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1.
Considerable advances in our understanding of physicochemical properties of geological fluids and their roles in many geological processes have been achieved by the use of synthetic fluid inclusions. We have developed a new method to synthesize fluid inclusions containing organic and inorganic material in fused silica capillary tubing. We have used both round (0.3 mm OD and 0.05 or 0.1 mm ID) and square cross-section tubing (0.3 × 0.3 mm with 0.05 × 0.05 mm or 0.1 × 0.1 mm cavities). For microthermometric measurements in a USGS-type heating-cooling stage, sample capsules must be less than 25 mm in length. The square-sectioned capsules have the advantage of providing images without optical distortion. However, the maximum internal pressure (P; about 100 MPa at 22 °C) and temperature (T; about 500 °C) maintained by the square-sectioned capsules are less than those held by the round-sectioned capsules (about 300 MPa at room T, and T up to 650 °C).The fused silica capsules can be applied to a wide range of problems of interest in fluid inclusion and hydrothermal research, such as creating standards for the calibration of thermocouples in heating-cooling stages and frequency shifts in Raman spectrometers. The fused silica capsules can also be used as containers for hydrothermal reactions, especially for organic samples, including individual hydrocarbons, crude oils, and gases, such as cracking of C18H38 between 350 and 400 °C, isotopic exchanges between C18H38 and D2O and between C19D40 and H2O at similar temperatures. Results of these types of studies provide information on the kinetics of oil cracking and the changes of oil composition under thermal stress.When compared with synthesis of fluid inclusions formed by healing fractures in quartz or other minerals or by overgrowth of quartz at elevated P-T conditions, the new fused-silica method has the following advantages: (1) it is simple; (2) fluid inclusions without the presence of water can be formed; (3) synthesized inclusions are large and uniform, and they are able to tolerate high internal P; (4) it is suitable for the study of organic material; and (5) redox control is possible due to high permeability of the fused silica to hydrogen.  相似文献   

2.
The solubilities of the assemblages albite + paragonite + quartz and jadeite + paragonite + quartz in H2O were determined at 500 and 600 °C, 1.0-2.25 GPa, using hydrothermal piston-cylinder methods. The three minerals are isobarically and isothermally invariant in the presence of H2O, so fluid composition is uniquely determined at each pressure and temperature. A phase-bracketing approach was used to achieve accurate solubility determinations. Albite + quartz and jadeite + quartz dissolve incongruently in H2O, yielding residual paragonite which could not be retrieved and weighed. Solution composition fixed by the three-mineral assemblage at a given pressure and temperature was therefore bracketed by adding NaSi3O6.5 glass in successive experiments, until no paragonite was observed in run products. Solubilities derived from experiments bounding the appearance of paragonite thus constrain the equilibrium fluid composition. Results indicate that, at a given pressure, Na, Al, and Si concentrations are higher at 600 °C than at 500 °C. At both 500 and 600 °C, solubilities of all three elements increase with pressure in the albite stability field, to a maximum at the jadeite-albite-quartz equilibrium. In the jadeite stability field, element concentrations decline with continued pressure increase. At the solubility maximum, Na, Al, and Si concentrations are, respectively, 0.16, 0.05, and 0.48 molal at 500 °C, and 0.45, 0.27, and 1.56 molal at 600 °C. Bulk solubilities are 3.3 and 10.3 wt% oxides, respectively. Observed element concentrations are everywhere greater than those predicted from extrapolated thermodynamic data for simple ions, monomers, ion pairs, and the silica dimer. The measurements therefore require the presence of additional, polymerized Na-Al-Si-bearing species in the solutions. The excess solubility is >50% at all conditions, indicating that polymeric structures are the predominant solutes in the P-T region studied. The solubility patterns likely arise from combination of the large solid volume change associated with the albite-jadeite-quartz equilibrium and the rise in Na-Al-Si polymerization with approach to the hydrothermal melting curves of albite + quartz and jadeite + quartz. Our results indicate that polymerization of Na-Al-Si solutes is a fundamental aspect of fluid-rock interaction at high pressure. In addition, the data suggest that high-pressure metamorphic isograds can impose unexpected controls on metasomatic mass transfer, that significant metasomatic mass transfer prior to melting should be considered in migmatitic terranes, and that polymeric complexes may be an important transport agent in subduction zones.  相似文献   

