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1.
Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al 2O 3–SiO 2 (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe 2+ content on partition coefficients ( DGrt/Melt). DGrt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius ri and valency Z in terms of three parameters: the effective radius of the site r0( Z), the strain-free partition coefficient D0( Z) for a cation with radius r0( Z), and the apparent compressibility of the garnet X-site given by its Young's modulus EX( Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r0(3+) and EX(3+) as a function of garnet composition ( X) and pressure ( P): r0(3+) [Å]=0.930XPy+0.993XGr+0.916XAlm+0.946XSpes+1.05(XAnd+XUv)−0.005(P [GPa]−3.0)(±0.005 Å) EX(3+) [GPa]=3.5×1012(1.38+r0(3+) [Å])−26.7(±30 GPa) Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa< P<5.0 GPa; 975°C< T<1640°C). DGrt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when DGrt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. DSmGrt/Melt/ DNdGrt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r0(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting DGrt/Melt for these elements as a function of P, T and X. 相似文献
2.
Pyrite and marcasite were precipitated by both slow addition of aqueous Fe 2+ and SiO 32− to an H 2S solution and by mixing aqueous Fe 2+ and Na 2S 4 solutions at 75°C. H 2S 2 or HS 2− and H 2S 4 or HS 4− were formed in the S 2O 32− and Na 2S 4 experiments, respectively. Marcasite formed at pH < pK 1 of the polysulfide species present (for H2S2, pK1 = 5.0; for H2S4, pK1 = 3.8 at 25° C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H 2S 2 and HS 2 are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures. The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H2S2 and HS2 are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS2 and S22− are strongly attracted to the positive pyrite growth sites. Masking of 1πg* electrons in the S2 group by the protons makes HS2 and H2S2 isoelectronic with AsS2− and As22−, respectively (
et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated. Marcasite occurs abundantly only for conditions below pH 5 and where H2S2 was formed near the site of deposition by either partial oxidation of aqueous H2S by O2 or by the reaction of higher oxidation state sulfur species that are reactive with H2S at the conditions of formation e.g., S2O32− but not SO42−. The temperature of formation of natural marcasite may be as high as 240°C (
and
, 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C (
, 1973;
and
, 1985). 相似文献
3.
The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH) 3, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH) 4) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: . This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10−5 kg m−2 s−1, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression: Rnet,boehmite=10-5.485{mOH-}{1-exp(ΔGr/RT)}, with Rnet in units of mol m−2 s−1. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH− concentration involving a single critical activated complex. The relationship applies over the experimental ΔGr range of 0.4–5.5 kJ mol−1 for precipitation and −0.1 to −1.9 kJ mol−1 for dissolution, and the pHm ≡ −log(mH+) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:Rnet,gibbsite=10-5.86{mOH-}{1-exp(ΔGr/RT)}, over a more limited experimental range of ΔGr (0.7–3.7 kJ mol−1) and pHm (8.2–9.7). 相似文献
4.
Landslides in the central Rif mountains (Morocco) were analyzed by multifractal analysis. Our results suggest that spatial distribution of landslides in the region is not a homogeneous fractal structure but a heterogeneous one with generalized dimensions D(1)=1.713> D(2)>…> D(12)=1.325. The value of D(12)= D(∞) is the fractal dimension of the most intensive clustering in the heterogeneous fractal set. It is worthwhile to note that we found D(0)< D(1). The analysis of areas affected by sliding from the geological map of Beni Ahmed at a scale 1:50 000 shows the power law size distribution: N( A> a)∝ a−1.57. This confirms the scale invariance of sliding and suggests that real landslides may exhibit a Self-Organized Criticality (SOC) behaviour. 相似文献
5.
