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1.
A synthetic Topopah Spring Tuff water representative of one type of pore water at Yucca Mountain, NV was evaporated at 95°C
in a series of experiments to determine the geochemical controls for brines that may form on, and possibly impact upon the
long-term integrity of waste containers and drip shields at the designated high-level, nuclear-waste repository. Solution
chemistry, condensed vapor chemistry, and precipitate mineralogy were used to identify important chemical divides and to validate
geochemical calculations of evaporating water chemistry using a high temperature Pitzer thermodynamic database. The water
evolved toward a complex "sulfate type" brine that contained about 45 mol % Na, 40 mol % Cl, 9 mol % NO3, 5 mol % K, and less than 1 mol % each of SO4, Ca, Mg, ∑CO2(aq), F, and Si. All measured ions in the condensed vapor phase were below detection limits. The mineral precipitates identified
were halite, anhydrite, bassanite, niter, and nitratine. Trends in the solution composition and identification of CaSO4 solids suggest that fluorite, carbonate, sulfate, and magnesium-silicate precipitation control the aqueous solution composition
of sulfate type waters by removing fluoride, calcium, and magnesium during the early stages of evaporation. In most cases,
the high temperature Pitzer database, used by EQ3/6 geochemical code, sufficiently predicts water composition and mineral
precipitation during evaporation. Predicted solution compositions are generally within a factor of 2 of the experimental values.
The model predicts that sepiolite, bassanite, amorphous silica, calcite, halite, and brucite are the solubility controlling
mineral phases. 相似文献
2.
The Warburton Basin of central Australia has experienced a complex tectonic and fluid-flow history, resulting in the formation of various authigenic minerals. Geochemical and geochronological analyses were undertaken on vein carbonates from core samples of clastic sediments. Results were then integrated with zircon U–Pb dating and uraninite U–Th–total Pb dating from the underlying granite. Stable and radiogenic isotopes (δ18O, Sr and εNd), as well as trace element data of carbonate veins indicate that >200 °C basinal fluids of evolved meteoric origin circulated through the Warburton Basin. Almost coincidental ages of these carbonates (Sm–Nd; 432 ± 12 Ma) with primary zircon (421 ± 3.8 Ma) and uraninite (407 ± 16 Ma) ages from the granitic intrusion point towards a substantial period of active tectonism and an elevated thermal regime during the mid Silurian. We hypothesise that such a thermal regime may have resulted from extensional tectonism and concomitant magmatic activity following regional orogenesis. This study shows that the combined application of geochemical and geochronological analyses of both primary and secondary species may constrain the timing of tectonomagmatic events and associated fluid flow in intraplate sedimentary basins. Furthermore, this work suggests that the Sm–Nd-isotopic system is surprisingly robust and can record geologically meaningful age data from hydrothermal mineral species. 相似文献
3.
The Chengchao and Jinshandian deposits in the southeast Hubei Province are the two largest skarn Fe deposits in the Middle–Lower Yangtze River Valley metallogenic belt (MLYRVMB), China. They are characterized by NW-striking orebodies that are developed along the contacts between the Late Mesozoic granitoid and Triassic carbonate and clastic rocks. New sensitive high-resolution ion microprobe and laser ablation inductively coupled plasma mass spectrometry zircon U–Pb dating of the mineralization-related quartz diorite and granite at Chengchao yield ages of 129 ± 2 and 127 ± 2 Ma, respectively, and those at Jinshandian of 127 ± 2 and 133 ± 1 Ma, respectively. These results are interpreted as the crystallization age of these intrusions. Hydrothermal phlogopite samples from the skarn ores at Chengchao and Jinshandian have the plateau 40Ar–39Ar ages of 132.6 ± 1.4 and 131.6 ± 1.2 Ma, respectively. These results confirm that both intrusions and associated skarn Fe mineralization were formed contemporaneously in the middle Early Cretaceous time. New zircon U–Pb and phlogopite 40Ar–39Ar ages in this study, when combined with available precise geochronological data, demonstrate that there were two discontinuous igneous events, corresponding to two episodes of skarn Fe-bearing mineralization in the southeast Hubei Province: (1) 140–136 Ma diorites and quartz diorites and 141–137 Ma skarn Cu–Fe or Fe–Cu deposits and (2) 133–127 Ma quartz diorites and granites and 133–132 Ma skarn Fe deposits. This scenario is similar to that proposed for the entire MLYRVMB. The intrusions related to skarn Fe deposits show obviously petrological and geochemical differences from those related to skarn Cu–Fe or Fe–Cu deposits. The former are quartz diorite and diorite in petrology and have similar adakitic geochemical signatures and in equilibrium with a garnet-rich residue, whereas the latter are petrologically granite and quartz diorite that are distinguishable from adakitic rocks and in equilibrium with a plagioclase residue. These features indicated that two episodes of magmatism and the formation of skarn Fe-bearing deposits in the southeast Hubei Province, MLYRVMB, might be associated lithosphere thinning induced by asthenosphere upwelling during the Late Mesozoic. 相似文献
4.
