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1.
Partitioning of Ni in calcite, CaCO3, was evaluated with the aim of collecting data on partition and distribution coefficients and to enhance understanding about the interaction of Ni with the calcite surface and further incorporation into the bulk. This information will aid in the interpretation of geological processes for safety assessment of waste repositories and contamination of groundwater. Coprecipitation experiments were carried out by the constant addition method at 25 °C and pCO2 = 1 and 10−3.5 atm. Ni was moderately partitioned from solution into calcite. For dilute solid solutions (XNi < 0.001), Ni partition coefficients were estimated to be ∼1 and found to be weakly dependent on calcite precipitation rate in the range of 3-230 nmol m−2 s−1. Ni molar fraction in the solid is directly proportional to Ni concentration in the solution. The fit of the data to such a model is good evidence that Ni is taken up as a true solid solution, not simply by physical trapping.  相似文献   

2.
Distribution coefficients, as a function of precipitation rate, were determined for the metals Sr2+, Co2+, Mn2+ and Cd2+in calcite. A pH-stat was used to maintain a constant degree of-saturation, and hence precipitation rate, during each coprecipitation run. The precipitation rate was proportional to the degree of supersaturation and the mass of seed crystal introduced. Distribution coefficients (λ) as a function of rate were determined using radioactive isotopes for solutions with saturations Ω = 1 to Ω = 5.5. Strontium distribution coefficients increased with increasing precipitation rate, while Co, Mn and Cd distribution coefficients decreased with increasing precipitation rate. The following rate expressions (at 25°C) were derived: logλSr = 0.249 log R ?1.57logλMn = ?0.266 log R + 1.35logλCo = ?0.173 log R + 0.68logλCd = ?0.194 log R + 1.46 where R is the observed precipitation rate in nmoles CaCO3 per mg seed crystal per min.In separate experiments the uptake of radioactive isotopes was monitored during the recrystallization of calcite seed crystals. Rates of recrystallization were from 100 to 10, 000 times slower than the pH-stat experiments, but yielded distribution coefficients consistent with the above rate expressions.Using gross estimates of biogenic crystal growth rates, aragonite to calcite transformation rates, and the above Sr rate expression, biogenic calcite and diagenetic calcite Sr contents are estimated. These experiments indicate that in addition to solution composition, precipitation rate is a significant factor influencing the trace metal content of naturally occurring calcite.  相似文献   

3.
The convective transfer of 137Cs and 90Sr by groundwater on the territory of the Russian Research Centre Kurchatov Institute (RRCKI) was modeled. Geological data on the RRCKI site and possible sources of radionuclides show that the uppermost aquifer, composed of Quaternary sediments, is the most probable region of spreading of radioactive contamination. Since the lateral migration of radionuclides is predominant, a 2D horizontal model was used for the forecasting of spreading of radioactive contaminants in the subsurface medium. Transient or long-term repositories of radioactive materials at the RRCKI site (concentrated sources) and aquifer rocks contaminated in the course of removal of radionuclides from these repositories (distributed source) are responsible for groundwater pollution. The initial 137Cs and 90Sr distributions used in the forecasting of radionuclide migration were determined from their contents in core samples taken from wells drilled in contaminated areas of the RRCKI site. The zone of radionuclide migration is limited by poorly permeable moraine loam from below and by the water table from above. To determine the upper and lower boundaries, these surfaces were mapped in plan view. The data of meteorological observations over a long period were used to map the intensity of precipitation in the studied territory. The density of rocks in the uppermost aquifer and partition coefficients of radionuclides between rocks and groundwater were estimated from the data of laboratory examination of the core samples. The available data on the permeability of rock samples and the results of test pumping out of some wells were involved in the consideration. The results obtained and the data on the water table allowed us to define a gauge problem for determining the distribution of the filtration coefficient in the uppermost aquifer. This problem was solved taking the intensity of precipitation into account. The properties of the uppermost aquifer and the initial radionuclide distribution therein were used as initial data for modeling 137Cs and 90Sr migration on the territory of the RRCKI over 50 years.  相似文献   