3.
The isotopic composition of carbon and oxygen in a calcite precipitating CO2-H2O-CaCO3 solution is preserved in the calcite precipitated. For the interpretation of isotopic proxies from stalagmites knowledge of the evolution of δ13C and δ18O in the solution during precipitation is required. A system of differential equations is presented from which this evolution can be derived. Both, irreversible loss of carbon and oxygen from the solution with precipitation time τ and exchange of oxygen in the carbonates with the oxygen in the water with exchange time T are considered. For carbon, where no exchange is active, a modified equation of Rayleigh-distillation is found, which takes into account that precipitation stops at ceq, the saturation concentration of DIC with respect to calcite, and that ceq as well as the precipitation time τ is slightly different for the heavy and the light isotope. This, however, requires introducing a new parameter γ = (Aeq/Beq)/(A0/B0), which has to be determined experimentally. (Aeq/Beq) is the isotopic ratio for the heavy (A) and the light isotope (B) at both chemical and isotopic equilibrium and (A0/B0) is the initial isotopic ratio of the solution. In the case of oxygen, where exchange is present, the isotopic shifts are reduced with increasing values of the precipitation time τ. For τ ? T the solution stays in isotopic equilibrium with the oxygen in the water during the entire time in which precipitation is active. The isotopic ratios in a calcite precipitating solution R(t)/R0 = (1 + δ(t)/1000) for carbon are plotted versus those of oxygen. R0 is the isotopic ratio at time t = 0, when precipitation starts and δ(t) the isotopic shift in the solution after time t. These show positive correlations for the first 50% of calcite, which can precipitate. Their slopes increase with increasing values of τ and they closely resemble Hendy-tests performed along growth layers of stalagmites. Our results show that stalagmites, which grow by high supply of water with drip times less than 50 s, exhibit positive correlations between δ13C and δ18O along a growth layer. But in spite of this the isotopic composition of oxygen in the solution at the apex is in isotopic equilibrium with the oxygen in the water, and therefore also that of calcite deposited at the apex.  相似文献   

4.
The thermal behaviour of silica rocks upon heat treatment is dependent on the constituent minerals and petrographic texture types. These constituents can be shown to be mainly quartz in the form of two types of chalcedony (Length-fast (LF) chalcedony and Length-slow (LS) chalcedony, the latter also being termed quartzine) and moganite. Even though the thermal behaviour of LF-chalcedony is well understood, major uncertainties persist concerning the high-temperature behaviour of LS-chalcedony and moganite. We present here a comparative study of these three constituents of common silica rocks. Our results show that the chemical reaction is the same in all three, Si–OH + HO–Si → Si–O–Si + H2O, but that the reaction kinetics and activation temperatures are very different. LS-chalcedony begins to react from 200 °C upwards, that is at temperatures 50 °C below the ones observed in LF-chalcedony, and shows the fastest reaction kinetics of this ‘water’ loss. Chemically bound water (SiOH) in moganite is more stable at high temperatures and no specific activation temperature is necessary for triggering the temperature-induced ‘water’ loss. Moganite is also found to act as a stabilizer in silica rocks preventing them from temperature-induced fracturing. These findings have implications for the study of potential heat treatment temperatures of silica rocks (in industry and heritage studies), but they also shed light on the different structures of SiO2 minerals and the role of OH impurities therein.  相似文献   

5.
Quantification of silicon and calcium recycling by plants is hampered by the lack of physico-chemical data on reactivity of plant litter in soil environments. We applied a laboratory experimental approach for determining the silica and calcium release rates from litter of typical temperate and boreal plants: pine (Pinus laricio), birch (Betula pubescens), larch (Larix gmelinii), elm (Ulmus laevis Pall.), tree fern (Dicksonia squarrosa), and horsetail (Equisetum arvense) in 0.01 M NaCl solutions, pH of 2-10 and temperature equals to 5, 25 and 40 °C. Open system, mixed-flow reactors equipped with dialysis compartment and batch reactors were used. Comparative measurements were performed on intact larch needles and samples grounded during different time, sterilized or not and with addition or not of sodium azide in order to account for the effect of surface to mass ratio and possible microbiological activity on the litter dissolution rates. Litter degradation results suggest that the silica release rate is independent on dissolved organic carbon release (cell breakdown) which implies the presence of phytoliths in a pure “inorganic” pool not complexed with organic matter. Calcium and DOC are released at the very first stage of litter dissolution while Si concentration increases gradually suggesting the presence of Ca and Si in two different pools. The dry-weight normalized dissolution rate at circum-neutral pH range (approx. 1-10 μmol/gDW/day) is 2 orders of magnitude higher than the rates of Si release from common soil minerals (kaolinite, smectite, illite). Minimal Ca release rates evaluated from batch and mixed-flow reactors are comparable with those of most reactive soil minerals such as calcite and apatite, and several orders of magnitude higher than the dissolution rates of major rock-forming silicates (feldspars, pyroxenes). The activation energy for Si liberation from plant litter is approx. 50 kJ/mol which is comparable with that of surface-controlled mineral dissolutions. It is shown that the Si release rate from the above-ground forest biomass is capable of producing the Si concentrations observed in soil solutions of surficial horizons and contribute significantly to the Si flux from the soil to the river.  相似文献   

