Various aspects of ion-molecule reactions for Titan ionospheric chemistry modeling are reviewed in this work: temperature/collision energy effects on reaction rates and, more importantly, on products distributions; differential reactivity of isomers of ions; reactivity of excited states of ions; pathways to the building of complex ions. We evaluate here the extent to which these points affect model predictions. We find that the present limiting factors to model predictivity are the model incompleteness for heavy ion production pathways; the differential reactivity of isomers; and, to a lesser degree, the temperature effects on the branching ratios of ion-molecule reactions. Extensive experimental studies are required to fill these gaps in ion-molecule reactivity knowledge. 相似文献
Feasibility of electrokinetic (EK) process combined with Fenton-like reaction was investigated for the removal of phenanthrene in a two-dimensional cell. Sandy soil and bentonite were selected as a model soil and a filling material to inhibit the leak of electrolyte solution within the electrode reservoirs into the soil by hydraulic pressure difference, respectively. The effects of parameters including current, electroosmotic flow (EOF), electrolyte pH, and moisture content on the removal efficiency were examined under constant voltage.
At the end of operation for 21 days, the concentration of phenanthrene near the anode was lower than the other positions of soil specimen and increased gradually towards the cathode because hydrogen peroxide solution was supplied from anode to cathode region following the direction of EOF. The concentration of phenanthrene at the bottom soil was lower than that at the top soil. Because capillary attraction in the sandy soil with high porosity was too low to maintain appropriate moisture at the top of the cell, EOF moved through the bottom soil with higher moisture content. Overall removal efficiency at 140 V was 81.6%, which was higher than 68.9% at 100 V because total EOF increased by a factor of 1.5 upon increase of the voltage from 100 to 140 V. In addition, power consumptions at 100 and 140 V were 7.2 and 19.4 kWh, respectively. 相似文献
Metagranodiorite samples from the Brossasco‐Isasca Unit, Dora‐Maira Massif, western Alps, show pseudomorphous and coronitic textures where igneous minerals were partially replaced by ultra‐high pressure (UHP) metamorphic assemblages. The original magmatic paragenesis consisted of quartz, plagioclase, K‐feldspar, biotite and minor phases. During UHP metamorphism, the plagioclase (site P) was replaced by zoisite, jadeite, quartz, K‐feldspar and kyanite, and coronitic reactions developed between biotite and adjacent minerals. At the original igneous biotite–quartz contact (site A), a single corona of poorly zoned garnet is developed, whereas at the biotite–K‐feldspar (site B) and biotite–plagioclase (site C) contacts, composite coronas are formed. Integration of results from petrographic observations, calculations of mineral stoichiometry and thermodynamic calculations of mineral stability has allowed the determination of the metamorphic reactions involved and the estimation of the metamorphic conditions, which reached as high as 24 kbar and 650 °C. Accurate microanalysis by energy‐dispersive spectroscopy (EDS) and statistical analysis of the data allowed us to identify, for the first time in a natural Na‐pyroxene of metagranitoid rocks, the end‐member Ca‐Eskola. 相似文献
Procedures based on ordinary and generalized least of squares for the estimation of kinetic parameters in laboratory pyrolysis experiments are compared. When the data consist of measurements on the degree of chemical reaction through time for a number of temperatures, a single regression procedure is preferred to the two-stage regression alternative. Methods are developed for the construction of confidence intervals for calibration curves used to infer formation temperature on the basis of the unreacted fraction of source material. 相似文献