The 2.7–3 Ma Ertsberg East Skarn System (Indonesia), adjacent to the giant Grasberg Porphyry Copper deposit, is part of the world’s largest system of Cu–Au skarn deposits. Published fluid inclusion and stable isotope data show that it formed through the flux of magma-derived fluid through contact metamorphosed carbonate rock sequences at temperatures well above 600° C and pressures of less than 50 MPa. Under these conditions, the fluid has very low density and the properties of a gas. Combining a range of micro-analytical techniques, high-resolution QEMSCAN mineral mapping and computer-assisted X-ray micro-tomography, an array of coupled gas–solid reactions may be identified that controlled reactive mass transfer through the ~ 1 km3 hydrothermal skarn system. Vacancy-driven mineral chemisorption reactions are identified as a new type of reactive transport process for high-temperature skarn alteration. These gas–solid reactions are maintained by the interaction of unsatisfied bonds on mineral surfaces and dipolar gas-phase reactants such as SO2 and HCl that are continuously supplied through open fractures and intergranular diffusion. Principal reactions are (a) incongruent dissolution of almandine-grossular to andradite and anorthite (an alteration mineral not previously recognized at Ertsberg), and (b) sulfation of anorthite to anhydrite. These sulfation reactions also generate reduced sulfur with consequent co-deposition of metal sulfides. Diopside undergoes similar reactions with deposition of Fe-enriched pyroxene in crypto-veins and vein selvedges. The loss of calcium from contact metamorphic garnet to form vein anhydrite necessarily results in Fe-enrichment of wallrock, and does not require Fe-addition from a vein fluid as is commonly assumed. 相似文献
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Phase equilibria in the system CaO–MgO–SiO2–CO2–H2O–NaCl are calculated to illustrate phase relations in metacarbonates over a wide-range of P–T–X[H2O–CO2–NaCl] conditions. Calculations are performed using the equation of state of Duan et al. (Geochim Cosmochim Acta 59:2869–2882, 1995) for H2O–CO2–NaCl fluids and the internally consistent data set of Gottschalk (Eur J Mineral 9:175–223, 1997) for thermodynamic properties of solids. Results are presented in isothermal-isobarical plots showing stable mineral assemblages as a function of fluid composition. It is shown that in contact-metamorphic P–T regimes the presence of very small concentrations of NaCl in the fluid causes almost all decarbonation reactions to proceed within the two fluid solvus of the H2O–CO2–NaCl system. Substantial flow of magma-derived fluids into marbles has been documented for many contact aureoles by shifts in stable isotope geochemistry of the host rocks and by the progress of volatile-producing mineral reactions controlled by fluid compositions. Time-integrated fluid fluxes have been estimated by combining fluid advection/dispersion models with the spatial arrangement of mineral reactions and isotopic resetting. All existing models assume that minerals react in the presence of a single phase H2O–CO2 fluid and do not allow for the effect that fluid immiscibility has on the flow patterns. It is shown that fluids emanating from calc-alkaline melts that crystallize at shallow depths are brines. Their salinity may vary depending mainly on pressure and fraction of crystallized melt. Infiltration-driven decarbonation reactions in the host rocks inevitably proceed at the boundaries of the two fluid solvus where the produced CO2 is immiscible and may separate from the brine as a low salinity, low density H2O–CO2 fluid. Most parameters of fluid–rock interaction in contact aureoles that are derived from progress of mineral reactions and stable isotope resetting are probably incorrect because fluid phase separation is disregarded. 相似文献
7.