6.
Solubilities of corundum (Al2O3) and wollastonite (CaSiO3) were measured in H2O-NaCl solutions at 800 °C and 10 kbar and NaCl concentrations up to halite saturation by weight-loss methods. Additional data on quartz solubility at a single NaCl concentration were obtained as a supplement to previous work. Single crystals of synthetic corundum, natural wollastonite or natural quartz were equilibrated with H2O and NaCl at pressure (P) and temperature (T) in a piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeves. The three minerals show fundamentally different dissolution behavior. Corundum solubility undergoes large enhancement with NaCl concentration, rising rapidly from Al2O3 molality (mAl2O3) of 0.0013(1) (1σ error) in pure H2O and then leveling off to a maximum of ∼0.015 at halite saturation (XNaCl ≈ 0.58, where X is mole fraction). Solubility enhancement relative to that in pure H2O, , passes through a maximum at XNaCl ≈ 0.15 and then declines towards halite saturation. Quenched fluids have neutral pH at 25 °C. Wollastonite has low solubility in pure H2O at this P and T(mCaSiO3=0.0167(6)). It undergoes great enhancement, with a maximum solubility relative to that in H2O at XNaCl ≈ 0.33, and solubility >0.5 molal at halite saturation. Solute silica is 2.5 times higher than at quartz saturation in the system H2O-NaCl-SiO2, and quenched fluids are very basic (pH 11). Quartz shows monotonically decreasing solubility from mSiO2=1.248 in pure H2O to 0.202 at halite saturation. Quenched fluids are pH neutral. A simple ideal-mixing model for quartz-saturated solutions that requires as input only the solubility and speciation of silica in pure H2O reproduces the data and indicates that hydrogen bonding of molecular H2O to dissolved silica species is thermodynamically negligible. The maxima in for corundum and wollastonite indicate that the solute products include hydrates and Na+ and/or Cl− species produced by molar ratios of reactant H2O to NaCl of 6:1 and 2:1, respectively. Our results imply that quite simple mechanisms may exist in the dissolution of common rock-forming minerals in saline fluids at high P and T and allow assessment of the interaction of simple, congruently soluble rock-forming minerals with brines associated with deep-crustal metamorphism.  相似文献   

7.
The Dead Sea brine is supersaturated with respect to gypsum (Ω = 1.42). Laboratory experiments and evaluation of historical data show that gypsum nucleation and crystal growth kinetics from Dead Sea brine are both slower in comparison with solutions at a similar degree of supersaturation. The slow kinetics of gypsum precipitation in the Dead Sea brine is mainly attributed to the low solubility of gypsum which is due to the high Ca2+/SO42− molar ratio (115), high salinity (∼280 g/kg) and to Na+ inhibition.Experiments with various clay minerals (montmorillonite, kaolinite) indicate that these minerals do not serve as crystallization seeds. In contrast, calcite and aragonite which contain traces of gypsum impurities do prompt precipitation of gypsum but at a considerable slower rate than with pure gypsum. This implies that transportation inflow of clay minerals, calcite and local crystallization of minerals in the Dead Sea does not prompt significant heterogeneous precipitation of gypsum. Based on historical analyses of the Dead Sea, it is shown that over the last decades, as inflows to the lake decreased and its salinity increased, gypsum continuously precipitated from the brine. The increasing salinity and Ca2+/SO42− ratio, which results from the precipitation of gypsum, lead to even slower kinetics of nucleation and crystal growth, which resulted in an increasing degree of supersaturation with respect to gypsum. Therefore, we predict that as the salinity of the Dead Sea brine continues to increase (accompanied by Dead Sea water level decline), although gypsum will continuously precipitate, the degree of supersaturation will increase furthermore due to progressively slower kinetics.  相似文献   