4.
Partitioning of Eu(III) in calcite, CaCO3, was evaluated with the aim of collecting data on partition coefficients and to enhance understanding of the incorporation mechanisms. This information will aid in the interpretation of geological processes from rare Earth element (REE) data and in the use of Eu(III) as a chemical analogue for the trivalent actinides, particularly Am(III) and Cm(III). Coprecipitation experiments were carried out by the constant addition method at 25°C and PCO2 = 1 atm. Eu(III) was strongly partitioned from the solution into calcite. For dilute solid solutions (XEu < 0.001), Eu partition coefficients were estimated to be 770 ± 290 and found to be independent of calcite precipitation rate in the range of 0.02 to 2.7 nmol mg−1 min−1. This could be explained by the approximately equal values of the Eu partition and adsorption coefficients. Several solid solution models were tested. A vacancy model for Eu2(CO3)3-CaCO3 is consistent with the experimental results and constraints on geometry for Eu fit in the calcite lattice. For low Eu content, vacancy density is independent of Eu concentration in the solid so logarithm of the ion activity product, log (Eu)2(CO32−)3, depends linearly on log XEu2. The fit of the data to such a model is good evidence that Eu(III) is taken up as a true solid solution, not simply by physical trapping. A model using EuOHCO3-CaCO3 is also consistent with the uptake stoichiometry, but EuOH2+ substitution for Ca2+ would be expected to distort the calcite structure more than is compatible with such a high KD. Several other models, including EuNa(CO3)2-CaCO3, were abandoned because their stoichiometric relationships did not fit the experimental data.  相似文献   

5.
We report results from in situ extended X-ray absorption fine structure (EXAFS) spectroscopy studies of Cu(II) and Zn(II) complexes forming at the calcite surface following adsorption from preequilibrated calcite-saturated solutions. Both Cu(II) and Zn(II) coordinate at Ca sites on the calcite surface, forming mononuclear inner-sphere adsorption complexes. The Zn adsorption complexes are in tetrahedral coordination with first-shell O neighbors with RZn-O = 1.95 Å, and the Cu complexes are Jahn-Teller distorted, with equatorial RCu-O = 1.95 Å. Results from EXAFS data of dilute Cu- and Zn-calcite solid solutions confirm substitution of these metals in the Ca site of the calcite structure as octahedral complexes during coprecipitation. X-ray fluorescence microanalyses of calcite (101?4) hillocks grown in coprecipitation experiments show that divalent Cu and Zn, which have ionic radii smaller than Ca, are preferentially incorporated into the parallel arrays of <4?41>+ steps that define one pair of symmetrically equivalent vicinal faces on polygonized growth spirals. In contrast, other divalent metals with sixfold ionic radii smaller than Ca (Co, Cd, Mn, Mg) have been shown to be preferentially incorporated into <4?41>− growth steps, which define the second pair of vicinal faces on the growth spirals, but which are symmetrically nonequivalent to the steps on the first pair. The distortion from octahedral symmetry observed for the Cu and Zn adsorption complexes likely plays a key role in the observed preference of Cu and Zn for incorporation into the <4?41>+ steps.  相似文献   

6.
This study reports on the seepage of metals, metalloids and radionuclides from the Mary Kathleen uranium mill tailings repository. Since rehabilitation in the 1980s, the capped tailings have developed a stratified hydrochemistry, with acid (pH 3.7), saline, metal-rich (Fe, Mn, Ni, U ± As, Pb, Zn), oxygenated (1.05 mg L−1 DO), radioactive waters in the upper tailings pile and near-neutral pH (pH 7.57), metal-poor, reduced (0.08 mg L−1 DO) waters at depth. Seepage (∼0.5 L s−1) of acid (pH 5.5), metal-rich (Fe, Mn ± Ni, U, Zn), radioactive (U-235, U-238, Ra-226, Ra-228, Ac-227) waters occurs from the base of the tailings dam retaining wall into the former evaporation pond and local drainage system. Oxygenation of the seepage waters causes the precipitation of Fe and coprecipitation and adsorption of other metals (U, Y), metalloids (As), rare earth elements (Ce, La) and radionuclides (U-235, U-238). By contrast, alkalis and alkaline–earth elements (Ca, K, Mg, Na, Sr), Mn, sulfate and to some degree metals (U, Zn, Ni), rare earth elements (Ce, La) and radionuclides (U-235, U-238, Ra-226, Ra-228) remain in solution until pH neutralisation and evaporation lead to their precipitation in efflorescences and sulfate-rich evaporative sediments. While the release of contaminant loads from the waste repository through seepage is insignificant (e.g. ∼5 kg of U per year), surface waters downstream of the tailings impoundment possess TDS, U and SO4 concentrations that exceed Australian water quality guideline values in livestock drinking water. Thus, in areas with a semi-arid climate, even insignificant load releases of contaminants from capped tailings repositories can still cause the deterioration of water quality in ephemeral creek systems.  相似文献   