V. M. Ryzhkov V. N. Anfilogov I. A. Blinov A. A. Krasnobaev P. M. Valizer 《Doklady Earth Sciences》2016,469(2):824-827
The results of study of phase equilibria in the MgO–SiO2–ZrO2 system at 1450–1550°C are reported. The studied system contains two eutectic points and six fields: (I) MgSiO3 + SiO2; (II) MgSiO3 + ZrO2; (III) ZrSiO4 + SiO2; (IV) MgSiO3 + Mg2SiO4; (V) ZrO2 + MgO; (VI) ZrSiO4 + ZrO2. The presence of fields (II) and (III) on the diagram shows that zircon in equilibrium with olivine and pyroxene crystallizes at very low concentrations of ZrO2 in the system. This provides a solution for one of the most important problems in zirconology of dunites: the probability of the formation and preservation of zircon in the course of the formation and evolution of dunite. 相似文献
8.
The phase state of the fluid in the H2O–KF ± KCl ± NaF system is studied in the presence of quartz for an experimental assay of the mutual influence of various salts of the fluid-forming mixture on heterogeneous fluid equilibria. The fluid inclusions were synthesized in quartz by the fracture healing method from solutions with KF + KCl and KF + NaF mixtures at 1 or 2 kbar and 700, 750, or 800°C. The results of the fluid inclusion study indicate a heterogeneous state of the fluid and variation in the fluid composition during experiments as a result of its interaction with quartz. The increase in temperature and pressure, as well as variation in the proportions of the salt contents in the fluid-forming mixture, changed the course of chemical reactions. After all the experiments, a glassy phase was observed in some types of inclusions. It is known that aqueous KF or KCl solutions, the solubility of which increases during heating, are characterized by phase equilibria of systems of the first type (Valyashko, 1990), when liquid and vapor are equilibrated for a heterogeneous state of the fluid. In this case, some inclusions should homogenize to vapor. However, no similar inclusions were observed in contrast to denser fluid phases (liquids), which are typical of the upper heterogeneous area of systems of the second (P–Q) type. Some inclusions host solid phases, the solubility of which decreases as the temperature increases. The results of experiments in the presence of KF + NaF solutions showed that the amount of inclusions of heterogeneous entrapment increases at higher temperatures simultaneously with a decrease in the H2O content of the glassy phase. 相似文献
9.
This paper reports experimental data on columbite solubility in model water-saturated Li- and F-rich silicic melts with different
contents of alumina and alkalis. It was found that the columbite solubility is strongly affected by melt composition and is
maximal in peralkaline melt. The maximum contents of Ta and Nb in subaluminous and peraluminous melts at the contact with
columbite are lower by at least an order of magnitude. The peralkaline melt is relatively enriched in Nb, and the peraluminous
melt is enriched in Ta. The temperature dependence of solubility is positive but less pronounced than the effect of melt composition.
It is most distinct in the subaluminous melts. The Nb/Ta ratio of melt usually decreases with decreasing temperature. The
effect of pressure is relatively small. It was shown that columbite cannot crystallize on the liquidus of both peralkaline
and peraluminous magmas. Perhaps, columbite crystallization from a melt is possible only at final near-solidus stages at the
high degrees of crystallization of strongly evolved low-temperature melts. 相似文献
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A new 190Pt–4He method for dating isoferroplatinum has been developed at the Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences. Here we publish the first results of dating of isoferroplatinum from the main mineralogical and geochemical types of PGE mineralization in dunite. The obtained 190Pt–4He age of isoferroplatinum is 129 ± 6 Ma. The gained 190Pt–4He age of isoferroplatinum specimens of different genesis (magmatic, fluid–metamorphogenic, and metasomatic) from the Kondyor Massif indicates that the PGM mineralization took place synchronously and successively with evolution of primarily picrite, followed by subalkaline and alkaline melts of the Mesozoic tectonic–magmatic activation of the Aldan Shield. 相似文献
14.