8.
Agates are natural hierarchicalal structural assemblies composed largely of silica minerals: chalcedony, quartz, and quartzine. Microstructural heterogeneities, most typical of those of agate-forming minerals, are characterized by variations in periods of helicoidal twisting of chalcedony and by micrometric rhythmic alternation of zones with a low refractive index within the matrix of normal chalcedony, quartz, and quartzine. A study of the degree of crystallization of chalcedony using the Barsanova-Yakovleva method showed that neither helicoidal twisting nor refractive index zoning brought about any significant disturbance in the chalcedony structure. Helicoidal twisting is a result of the stresses caused by substitution of Si4+ for Al3+ asymmetric with respect to chalcedony crystal. It is suggested that layering by the refractive index developed due to accumulation of small portions of gel consisting of high silica polymers at the front of crystal growth.  相似文献   

9.
Surface alteration-layers often coat minerals in acid-mine drainage systems and the characterization of their chemical composition is required to understand the uptake or release of potentially toxic elements. Samples with micrometer-thick rock coatings were collected from bedrock in contact with three acidic tailings ponds and a small lake, all located within the Copper Cliff mine tailings disposal area in Sudbury, Ontario, Canada. Distribution and concentration of trace-metals in the rock coatings were characterized with Laser-Ablation Inductively-Coupled Plasma Mass Spectroscopy and Micro X-ray Fluorescence Spectroscopy. The rock coatings are composed of goethite, ferrihydrite, schwertmannite, jarosite and amorphous silica. The latter phase is a product of the non-stoichiometric weathering of the underlying siliceous rock. Layers within the coatings are distinguished on the basis of their atomic Fe:Si ratios: FeOx coatings have Fe:Si > 4:1, Si-FeOx coatings have Fe:Si = 4:1 to 1:1 and SiOx coatings have Si > Fe. Iron-rich coatings (FeOx) in contact with acidic tailings ponds (pH < 3.5) have lower trace-metal concentrations than their Si-rich counterparts, whereas FeOx in contact with lake water at near neutral pH have similar trace-metal concentrations than Si-FeOx and SiOx, most likely the result of higher adsorption rates of metals at near neutral pH conditions. High trace-metal concentrations in Si-FeOx and SiOx are explained by the presence of jarosite-group minerals, which formed within Si-rich alteration layers through mixing of leached alkaline cations and trace elements from the underlying rock and Fe3+-sulfate solutions from the pond. Calculated enrichment factors for trace metals and metalloids in the coatings (relative to the pond) indicate that the mobility for Pb, As, Cr and Cu in the upper part of tailings ponds is commonly lower than the mobility for Zn, Mn, Co and Ni. The environmental significance of these findings is discussed in terms of the attenuation of trace metals in the coatings and the widespread occurrences of silica gels and jarosite-group minerals.  相似文献   

10.
Soil n-alkane δD vs. altitude gradients along Mount Gongga, China   总被引：1，自引：0，他引：1  
The altitude effect on the isotopic composition of precipitation and its application to paleoelevation reconstruction using authigenic or pedogenic minerals have been intensively studied. However, there are still no studies on variations in biomarker δD along altitude transects to investigate its potential as a paleoelevation indicator, although it has been observed that δD of higher plant lipid may record changes in precipitation δD (δDp). Here, we present δD values of higher plant-derived C27, C29, and C31n-alkanes from surface soil along the eastern slope of Mount Gongga, China with great changes in physical variables and vegetation over a range from 1000 to 4000 m above sea level. The weighted-mean δD values of these n-alkanes (δDwax) show significant linear correlations with predicted δDp values (R2 = 0.76) with an apparent isotopic enrichment (εwax-p) of −137 ± 9‰, indicating that soil δDwax values track overall δDp variation along the entire altitudinal transect. Leaf δDwax is also highly correlated with mountain altitude by a significant quadratic relationship (R2 = 0.80). Evapotranspiration is found declining with altitude, potentially lowering δDwax values at higher elevations. However, this evapotranspiration effect is believed to be largely compensated by the opposing effect of vegetation changes, resulting in less varied εwax-p values over the slope transect. This study therefore confirms the potential of using leaf δDwax to infer paleoelevations, and more generally, to infer the δD of precipitation.  相似文献   