ABSTRACT A suite of garnet-wollastonite-scapolite-bearing calcsilicate granulites from the Eastern Ghats has been investigated to document the controls of mineral reactions during the metamorphic evolution of the deep continental crust. The rocks studied show heterogeneity in modal mineralogy and phase compositions in millimetre-sized domains. Textural relations, and the compositional plots of the phases, established that the clinopyroxene exerts a strong influence on the formation and composition of garnet in the complex natural system. P-T estimates using the vapour-independent equilibria involving garnet define a near isobaric cooling path from c. 850C at c. 5.5–5.2 kbar. The deduced trajectory tallies well with the terminal segment of the overall retrograde P-T path construed from the associated rocks using well-calibrated thermobarometers. The ubiquitous occurrence of wollastonite and scapolite in the main calcsilicate body suggests low aCO2 during peak metamorphic condition. Fluid compositions constrained from mineral-fluid equilibria of the garnet-bearing assemblages show domainal variations as a function of the compositions of the solid phases, e.g. garnet and clinopyroxene. A quantitative log/CO2-log/O2 diagram has been constructed to depict the stability of the different calcsilicate assemblages as functions of the compositions and the behaviour of these fugitive species. The results of the mineral-fluid equilibria and the quantitative fluid/rock ratio calculations, in conjunction with the topological constraints, imply vapour-deficient meta-morphism in the rocks studied. It is argued that fO2 during peak metamorphism was monitored by the ambient fO2. Subsequently, during retrogression, different domains evolved independently, whereas the fluid composition was controlled by the mineral-fluid equilibria. 相似文献
Aluminous reaction textures in orthoamphibole-bearing rocks from the Froland area, Bamble, south Norway, record the prograde pressure–temperature path of the high-grade Kongsbergian Orogeny (c. 1600–1500 Ma) and the low–mid amphibolite facies overprint during the Sveconorwegian Orogeny (c. 1100–1000 Ma). The rocks contain anthophyllite/gedrite, garnet, cordierite, biotite, quartz, andalusite, kyanite, Cr-rich staurolite, tourmaline, ilmenite, rutile and corundum in a variety of parageneses. The P–T path is deduced from petrographic observations, mineral chemistry and zoning, geothermometry and (N)FMASH equilibria. The results indicate the sequence of metamorphic stages outlined below. (a) An M1 phase characterized by the presence of strongly deformed andalusite, gedrite and tourmaline. (b) An M2 phase with the development of kyanite after andalusite and the growth of staurolite associated with strong Na–Al–Mg zoning in orthoamphibole, indicating an increase in pressure (4 8 kbar) and temperature (500° 650°C). (c) Pressure decrease at high P (6–7 kbar) and high T (600–700 °C) during M3a with the production of cordierite ° Corundum between kyanite, staurolite and orthoamphibole and cordierite growth between corundum and orthoamphibole. (d) Temperature increase to 740 ± 60 °C and 7 kbar; static growth of garnet (M3b) at the metamorphic climax (peak T). The heat supply necessary to explain the temperature increase between the M3a and M3b phases is correlated with synkinematic enderbitic–charnockitic and basic intrusions in the Arendal granulite facies terrain. (e) M3b metamorphic conditions were followed by an initial isobaric cooling path (early M4) and late-stage pressure decrease (late M4). Early M4 conditions of 6–7 kbar and 550–600 °C, assuming PH2O < Ptotal are indicated by a retrograde talc–kyanite–quartz assemblage in late quartz–cordierite veins. Late M4 conditions of 3–4 kbar and 420–530 °C are inferred from a kyanite–andalusite–chlorite–quartz assemblage in vein-cordierite. The M1–M3 stages are interpreted as being the result of the same metamorphic P–T path, which was caused by both tectonic and magmatic thickening. A prolonged crustal residence time is proposed for the Bamble sector before uplift during the later stages of M4 occurred. 相似文献
Selenomethionine (SeM) is an organic toxicant that is present in seleniferous environments. No kinetic data is yet available
regarding SeM reactions in coal mine environments, where selenium (Se) toxicity is a potential concern. A kinetic study was
conducted on two reclaimed coal mine soils (Typic Torriorthents) from Wyoming having sandy and clayey textures. Four levels