The deuterium abundance of natural water of various sources has been determined by the use of a deuterium mass spectrometer. The absolute deuterium contents of the reference sample nos. 1 and 1a of the U.S. National Bureau of Standards were found to be 0·0149 and 0·0128 mole % D 2O, respectively, by the comparison of the samples with the standard samples of known deuterium content. Relative enrichment of no. la to no. 1 ( R1a− R1)/ R1×100 was 14·13 ± 0·23, which agrees perfectly to the value reported by
. The variation of deuterium contents of tap waters of Tokyo and Osaka during last 2 years were within ± 1 per cent and any seasonal regularities could not be detected. Marine waters of the West Pacific have almost the same deuterium content as those of the Pacific coast of the United States. Marine waters at various depths of the Antarctic showed relatively large variation of deuterium content (from +0·84 to −1·16 per cent on the SMOW-scale), whereas the samples of Black Current of the Pacific showed little variation. It was found that the deuterium content of spring water suggests the origin of springs in some cases. 相似文献
6.
It is widely recognised that soil slips and debris flows are triggered by short intense storms. Owing its geologic, geomorphologic and climatic settings, the Piedmont Region (NW Italy) is highly prone to the occurrence of this kind of landslides. In the last two centuries, in fact, a total of 105 severe meteoric events which triggered shallow failures occurred and, of these, 18 events took place from 1990 to 2002. A fair number of rainfall thresholds have been proposed in the literature, defined both on empirical or on physical bases. Empirical thresholds are defined collecting rainfall data for landslide meteoric events and for events without landslides, while physical thresholds are based on numerical models that consider the relation between rainfall, pore pressure and slope stability. The main objective of this paper is the identification of the empirical triggering thresholds for the Piedmont Region. Four meteoric events were selected and analysed (November 4–5, 1994; July 7–8, 1996; April 27–30, 2000; October 13–16, 2000) because they supply a wide range of variation for both rainfall parameters (duration, intensity, cumulative rainfalls) and the number of induced landslides. In the intensity–duration plot, the critical limit is described by the equation: I=19 D−0.50 (where I=rainfall intensity expressed in mm/h and D=rainfall duration expressed in hours). Such a limit is traced to envelop 90% of the points on the graph. In the NI– D diagram the triggering thresholds are given by the equations NI=0.76 D−0.33 and NI=4.62 D−0.79 (where NI=normalised intensity with respect to the annual precipitation, MAP, expressed in %, [(mm/h)/PMA]×100). In the article the different meaning of these thresholds is discussed. Finally, the diagram NI–NCR is proposed; the triggering threshold is given by the expression: NI=−0.09ln[NCR]+0.54 (where NCR is the normalised cumulative critical rainfall, [mm/PMA]×100). The application of the triggering thresholds as a fundamental element in a warning system dedicated to the safeguarding of population in landslide-prone areas is discussed. In detail an operating procedure which is presently being verified and tested in the studied area is described. 相似文献
7.
Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na +), 0.032 (K +), 0.165 (Li +), 0.292 (Ca 2+, Mg 2+), −0.139 (SO 42−), and −0.009 (NO 3−). A set of polynomial equations has been derived which can be used to calculate λ SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ SiO2(aq)−i) and the surface electrostatic field ( Zi/ re,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ SiO2(aq) in the Na---K---Ca---Mg---Cl---SO 4---HCO 3---SiO 2---H 2O system, over a large range of salt concentrations and up to temperatures of 250°C. 相似文献
8.
Carbon and nitrogen abundance and isotopic compositions, from four EH4, one EH5, five EL6 chondrites and one aubrite, were determined by using stepped pyrolysis (N only) and combustion (N and C) extractions in attempts to distinguish the components present. Carbon contents range from 0.15 to 0.70 wt%, with no systematic relationship between carbon content and meteorite group or petrologic type. Whole-rock δ 13C values range from −28.5 to −4.1 %., Most C occurs as graphite and when temperature steps above 700°C are considered, there is a difference between EH4,5 (δ 13C = −9.1 to -5.8%.) and EL6 chondrites (δ 13C = −6.7 to +4.2%.). Carbon in Bustee aubrite is isotopically lighter (δ 13C = −24%.) than in any enstatite chondrite. Nitrogen occurs as osbornite, sinoite and in isostructural substitution for oxygen in silicate lattice sites. Nitrogen abundances and isotopic compositions are more variable than C, due to the heterogenous distribution of N-bearing minerals. Three EL6's containing osbornite have higher N concentrations than other type 6 enstatite chondrites. Sinoite, where present, is depleted in 15N relative to osbornite. Nitrogen in the Bustee aubrite has a similar abundance and δ15N value to those of EL6's, again dominated by the presence of osbornite. In addition to the refractory C-and N-bearing minerals there is also organic material (largely terrestrial contamination) and evidence for at least two “exotic” components. The first is a host for Xe (HL) and is characterized by δ13C <-−47%. and δ15N ≤−73%., whereas the second is less well-defined, but is marked by δ15N = +269%. 相似文献
9.