11.
In soils, silicon released by mineral weathering can be retrieved from soil solution through clay formation, Si adsorption onto secondary oxides and plant uptake, thereby impacting the Si-isotopic signature and Ge/Si ratio of dissolved Si (DSi) exported to rivers. Here we use these proxies to study the contribution of biogenic Si (BSi) in a soil-plant system involving basaltic ash soils differing in weathering degree under intensive banana cropping. δ30Si and Ge/Si ratios were determined in bulk soils (<2 mm), sand (50-2000 μm), silt (2-50 μm), amorphous Si (ASi, 2-50 μm) and clay (<2 μm) fractions: δ30Si by MC-ICP-MS Nu Plasma in medium resolution, operating in dry plasma with Mg doping (δ30Si vs. NBS28 ± 0.12‰ ± 2σSD), Ge/Si computed after determination of Ge and Si concentrations by HR-ICP-MS and ICP-AES, respectively. Components of the ASi fraction were quantified by microscopic counting (phytoliths, diatoms, ashes). Compared to fresh ash (δ30Si = −0.38‰; Ge/Si = 2.21 μmol mol−1), soil clay fractions (<2 μm) were enriched in light Si isotopes and Ge: with increasing weathering degree, δ30Si decreased from −1.19 to −2.37‰ and Ge/Si increased from 4.10 to 5.25 μmol mol−1. Sand and silt fractions displayed δ30Si values close to fresh ash (−0.33‰) or higher due to saharian dust quartz deposition, whose contribution was evaluated by isotopic mass balance calculation. Si-isotopic signatures of bulk soils (<2 mm) were strongly governed by the relative proportions of primary and secondary minerals: the bulk soil Si-isotopic budget could be closed indicating that all the phases involved were identified. Microscopic counting highlighted a surface accumulation of banana phytoliths and a stable phytolith pool from previous forested vegetation. δ30Si and Ge/Si values of clay fractions in poorly developed volcanic soils, isotopically heavier and Ge-depleted in surface horizons, support the occurrence of a DSi source from banana phytolith dissolution, available for Si sequestration in clay-sized secondary minerals (clay minerals formation and Si adsorption onto Fe-oxide). In the soil-plant system, δ30Si and Ge/Si are thus highly relevant to trace weathering and input of DSi from phytoliths in secondary minerals, although not quantifying the net input of BSi to DSi.  相似文献   

12.
The behavior of ammonium, NH4+, in aqueous systems was studied based on Raman spectroscopic experiments to 600 °C and about 1.3 GPa. Spectra obtained at ambient conditions revealed a strong reduction of the dynamic three-dimensional network of water with addition of ammonium chloride, particularly at small solute concentrations. The differential scattering cross section of the ν1-NH4+ Raman band in these solutions was found to be similar to that of salammoniac.The Raman band of silica monomers at ∼780 cm−1 was present in all spectra of the fluid at high temperatures in hydrothermal diamond-anvil cell experiments with H2O ± NH4Cl and quartz or the assemblage quartz + kyanite + K-feldspar ± muscovite/tobelite. However, these spectra indicated that dissolved silica is less polymerized in ammonium chloride solutions than in comparable experiments with water. Quantification based on the normalized integrated intensity of the H4SiO40 band showed that the silica solubility in experiments with H2O + NH4Cl was significantly lower than that in equimolal NaCl solutions. This suggests that ammonium causes a stronger decrease in the activity of water in chloridic solutions than sodium.The Raman spectra of the fluid also showed that a significant fraction of ammonium was converted to ammonia, NH3, in all experiments at temperatures above 300 °C. This indicates a shift towards acidic conditions for experiments without a buffering mineral assemblage. The estimated pH of the fluid was ∼2 at 600 °C, 0.26 GPa, 6.6 m initial NH4Cl, based on the ratio of the integrated ν1-NH3 and ν1-NH4+ intensities and the HCl0 dissociation constant. The NH3/NH4+ ratio increased with temperature and decreased with pressure. This implies that more ammonium should be retained in K-bearing minerals coexisting with chloridic fluids upon high-P low-T metamorphism. At 500 °C, 0.73 GPa, ammonium partitions preferentially into the fluid, as constrained from infrared spectroscopy on the muscovite and from mass balance.The conversion of K-feldspar to muscovite proceeded much faster in experiments with NH4Cl solutions than in comparable experiments with water. This is interpreted as being caused by enhancement of the rate-limiting alumina solubility, suggesting complexation of Al with NH4. Nucleation and growth of mica at the expense of K-feldspar and NH4+/K+ exchange between fluid and K-feldspar occurred simultaneously, but incorporation of NH4+ into K-feldspar was distinctly faster than K-feldspar consumption.  相似文献   

