evaluation system, and its relevance within the international MRV context, is also discussed. Some recommendations are made: most importantly, there is a need for a coherent approach to be developed, one that is coordinated by government and built on existing MRV systems.     

Estimation and testing of higher-order spatial autoregressive panel data error component models

This paper develops an estimator for higher-order spatial autoregressive panel data error component models with spatial autoregressive disturbances, SARAR(R,S). We derive the moment conditions and optimal weighting matrix without distributional assumptions for a generalized moments (GM) estimation procedure of the spatial autoregressive parameters of the disturbance process and define a generalized two-stage least squares estimator for the regression parameters of the model. We prove consistency of the proposed estimators, derive their joint asymptotic distribution, and provide Monte Carlo evidence on their small sample performance.