The palaeomagnetism of basic rocks and sulphide ores has been studied in the Küre area, Pontic Ranges, Turkey. Progressive alternating-field demagnetization revealed a characteristic remanent magnetization in all investigated rock types except a dacite. The following virtual geomagnetic poles were obtained: Basalt and quartz diabase (oldest): D = 59°, I = +66°, 95 = 4.8, pole 49°N, 93°E. Diabase: D = 210°, I = −15°, 95 = 15.0, pole 47°N, 167°E. Massive sulphide ores: D = 107°, I = +63°, 95 = 8.7, pole 18°N, 80°E. Peridotite: D = 131°, I = +54°, 95 = 10.9, pole 2°S, 72°E. Amphibolitized diabase (youngest): D = 293°, I = +59°, 95 = 12.6, pole 40°S, 145°E. The longidutinal difference in pole positions between the oldest and the youngest rocks is interpreted as being due to a post-Permian counterclockwise rotation of the studied region in relation to the African continent. In addition, there are indications of local rotational movements within the Küre area. 相似文献
10.
We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10 5 Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10 −10 oxygen equivalent moles (o.e.m.) cm −2 s −1 for olivine in a basaltic melt to 1.3·10 −5 o.e.m. cm −2 s −1 for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively. The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions. 相似文献
11.
We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na 2O–CaO–MgO–Al 2O 3–SiO 2, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients ( D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations ( D0), with site radius r0, and for the site's Young's Modulus ( E). In agreement with earlier data our results show that increasing ivAl concentration in cpx is matched by increasing D, EM1, EM2 and D0 for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D0, r0 and E. We have found that D0 and r0 decrease with increasing cation charge, e.g. r0=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of EM1 and EM2 increase with cation charge as well as with increasing ivAl content. The increase in EM2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. EM1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship. 相似文献
12.
Shales and graywackes were first metamorphosed at 650°C and then partially melted at 700 and 750°C at 2, 4, 6, and 8 kilobars in the presence of 0.75 m NaCl−0.45 m KCl and 0.225 m CaCl 2−0.750 m NaCl solutions. In experiments with shales, KK+Na ratio in the decreases with increasing pressure at 650 and 700°C; however, at 750°C this ratio is equal to 0.5 at all pressures investigated. This suggests that melts at 700°C and at 2 to 8 kilobars pressure may be affected metasomatically whereas melts at 700°C and in the same pressure range will not. Melt composition produced in the shale-KClNaCl experiments is granite at 2, 4 and 6 kilobars pressure, whereas the melt compositions in the shale-CaCl 2NaCl experiments range from quartz monzonite (2–5 kilobars) to granodiorite (above 5 kilobars). Experiments with graywacke-KClNaCl produced melts of trondhjemite composition at 2, 2.5, 4, 6, and 7.5 kilobars. These results indicate that partial melting of crustal rocks such as metamorphosed shales and graywackes in the deeper parts of the crust can produce large volumes of granitic magmas ranging in composition from true granite to trondhjemite to quartz monzonite and granodiorite. 相似文献
13.