13.
Banded iron formations (BIFs) are chemical marine sediments dominantly composed of alternating iron-rich (oxide, carbonate, sulfide) and silicon-rich (chert, jasper) layers. Isotope ratios of iron, carbon, and sulfur in BIF iron-bearing minerals are biosignatures that reflect microbial cycling for these elements in BIFs. While much attention has focused on iron, banded iron formations are equally banded silica formations. Thus, silicon isotope ratios for quartz can provide insight on the sources and cycling of silicon in BIFs. BIFs are banded by definition, and microlaminae, or sub-mm banding, are characteristic of many BIFs. In situ microanalysis including secondary ion mass spectrometry is well-suited for analyzing such small features. In this study we used a CAMECA IMS-1280 ion microprobe to obtain highly accurate (±0.3‰) and spatially resolved (∼10 μm spot size) analyses of silicon and oxygen isotope ratios for quartz from several well known BIFs: Isua, southwest Greenland (∼3.8 Ga); Hamersley Group, Western Australia (∼2.5 Ga); Transvaal Group, South Africa (∼2.5 Ga); and Biwabik Iron Formation, Minnesota, USA (∼1.9 Ga). Values of δ18O range from +7.9‰ to +27.5‰ and include the highest reported δ18O values for BIF quartz. Values of δ30Si have a range of ∼5‰ from −3.7‰ to +1.2‰ and extend to the lowest δ30Si values for Precambrian cherts. Isua BIF samples are homogeneous in δ18O to ±0.3‰ at mm- to cm-scale, but are heterogeneous in δ30Si up to 3‰, similar to the range in δ30Si found in BIFs that have not experienced high temperature metamorphism (up to 300 °C). Values of δ30Si for quartz are homogeneous to ±0.3‰ in individual sub-mm laminae, but vary by up to 3‰ between multiple laminae over mm-to-cm of vertical banding. The scale of exchange for Si in quartz in BIFs is thus limited to the size of microlaminae, or less than ∼1 mm. We interpret differences in δ30Si between microlaminae as preserved from primary deposition. Silicon in BIF quartz is mostly of marine hydrothermal origin (δ30Si < −0.5‰) but silicon from continental weathering (δ30Si ∼ 1‰) was an important source as early as 3.8 Ga.  相似文献   

14.
The transport of H2SO4 (at pH = 1.0, −1.0 and −3.0) through two mineralogically different compacted clays (Kc and Km) was examined using single-reservoir diffusion cells with constant source concentrations. At the end of the 216 day test period, geochemical analyses indicated increased depth of acid diffusion with increased reservoir acidity for both Kc and Km cells. Elevated Ca, Al, Fe and Si concentrations were associated with decreased pH values in all cells. XRD results showed that these elevated concentrations corresponded to the loss of carbonate and montmorillonite peaks and decreased peak intensities for illite and kaolinite in the Kc and Km pH −1.0 and −3.0 Km cells. Moreover, Si X-ray absorption near-edge structure (XANES) indicated dissolution of the phyllosilicate phases, a relative increase in the amount of quartz, and the potential formation of an amorphous silica phase. The results of this study showed that, despite the extreme pH values considered, movement of H2SO4 solutions with pH < 1.0 may be greatly retarded in the presence of a strongly neutralizing mineral phase, such as dolomite, within the clay.  相似文献   

15.
The silicon isotope fractionation between rice plant and nutrient solution was studied experimentally. Rice plants were grown to maturity with the hydroponic culture in a naturally lit glasshouse. The nutrient solution was sampled for 14 times during the whole rice growth period. The rice plants were collected at various growth stages and different parts of the plants were sampled separately. The silica contents of the samples were determined by the gravimetric method and the silicon isotope compositions were measured using the SiF4 method.In the growth process, the silicon content in the nutrient solution decreased gradually from 16 mM at starting stage to 0.1-0.2 mM at harvest and the amount of silica in single rice plant increased gradually from 0.00013 g at start to 4.329 g at harvest. Within rice plant the SiO2 fraction in roots reduced continuously from 0.23 at the seedling stage, through 0.12 at the tiller stage, 0.05 at the jointing stage, 0.023 at the heading stage, to 0.009 at the maturity stage. Accordingly, the fraction of SiO2 in aerial parts increased from 0.77, through 0.88, 0.95, 0.977, to 0.991 for the same stages. The silicon content in roots decreased from the jointing stage, through the heading stage, to the maturity stage, parallel to the decrease of silicon content in the nutrient solution. At the maturity stage, the silicon content increased from roots, through stem and leaves, to husks, but decreased drastically from husks to grains. These observations show that transpiration and evaporation may play an important role in silica transportation and precipitation within rice plants.It was observed that the δ30Si of the nutrient solution increased gradually from −0.1‰ at start to 1.5‰ at harvest, and the δ30Si of silicon absorbed by bulk rice plant increased gradually from −1.72‰ at start to −0.08‰ at harvest, reflecting the effect of the kinetic silicon isotope fractionation during silicon absorption by rice plants from nutrient solutions. The calculated silicon isotope fractionation factor between the silicon instantaneously absorbed by rice roots and the silicon in nutrient solution vary from 0.9983 at start to 0.9995 at harvest, similar to those reported for bamboo, banana and diatoms in direction and extent. In the maturity stage, the δ30Si value of rice organs decreased from −1.33‰ in roots to −1.98‰ in stem, and then increased through −0.16‰ in leaves and 1.24‰ in husks, to 2.21‰ in grains. This trend is similar to those observed in the field grown rice and bamboo.These quantitative data provide us a solid base for understanding the mechanisms of silicon absorption, transportation and precipitation in rice plants and the role of rice growth in the continental Si cycle.  相似文献   