Verónica Oliveros Dania Tristá-Aguilera Gilbert Féraud Diego Morata Luis Aguirre Shoji Kojima Fernando Ferraris 《Mineralium Deposita》2008,43(1):61-78
The Michilla mining district comprises one of the most important stratabound and breccia-style copper deposits of the Coastal
Cordillera of northern Chile, hosted by the Middle Jurassic volcanic rocks of the La Negra Formation. 40Ar/39Ar analyses carried out on igneous and alteration minerals from volcanic and plutonic rocks in the district allow a chronological
sequence of several magmatic and alteration events of the district to be established. The first event was the extrusion of
a thick lava series of the La Negra Formation, dated at 159.9 ± 1.0 Ma (2σ) from the upper part of the series. A contemporaneous intrusion is dated at 159.6 ± 1.1 Ma, and later intrusive events are
dated at 145.5 ± 2.8 and 137.4 ± 1.1 Ma, respectively. Analyzed alteration minerals such as adularia, sericite, and actinolite
apparently give valid 40Ar/39Ar plateau and miniplateau ages. They indicate the occurrence of several alteration events at ca. 160–163, 154–157, 143–148,
and 135–137 Ma. The first alteration event, being partly contemporaneous with volcanic and plutonic rocks, was probably produced
in a high thermal gradient environment. The later events may be related either to a regional low-grade hydrothermal alteration/metamorphism
process or to plutonic intrusions. The Cu mineralization of the Michilla district is robustly bracketed between 163.6 ± 1.9
and 137.4 ± 1.1 Ma, corresponding to dating of actinolite coexisting with early-stage chalcocite and a postmineralization
barren dyke, respectively. More precisely, the association of small intrusives (a dated stock from the Michilla district)
with Cu mineralization in the region strongly suggests that the main Michilla ore deposit is related to a magmatic/hydrothermal
event that occurred between 157.4 ± 3.6 and 163.5 ± 1.9 Ma, contemporaneous or shortly after the extrusion of the volcanic
sequence. This age is in agreement with the Re–Os age of 159 ± 16 Ma obtained from the mineralization itself (Tristá-Aguilera
et al., Miner Depos, 41:99–105,2006). 相似文献
15.
Massimo Chiaradia Jean Vallance Lluis Fontboté Holly Stein Urs Schaltegger Joshua Coder Jeremy Richards Mike Villeneuve Ian Gendall 《Mineralium Deposita》2009,44(4):371-387
New U–Pb, Re–Os, and 40Ar/39Ar dates are presented for magmatic and hydrothermal mineral phases in skarn- and porphyry-related ores from the Nambija and
Pangui districts of the Subandean zone, southeastern Ecuador. Nambija has been one of the main gold-producing centers of Ecuador
since the 1980s due to exceptionally high-grade ores (average 15 g/t, but frequently up to 300 g/t Au). Pangui is a recently
discovered porphyry Cu–Mo district. The geology of the Subandean zone in southeastern Ecuador is dominated by the I-type,
subduction-related, Jurassic Zamora batholith, which intrudes Triassic volcanosedimentary rocks. The Zamora batholith is in
turn cut by porphyritic stocks, which are commonly associated with skarn formation and/or porphyry-style mineralization. High
precision U–Pb and Re–Os ages for porphyritic stocks (U–Pb, zircon), associated prograde skarn (U–Pb, hydrothermal titanite),
and retrograde stage skarn (Re–Os, molybdenite from veins postdating gold deposition) of the Nambija district are all indistinguishable
from each other within error (145 Ma) and indicate a Late Jurassic age for the gold mineralization. Previously, gold mineralization
at Nambija was considered to be Early Tertiary based on K–Ar ages obtained on various hydrothermal minerals. The new Jurassic
age for the Nambija district is slightly younger than the 40Ar/39Ar and Re–Os ages for magmatic–hydrothermal minerals from the Pangui district, which range between 157 and 152 Ma. Mineralization