7.
Radioactive nuclear waste containing long-lived actinides (Np, Pu, Am, and Cm) is proposed to be placed in well repositories with a depth of up to 5 km. The optimum form of such wastes is crystalline phases that are capacious in relation to radionuclides and stable in mineralized groundwater (brines) heated due to heat generation in the waste and due to the geothermal gradient. In order to find possible phases, we have studied samples of the Nd–Ti–Zr–O system, where Nd3+ acts as an imitator of the rare-earth-actinide fraction of highly radioactive wastes of reprocessed nuclear fuel. The samples were obtained by induction melting in a cold crucible with subsequent melt crystallization. It has been concluded that the Nd2–x(Ti,Zr)2O7–1.5х and Nd4Ti9O24 phases are promising as potential matrices for these wastes. The structure of NdO1.5–TiO2–ZrO2 system at a high temperature has been revealed.  相似文献   

8.
The potential for incorporation of strontium (Sr) into biogenic Fe(II)-bearing minerals formed during microbial reduction of synthetic hydrous ferric oxide (HFO) was investigated in circumneutral bicarbonate-buffered medium containing SrCl2 at concentrations of 10 μM, 100 μM, or 1.0 mM. CaCl2 (10 mM) was added to some experiments to simulate a Ca-rich groundwater. In Ca-free systems, 89 to 100% of total Sr was captured in solid-phase compounds formed during reduction of 30 to 40 mmol Fe(III) L−1 over a 1-month period. A smaller fraction of total Sr (25 to 34%) was incorporated into the solid phase in cultures amended with 10 mM CaCl2. X-ray diffraction identified siderite and ferroan ankerite as major end products of HFO reduction in Ca-free and Ca-amended cultures, respectively. Scanning electron microscopy-energy dispersive x-ray spectroscopy revealed the presence of Sr associated with carbonate phases. Selective extraction of HFO reduction end products indicated that 46 to 100% of the solid-phase Sr was associated with carbonates. The sequestration of Sr into carbonate phases in the Ca-free systems occurred systematically according to a heterogeneous (Doerner-Hoskins) partition coefficient (DD-H) of 1.81 ± 0.15. This DD-H value was 2 to 10 times higher than values determined for incorporation of Sr (10 μM) into FeCO3(s) precipitated abiotically at rates comparable to or greater than rates observed during HFO reduction, and fivefold higher than theoretical partition coefficients for equilibrium Fe(Sr)CO3 solid solution formation. Surface complexation and entrapment of Sr by rapidly growing siderite crystals (and possibly other biogenic Fe(II) solids) provides an explanation for the intensive scavenging of Sr in the Ca-free systems. The results of abiotic siderite precipitation experiments in the presence and absence of excess Ca indicate that substitution of Ca for Sr at foreign element incorporation sites (mass action effect) on growing FeCO3(s) surfaces can account for the inhibition of Sr incorporation into the siderite component of ankerite formed in the Ca-amended HFO reduction experiments. Likewise, substitution of Fe(II) for Sr may explain the absence of major Sr partitioning into the calcite component of ankerite. The findings indicate that under appropriate conditions, sequestration of metals in siderite produced during bacterial Fe(III) oxide reduction may provide a mechanism for retarding the migration of Sr and other divalent metal contaminants in anaerobic, carbonate-rich sedimentary environments.  相似文献   