We report Sr, Nd and Pb isotopic compositions of mid-Proterozoic anorthosites and related rocks (1.45-1.65 Ga) and of younger olivine diabase dikes (1.4 Ga) from two complexes on either side of the Grenville Front in Labrador. Anorthositic or diabasic samples from the Mealy Mountains (Grenville Province) and Harp Lake (Nain-Churchill Provinces) complexes have very similar major, minor and trace element compositions, but distinctly different isotopic signatures. All Mealy Mountains samples have ISr = 0.7025−0.7033, ε Nd = +0.6 to +5.6 and Pb isotopic compositions consistent with derivation from a mantle source depleted with respect to Nd/Sm and Rb/Sr. Pb isotopic compositions for the Mealy Mountains samples are slightly more radiogenic than model mantle compositions. All Harp Lake samples have ISr = 0.7032−0.7066, ε Nd = −0.3 to −4.4 and variable, but generally unradiogenic 207Pb/ 204Pb and 206Pb/ 204Pb compared to model mantle, suggesting mixing between a mantle-derived component and a U-depleted crustal contaminant. Crustal contaminants are probably a variety of Archean high-grade quartzofeldspathic gneisses with low U/Pb ratios and include a component that must be isotopically similar to the early Archean (>3.6 Ga) Uivak gneisses of Labrador or the Amitsoq gneisses of west Greenland. This would imply that the ancient gneiss complex of coastal Labrador and Greenland is larger than indicated by present surface exposure and may extend in the subsurface as far west as the Labrador Trough. If Harp Lake and Mealy Mountains samples were subjected to the same degree of contamination, as suggested by their chemical similarities, then the Mealy contaminants must be much younger, probably early or middle Proterozoic in age. The Labrador segment of the Grenville Front, therefore, appears to coincide with the southern margin of the Archean North Atlantic craton and may represent a pre mid-Proterozoic suture. 相似文献
14.
The 2685–2752 Ma old granite-greenstone crust in the Rainy Lake area, Ontario, consists of metaigneous and metasedimentary rocks that range in composition from tholeiite to monzogranite and include anorthosite, trachyandesite, monzodiorite and high-silica rhyodacite. Major element, rare earth and other trace element data are the basis for modelling the formation of the crust by melting of large-ionlithophile element enriched and unenriched mantle, by melting of basalt at mantle to crustal levels and by melting of monzodiorite and tonalite at crustal levels. All metaigneous rocks lie on a 143Nd/144Nd vs. 147Sm/144Nd isochron with an age of 2737 ±42 Ma and an initial 143Nd/144Nd of 0.509178 ±33 (εNd = +1.9). This age is consistent with U-Pb zircon ages, which suggests the Nd isotopic system has been unaffected since the crust-forming events. The positive initial εNd's are further evidence for time-averaged depletion in Sm/Nd relative to CHUR for the Archean mantle. The similarity of the initial Nd isotopic composition for both mantle-derived and crustally-derived rocks suggests rapid recycling of crustal components, which were previously derived from depleted mantle sources. Initial 143Nd/144Nd ratios on individual rocks range from εNd = +3.3 to εNd = −0.4. Younger granitoids have lower εNd values (+1.5 to −0.1) relative to tholeiites and monzodiorites crystallized from mantle-derived melts (+3.3 to +1.0). Thus, incorporation of slightly older crust (ca. 100–200 Ma) in some of the granitoid source areas is possible. Mantle-derived rocks form an isochron of 2764 ±58 Ma that represents a minimum age for enrichment processes in the mantle sources for the Rainy Lake area. Consideration of data from the Abitibi belt suggests such enrichment processes in the mantle may have preceded crust-forming events in a wide area of the Superior Province, perhaps by as much as 50–70 Ma. 相似文献
15.