16.
We present some of the first analyses of the stable isotopic composition of dissolved silicon (Si) in groundwater. The groundwater samples were from the Navajo Sandstone aquifer at Black Mesa, Arizona, USA, and the Si isotope composition of detrital feldspars and secondary clay coatings in the aquifer were also analyzed. Silicon isotope compositions were measured using high-resolution multi-collector inductively coupled mass spectrometry (HR-MC-ICP-MS) (Nu1700 & NuPlasma HR). The quartz dominated bulk rock and feldspar separates have similar δ30Si of −0.09 ± 0.04‰ and −0.15 ± 0.04‰ (±95% SEM), respectively, and clay separates are isotopically lighter by up to 0.4‰ compared to the feldspars. From isotopic mass-balance considerations, co-existing aqueous fluids should have δ30Si values heavier than the primary silicates. Positive δ30Si values were only found in the shallow aquifer, where Si isotopes are most likely fractionated during the dissolution of feldspars and subsequent formation of clay minerals. However, δ30Si decreases along the flow path from 0.56‰ to −1.42‰, representing the most negative dissolved Si isotope composition so far found for natural waters. We speculate that the enrichment in 28Si is due to dissolution of partly secondary clay minerals and low-temperature silcretes in the Navajo Sandstone. The discovery of the large range and systematic shifts of δ30Si values along a groundwater flow path illustrates the potential utility of stable Si isotopes for deciphering the Si cycling in sedimentary basins, tracing fluid flow, and evaluating global Si cycle.  相似文献   

17.
Mineral weathering in soils is an important source of many nutrients to forest ecosystems. Apatite, a Ca phosphate mineral, occurs in trace amounts in virtually all igneous and metamorphic rocks and is often found as small mineral inclusions in more weathering-resistant silicate minerals. To better understand the distribution of apatite in soils and its exposure to soil solutions, a sequential extraction method was developed to selectively dissolve minerals from soils so that the amount of apatite in contact with soil solutions versus that armored by silicate minerals could be quantified. The use of three molarities of HNO3 (0.01, 0.1 and 1 M) at three temperatures (0, 10, or 20 °C) was explored and it was found that apatite congruently dissolved in 1 M HNO3 at all three temperatures, but did not completely dissolve in weaker HNO3 solutions. Soil horizons, glacial till (i.e., soil parent material), and individual minerals separated from till collected from the Hubbard Brook Experimental Forest (HBEF), NH, were subjected to a 4-step sequential extraction. Chemical analyses of the extracts indicate that 1 M NH4Cl (pH 7; 20 °C) removes exchangeable ions, 1 M HNO3 at 20 °C primarily dissolves apatite in contact with solutions, 1 M HNO3 at 200 °C primarily dissolves biotite and chlorite (and apatite armored by them), and a mixture of concentrated HNO3, HCl, and HF at 200 °C dissolves the more refractory minerals including muscovite, alkali feldspar, plagioclase feldspar and quartz (and apatite armored by these minerals). This extraction method was applied to soil profiles from HBEF to demonstrate that it could be used to interpret the abundance of apatite and other minerals as a function of depth. Approximately 70% of the apatite in the HBEF soil parent material is exposed to soil solutions; the remaining 30% is armored in more weathering-resistant micas and feldspars. In the upper soil horizons, the only apatite that has not been weathered from the soil occurs as inclusions in micas and feldspars and thus the rate of dissolution of apatite in weathered soil horizons is controlled by silicate mineral dissolution.  相似文献   