of SeM treatments (0, 50, 100 μM, and plant amendment from the mine vegetation) were reacted with the soils for 4, 7, 14,
28, 42, 56, and 84 days to characterize the kinetic behavior of overall SeM disappearance from soil solutions. Detection of
SeM in soil solutions at the control level (0 μM SeM) indicated occurrence of indigenous SeM in the soils. In the plant-amended
soil solutions, much greater concentrations of SeM were observed as compared with the soil-only systems. This indicated the
plant material was a more potential source of SeM than the mine soils. A time-dependent loss in solution SeM concentrations
was observed for both soils under 0, 50, 100 μM SeM treatments. For the soil-plant mixtures, the solution SeM concentration
increased initially, reached a maximum after 14 days, and then decreased thereafter. In the plant-amended soil solutions,
SeM concentrations at all time intervals were higher for the sandy as compared to the clayey soil. At 50 and 100 μM SeM treatments,
the solution pH was linearly related to the percentages of SeM disappeared from the solutions; greater percentage of SeM was
removed from solutions at comparatively lower pH levels, which was ≥90% at pH 7.7 for both soils. Solution SeM concentrations
decreased exponentially with time following first-order kinetic reactions. Under all applications (except for the control),
C0 (SeM concentration at t=0) values for the sandy soil were greater than those determined for the clayey soil, indicating higher solution SeM availability
for the former and more SeM retention by the latter at t=0. Comparison of C0 in controls (0 μM SeM addition) suggested greater indigenous SeM in the clayey soil. For both soils, C0 values under different treatments followed the order, (soil+100 μM)>(soil+50 μM)>(soil+0 μM). The specific reaction rate
constants (Kr) of SeM for both soils were similar (0.031 and 0.029 day–1 for sandy and clayey soils, respectively); low Kr values indicated that SeM loss from our reclaimed coal mine soil solutions would follow rather slow kinetics. The half-life
(t0.5) of SeM varied from 15 to 55 days depending on treatment level. The knowledge obtained from this study should contribute
in developing time-based Se reclamation strategies in coal mine environments.
Received: 18 September 1995 · Accepted: 28 December 1995 相似文献
Two types of aluminous paragneiss from the Loosdorf complex (Bohemian Massif, NE Austria) contain coarse-grained granulite assemblages and retrograde reaction textures that are investigated to constrain the post-peak history of the Gföhl unit in the southern Bohemian Massif. Both types have a peak assemblage garnet–biotite–sillimanite–plagioclase–K-feldspar–quartz–granitic melt ± kyanite ± ilmenite ± rutile, recording peak metamorphic conditions of 0.9–1.1 GPa and 780–820°C estimated by isochemical phase equilibrium modelling. The first sample type (Ysper paragneiss) developed (i) cordierite coronae around garnet and (ii) cordierite–spinel and cordierite–quartz reaction textures at former garnet–sillimanite interfaces. Calculated chemical potential relationships indicate that the textures formed in the course of a post-peak near-isothermal decompression path reaching 0.4 GPa. Texture formation follows a two-step process. Initially, cordierite coronae grow between garnet and sillimanite. As these coronae thicken, they facilitate the development of local compositional domains, leading to the formation of cordierite–spinel and cordierite–quartz symplectites. The second sample type (Pielach paragneiss) exhibits only discontinuous cordierite coronae around garnet porphyroblasts but lacks symplectites. The formation of cordierite there also indicates near-isothermal decompression to 0.4–0.5 GPa and 750–800°C. This relatively hot decompression path is explained by the contemporaneous exhumation of a large HP–UHT granulite body now underlying the Loosdorf complex. The timing of regional metamorphism in the granulites and the southern Bohemian Massif in general is well constrained and has its peak at 340 Ma. Monazite from Loosdorf paragneiss samples yield a slightly younger age of 335 Ma. Although the ages overlap within error, they are interpreted to reflect near-isothermal decompression and exhumation resulting in the formation of the observed reaction textures. 相似文献