at Nambija and Pangui is associated with porphyritic stocks that represent the last known episodes of a long-lived Jurassic
arc magmatism (∼190 to 145 Ma). A Jurassic age for mineralization at Nambija and Pangui suggests that the Northern Andean
Jurassic metallogenic belt, which starts in Colombia at 3° N, extends down to 5° S in Ecuador. It also adds a new mineralization
style (Au-skarn) to the metal endowment of this belt.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
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Shi-Hua Sang Rui-Zhi Cui Xue-Ping Zhang Kai-Jie Zhang 《Geochemistry International》2017,55(12):1131-1139
According to the compositions of the underground brine resources in the west of Sichuan Basin, solubilities of the ternary systems NaBr–Na2SO4–H2O and KBr–K2SO4–H2O were investigated by isothermal method at 348 K. The equilibrium solid phases, solubilities of salts, and densities of the solutions were determined. On the basis of the experimental data, the phase diagrams and the density-composition diagrams were plotted. In the two ternary systems, the phase diagrams consist of two univariant curves, one invariant point and two crystallization fields. Neither solid solution nor double salts were found. The equilibrium solid phases in the ternary system NaBr–Na2SO4–H2O are NaBr and Na2SO4, and those in the ternary system KBr–K2SO4–H2O are KBr and K2SO4. Using the solubilities data of the two ternary subsystems at 348 K, mixing ion-interaction parameters of Pitzer’s equation θxxx, Ψxxx and Ψxxx were fitted by multiple linear regression method. Based on the chemical model of Pitzer’s electrolyte solution theory, the solubilities of phase equilibria in the two ternary systems NaBr–Na2SO4–H2O and KBr–K2SO4–H2O were calculated with corresponding parameters. The calculation diagrams were plotted. The results showed that the calculated values have a good agreement with experimental data. 相似文献
18.
Pia Söderlund Tobias Hermansson Laurence M. Page Michael B. Stephens 《International Journal of Earth Sciences》2009,98(8):1835-1851
In order to characterize the post-Svecofennian tectonothermal evolution of the Fennoscandian Shield, 40Ar–39Ar biotite and some 40Ar–39Ar muscovite geochronological data are reported from a total of 30 surface outcrop and 1,000 m long borehole samples at Forsmark,
central Sweden. The 13 surface samples were collected across 3 branches of a major WNW to NW trending system of deformation
zones, whereas the boreholes were drilled within a tectonic lens, in between two of these zones. The 40Ar–39Ar biotite ages indicate that the present erosion surface, in central Sweden, cooled below c. 300°C at 1.73–1.66 Ga, and that
the rocks could have accommodated strain in a brittle manner between 1.8 and 1.7 Ga. The variation in surface ages is suggested
to be due to fault along the large WNW to NW trending deformation zones, following the establishment of a sub-Cambrian peneplain.
The minor variation of ages within a single crustal block may be due to disturbance along ENE to NNE trending fracture zones.
Possible cooling paths, derived from 40Ar–39Ar hornblende, muscovite and biotite ages, were calculated for the time interval from 1.80 to 1.67 Ga, when the area cooled
from c. 500 to 300°C. Cooling rates of 1.9–4°C/m.y. have been attained. Between 1.68 and 1.64 Ga, uplift rates of c. 22 m/m.y.
were calculated from borehole 40Ar–39Ar biotite data. Tectonothermal histories, inferred from the combined cooling and uplift rates, are related to simple cooling
after the Svecofennian orogeny, to crustal movement in response to far-field effects of c. 1.7 Ga orogenic activities further
to the west or to a combination of these possibilities. 相似文献
19.