18.
Samples produced in piston cylinder experiments were used to document the thermal isotopic fractionation of all the major elements of basalt except for aluminum and the fractionation of iron isotopes by chemical diffusion between a natural basalt and rhyolite. The thermal isotopic fractionations are summarized in terms of a parameter Ωi defined as the fractionation in per mil per 100 °C per atomic mass units difference between the isotopes. For molten basalt we report ΩCa = 1.6, ΩFe = 1.1, ΩSi = 0.6, ΩO = 1.5. In an earlier paper we reported ΩMg = 3.6. These fractionations represent a steady state balance between thermal diffusion and chemical diffusion with the mass dependence of the thermal diffusion coefficient being significantly larger than the mass dependence of the chemical diffusion coefficients for isotopes of the same element. The iron isotopic measurements of the basalt-rhyolite diffusion couple showed significant fractionation that are parameterized in terms of a parameter βFe = 0.03 when the ratio of the diffusion coefficients D54 and D56 of 54Fe and 56Fe is expressed in terms of the atomic mass as D54/D56 = (56/54)βFe. This value of βFe is smaller than what we had measured earlier for lithium, magnesium and calcium (i.e., βLi = 0.215, βCa = 0.05, βMg = 0.05) but still significant when one takes into account the high precision with which iron isotopic compositions can be measured (i.e., ±0.03‰) and that iron isotope fractionations at magmatic temperatures from other causes are extremely small. In a closing section we discuss technological and geological applications of isotopic fractionations driven by either or both chemical and thermal gradients.  相似文献   

19.
The heat of precipitation, the mean crystal size and the broadness of crystal size distribution of barium sulfate precipitating in aqueous solutions of different background electrolytes (KCl, NaCl, LiCl, NaBr or NaF), was shown to vary at constant thermodynamic driving force (supersaturation) and constant ionic strength depending on the salt present in solution. The relative inversion in the effect of respective background ions on the characteristics of barite precipitate was observed between two studied supersaturation (Ω) and ionic strength (IS) conditions. The crystal size variance (β2) increased in the presence of background electrolytes in the order LiCl < NaCl < KCl at Ω = 103.33 and IS = 0.03 M and KCl < NaCl < LiCl at Ω = 103.77 and IS = 0.09 M. At a given Ω and IS the respective size of barite crystals decreased with increasing β2 in chloride salts of different cations and remained constant in sodium salts of different anions.We suggest that ionic salts affect the kinetics of barite nucleation and growth due to their influence on water of solvation and bulk solvent structure. This idea is consistent with the hypothesis that the kinetic barrier for barium sulfate nucleation depends on the frequency of water exchange around respective building units that can be modified by additives present in solution. In electrolyte solution the relative switchover between long range electrostatic interactions and short range hydration forces, which influence the dynamics of solvent exchange between an ion solvation shell and bulk fluid, results in the observed inversion in the effect of differently hydrated salts on nucleation rates and the resulting precipitate characteristics.  相似文献   

20.
Hyperalkaline and saline radioactive waste fluids with elevated temperatures from S-SX high-level waste tank farm at Hanford, WA, USA accidentally leaked into sediments beneath the tanks, initiating a series of geochemical processes and reactions whose significance and extent was unknown. Among the most important processes was the dissolution of soil minerals and precipitation of stable secondary phases. The objective of this investigation was to study the release of Fe into the aqueous phase upon dissolution of Fe-bearing soil minerals, and the subsequent formation of Fe-rich precipitates. Batch reactors were used to conduct experiments at 50 °C using solutions similar in composition to the waste fluids. Results clearly showed that, similarly to Si and Al, Fe was released from the dissolution of soil minerals (most likely phyllosilicates such as biotite, smectite and chlorite). The extent of Fe release increased with base concentration and decreased with Al concentration in the contacting solution. The maximum apparent rate of Fe release (0.566 × 10−13 mol m−2 s−1) was measured in the treatment with no Al and a concentration of 4.32 mol L−1 NaOH in the contact solution. Results from electron microscopy indicated that while Si and Al precipitated together to form feldspathoids in the groups of cancrinite and/or sodalite, Fe precipitation followed a different pathway leading to the formation of hematite and goethite. The newly formed Fe oxy-hydroxides may increase the sorption capacity of the sediments, promote surface mediated reactions such as precipitation and heterogeneous redox reactions, and affect the phase distribution of contaminants and radionuclides.  相似文献   

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