The thermal expansivities of eight sodium aluminosilicate liquids were derived from the slope of new volume data at low temperatures (713−1072 K) combined with the high temperature (1300−1835 K) volume measurements of Stein et al. (1986) on the same liquids. Melt compositions range from 47−71 wt% SiO 2, 0−31 wt% A1203, and 17−33 wt% Na 2O; the volume of albite supercooled liquid at 1092 K was also determined. The low temperature volumes were derived from measurements of the glass density of each sample at 298 K, followed by measurements of the glass thermal expansion coefficient from 298 K to the respective glass transition interval. This technique takes advantage of the fact that the volume of a glass is equal to the volume of the corresponding liquid at the limiting fictive temperature ( T′ f), and that T′ f can be approximated as the onset of the rapid rise in thermal expansion at the glass transition in a heating curve (Moynihan, 1995). No assumptions were made regarding the equivalence of enthalpy and volume relaxation through the glass transition. The propagated error on the volume of each supercooled liquid at T′ f is 0.25%. Combination of these low temperature data with the high temperature measurements of Stein et al. (1986) allowed a constant thermal expansivity of each liquid to be derived over a wide temperature interval (763−1001 degrees) with a fitted 1σ error of 0.6–4.6%; in every case, no temperature dependence to dV/ dTliq could be resolved. Calibration of a linear model equation leads to fitted values ± 1σ (units of cm 3/mole) for
(26.91 ± .04),
(37.49 ± .12),
(26.48 ± .06) at 1373 K, and
(7.64 ± .08 × 10 -3 cm 3/mole-K). The results indicate that neither Si02 nor Al 2O 3 contribute to the thermal expansivity of the liquids, and that dV/ dTliq is independent of temperature between 713–1835 K over a wide range of liquid composition. Calculated volumes based on this model recover both low and high temperature measurements with a standard deviation <0.25%, whereas values of dV/ dTliq can be predicted within 5.6%. 相似文献
16.
As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m 2 g −1). The dissolution rate law of sludge obtained is r=10−6.1(±0.3) [O2(aq)]0.41(±0.04) aH+0.09(±0.06) gsludge m−2 s−1 (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10−7.8(±0.3) [O2(aq)]0.50(±0.04) aH+0.10(±0.08) mol m−2 s−1 (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively. A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O2 onto pyrite surface is proposed. 相似文献
17.
We investigate the use of a ductile material with temperature-sensitive viscosity for thermomechanical modelling of the lithosphere. First, we consider the scaling of mechanical and thermal properties. For a normal field of gravity, the balance of stresses and body forces sets the stress scale, in proportion to the linear dimensions and the densities. The equation of thermal conduction sets the time scale. The activation enthalpy for creep sets the temperature scale; but the thermal expansivity provides an additional constraint on this temperature scale. Gum rosin appears to be a suitable material for lithospheric modelling. We have measured its flow properties, at various temperatures, in a specially designed rotary viscometer with unusually low machine friction. The rosin is almost Newtonian. Strain rate depends upon stress to the power n, where 1.0 <n < 1.14. The viscosity varies over 5 orders of magnitude, from about 102 Pa s at 80°C, to about 107 Pa s at 40°C. The activation enthalphy is thus about 250 kJ/mol. Measured with a needle probe, the thermal conductivity is 0.113 ± 0.001 W m−1K−1; the thermal diffusivity, (6±3) ×10−7 m2 s−1. Calculated from X-ray profiles, the thermal expansivity is about 3 × 10−4 K−1. These thermal and mechanical properties make gum rosin suitable for thermomechanical models, where linear dimensions scale down by a factor of 106; time, by 1011; viscosity, by 1017; and temperature change, by 101. 相似文献
18.
The process of shape-transformation of quartz inclusions from polyhedral to spherical grains in albite single crystals during metamorphism is mainly controlled by the grain boundary diffusion of oxygen along the quartz/albite interface to reduce the interfacial free energy. The rate of the process, which is represented by the growth rate of the curvature of the edge surface of the grain, depends significantly on temperature and on the grain size of the quartz inclusion. The relations between temperature, T, the time, tr, and the critical radius, Rc, which is equal to the radius of maximum spherical grains, are given by log Rc = −0.11 Eb/ RT + 0.25log tr + C, in which Eb is the activation energy of the grain boundary diffusion of oxygen along the quartz/albite interface and C is a material constant. The mean critical radius of spherical quartz inclusions in albite is 5 μm for the upper chlorite zone and garnet zone, 10 μm for the lower biotite zone, and 20 μm for the upper biotite zone in the Sambagawa metamorphic terrain. The mean values of the critical radii of spherical quartz inclusions in oligoclase of the Ryoke metamorphic rocks is about 5 μm for the chlorite zone and about 10–20 μm for the sillimanite zone. Assuming temperatures of about 350°C for the upper chlorite and garnet zones, 400°C for the lower biotite zone, 550°C for the upper biotite zone, and 700°C for the sillimanite zone, the activation energy for the grain boundary diffusion of oxygen along the quartz/plagioclase interfase is estimated to be about 30 kcal/mol. 相似文献
19.