The solubility of chromium in chlorite as a function of pressure, temperature, and bulk composition was investigated in the system Cr2O3–MgO–Al2O3–SiO2–H2O, and its effect on phase relations evaluated. Three different compositions with X Cr = Cr/(Cr + Al) = 0.075, 0.25, and 0.5 respectively, were investigated at 1.5–6.5 GPa, 650–900 °C. Cr-chlorite only occurs in the bulk composition with X Cr = 0.075; otherwise, spinel and garnet are the major aluminous phases. In the experiments, Cr-chlorite coexists with enstatite up to 3.5 GPa, 800–850 °C, and with forsterite, pyrope, and spinel at higher pressure. At P > 5 GPa other hydrates occur: a Cr-bearing phase-HAPY (Mg2.2Al1.5Cr0.1Si1.1O6(OH)2) is stable in assemblage with pyrope, forsterite, and spinel; Mg-sursassite coexists at 6.0 GPa, 650 °C with forsterite and spinel and a new Cr-bearing phase, named 11.5 Å phase (Mg:Al:Si = 6.3:1.2:2.4) after the first diffraction peak observed in high-resolution X-ray diffraction pattern. Cr affects the stability of chlorite by shifting its breakdown reactions toward higher temperature, but Cr solubility at high pressure is reduced compared with the solubility observed in low-pressure occurrences in hydrothermal environments. Chromium partitions generally according to \(X_{\text{Cr}}^{\text{spinel}}\) ? \(X_{\text{Cr}}^{\text{opx}}\) > \(X_{\text{Cr}}^{\text{chlorite}}\) ≥ \(X_{\text{Cr}}^{\text{HAPY}}\) > \(X_{\text{Cr}}^{\text{garnet}}\). At 5 GPa, 750 °C (bulk with X Cr = 0.075) equilibrium values are \(X_{\text{Cr}}^{\text{spinel}}\) = 0.27, \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.08, \(X_{\text{Cr}}^{\text{garnet}}\) = 0.05; at 5.4 GPa, 720 °C \(X_{\text{Cr}}^{\text{spinel}}\) = 0.33, \(X_{\text{Cr}}^{\text{HAPY}}\) = 0.06, and \(X_{\text{Cr}}^{\text{garnet}}\) = 0.04; and at 3.5 GPa, 850 °C \(X_{\text{Cr}}^{\text{opx}}\) = 0.12 and \(X_{\text{Cr}}^{\text{chlorite}}\) = 0.07. Results on Cr–Al partitioning between spinel and garnet suggest that at low temperature the spinel- to garnet-peridotite transition has a negative slope of 0.5 GPa/100 °C. The formation of phase-HAPY, in assemblage with garnet and spinel, at pressures above chlorite breakdown, provides a viable mechanism to promote H2O transport in metasomatized ultramafic mélanges of subduction channels. 相似文献
20.
Peng Lu Qi Fu William E. SeyfriedJr Anne Hereford Chen Zhu 《Environmental Earth Sciences》2011,62(1):101-118
The injection of CO2 into deep saline aquifers is being considered as an option for greenhouse gas mitigation. However, the response of an aquifer
to the injected CO2 is largely unknown. Experiments involving the reaction of Navajo Sandstone with acidic brine were conducted at 200°C and
25 or 30 MPa to evaluate the extent of fluid–rock interactions. The first experiment examined sandstone interaction with CO2-impregnated brine; the second experiment examined sandstone dissolution in CO2-free acidic brine; the third one is carried out in a mixed-flow reactor and designed to measure sandstone dissolution rates
based on time-series Si concentrations. The solution chemistry data indicate that the SiO2(aq) increases gradually and pH increases slowly with reaction progress. Silicate minerals in the sandstone display textures
(dissolution features, secondary mineralization), indicating that these phases are reacting strongly with the fluid. Dissolution
of feldspars and conversion of smectite to illite are likely to be the two reactions that contribute to the release of SiO2(aq). The product minerals present at the end of the experiments are illite, illite/smectite, allophane, and carbonate minerals
(for the CO2-charged system). Dissolved CO2 is likely to acidify the brine and to provide a source of carbon for the precipitation of carbonate minerals. Mineral trapping
through the precipitation of carbonate minerals is favored thermodynamically and was observed in the experiments. The chemical
reactions likely increase the bulk porosity of the sandstone due to dissolution of silicate minerals. However, allophane and
illite/smectite fill voids in sandstone grains. There is no evidence for the removal of clay coatings due to chemical reactions.
It is uncertain whether the mechanical forces near an injection well would mobilize the smectite and allophane and clog pore
throats. Trace amounts of metals, including Cu, Zn, and Ba, were mobilized. 相似文献