In low-temperature aqueous solutions (< 100°C, pH 2–4.5), chalcopyrite (CuFeS 2) does not form through direct precipitation from solution. The pathway is exclusively via precursor iron sulphides and dissolved Cu salts. The reaction of dissolved Cu (II) salts with natural hexagonal pyrrhotite (Fe 0.9S) is diffusion controlled. The initial stage has an apparent activation energy of 11.4 ± 1.8 kJ mol −1 and the rate (in units of mol dm −3s −1 cm −2) is independent of the solid reactant surface area. The reaction proceeds through a series of metastable Cu-Fe-sulphide intermediaries. These phases form a series of ephemeral layers penetrating into the pyrrhotite surface. The first phase formed has the stoichiometry Cu 0.1Fe 0.9S. No Fe is released into the solution during its formation and this, together with the extremely low apparent activation energy and the stoichiometry, suggest that it is formed by stuffing of electron holes in the pyrrhotite structure with Cu ions. The transformation from the hexagonal close-packed arrangement of the pyrrhotite structure to the essentially cubic packing in chalcopyrite proceeds through a series of intermediaries, approximating in composition to members of the cubanite group. The rate of formation of these phases is controlled by the coupled diffusion of Fe (II), Fe (III), Cu (I) and Cu (II) species through the surface reaction zone, although the process as a whole can be approximated by steady-state diffusion of total Cu into a semi-infinite medium. Experiments with metastable precursor iron monosulphide phases, including amorphous FeS and synthetic mackinawite indicate similar reaction pathways. The results suggest that chalcopyrite formation in low-temperature natural systems may be significantly constrained by kinetic factors. Chalcopyrite is, at least, a diagenetic mineral since its formation requires the prior formation of iron sulphides. However, at ambient temperatures its formation is probably limited to very early diagenesis. 相似文献
20.
Variation of Nernst partition coefficients ( D) between olivine and silicate melts cannot be neglected when modeling partial melting and fractional crystallization. Published natural and experimental olivine/liquidD data were examined for covariation with pressure, temperature, olivine forsterite content, and melt SiO 2, H 2O, MgO and MgO/MgO + FeO total. Values of olivine/liquidD generally increase with decreasing temperature and melt MgO content, and with increasing melt SiO 2 content, but generally show poor correlations with other variables. Multi-element olivine/liquidD profiles calculated from regressions of D REE–Sc–Y vs. melt MgO content are compared to results of the Lattice Strain Model to link melt MgO and: D0 (the strain compensated partition coefficient), EM3+ (Young's Modulus), and r0 (the size of the M site). Ln D0 varies linearly with Ln MgO in the melt; EM3+ varies linearly with melt MgO, with a dog-leg at ca. 1.5% MgO; and r0 remains constant at 0.807 Å. These equations are then used to calculate olivine/liquidD for these elements using the Lattice Strain Model. These empirical parameterizations of olivine/liquidD variations yield results comparable to experimental or natural partitioning data, and can easily be integrated into existing trace element modeling algorithms. The olivine/liquidD data suggest that basaltic melts in equilibrium with pure olivine may acquire small negative Ta–Hf–Zr–Ti anomalies, but that negative Nb anomalies are unlikely to develop. Misfits between results of the Lattice Strain Model and most light rare earth and large ion lithophile partitioning data suggest that kinetic effects may limit the lower value of D for extremely incompatible elements in natural situations characterized by high cooling/crystallization rates. 相似文献
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