9.
Surface reactions on calcite play an important role in geochemical and environmental systems, as well as many areas of industry. In this review, we present investigations of calcite that were performed in the frame of the joint research project “RECAWA” (reactivity of calcite–water-interfaces: molecular process understanding for technical applications). As indicated by the project title, work within the project comprised a large range of length scales. The molecular scale structure of the calcite (1 0 4)–water-interface is refined based on surface diffraction data. Structural details are related to surface charging phenomena, and a simplified basic stern surface complexation model is proposed. As an example for trace metal interactions with calcite surfaces we review and present new spectroscopic and macroscopic experimental results on Selenium interactions with calcite. Results demonstrate that selenate (SeO42−) shows no significant interaction with calcite at our experimental conditions, while selenite (SeO32−) adsorbs at the calcite surface and can be incorporated into the calcite structure. Atomistic calculations are used to assess the thermodynamics of sulfate (SO42−), selenate (SeO42−), and selenite (SeO32−) partitioning in calcite and aragonite. The results show that incorporation of these oxo-anions into the calcite structure is so highly endothermic that incorporation is practically impossible at bulk equilibrium and standard conditions. This indicates that entrapment processes are involved when coprecipitation is observed experimentally. The relevance of nano-scale surface features is addressed in an investigation of calcite growth and precipitation in the presence of phosphonates, demonstrating the influence of phosphonates on the morphology of growth spirals and macroscopic growth rates. It is investigated how physical properties of limestone containing cement suspensions may influence the workability of the cement suspensions and thus the efficacy of limestone in industrial applications. The largest scale is reached in iron filtration experiments in a water-purification-pilot-plant using limestone as filter material, which appeared to be highly effective for removing iron from drinking water. Investigations presented cover a whole series of methods to study the calcite–water-interface. Many calcite related topics are addressed, demonstrating how broad the field of calcite–water-interface research is and how manifold the applications are, for which calcite–water-interface phenomena are of major relevance.  相似文献   

10.
《Applied Geochemistry》1998,13(1):43-47
Although 14C occurs naturally, it is also a waste product of the nuclear industry, and can be important because of its long half-life, high mobility as an anion, and ready incorporation into biota. Some aqueous inorganic species are anionic with migration minimally retarded by most geological and soil materials. Substantial retardation is expected when calcite is present, but there are few data to quantify this effect. The present study measured partition coefficient values, Rd (concentration on solids divided by concentration in liquids), of 8–85 l kg−1 for a series of calcite materials and for a carbonated soil. In contrast, Rd was zero for montmorillonite. The series of calcite materials varied in particle size. In order to investigate the effects of particle size, dissolution and degassing of 14C and 12C were monitored as pH was slowly decreased. The change in pH with addition of acid was strongly affected by particle size, as expected, but there was no systematic effect of particle size on the relative dissolution rates of 14C vs 12C, or on Rd. Apparently, surface area was not a limiting factor in the interaction of 14C with these materials. The 14C in soil behaved most like the very fine calcite, indicating that the specific surface of the soil carbonate was similar to that of the very fine calcite.  相似文献   

11.
Sorption and catalytic oxidation of Fe(II) at the surface of calcite   总被引：1，自引：0，他引：1  
The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO3Fe+ and >CO3FeCO3H0. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t1/2 = 41 ± 1 min and t1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO3FeCO3H0, for which the species specific rate constant was estimated.  相似文献   

12.
The Quaternary sediments representing the interface between the granite host rock and the Earth surface are of paramount importance when determining the potential cycling of anthropogenic and natural radionuclides in near-surface systems. This is particularly true in the case of high-level nuclear waste (HLNW) repositories placed in granite. In this work a modelling procedure is presented to quantitatively determine the retention capacity of a Quaternary till in the Forsmark area, which has been recently selected to host the deep geologic storage of HLNW in Sweden. Reactive transport numerical models have been used to simulate the intrusion of a deep groundwater carrying radionuclides potentially released from a repository into a Quaternary till. Four radionuclides (235U, 135Cs, 226Ra and 90Sr) have been selected according to their different geochemical behaviour and potential dose relevance to surface ecosystems. Numerical results indicate that repository-derived: (i) U will have a minor impact in the till, mainly due to the high natural concentration of U and its adsorption on ferrihydrite; (ii) Cs will be efficiently retained by cation exchange on illite; (iii) Ra will be retained via co-precipitation with barite; and although (iv) Sr will be retained via co-precipitation with calcite and cation exchange on illite, the retention capacity of the Quaternary till for Sr is limited.  相似文献   

13.
Mn K-edge EXAFS spectroscopy of solid-solution samples encompassing the complete MnCO3–CaCO3 series shows that first-shell Mn–O distances deviate little from the 2.19-Å distance observed in pure MnCO3. Very slight lengthening is observed only in the limiting case of dilute Mn(II) calcite solid solutions, where the Mn–O distance is 2.21 Å. The observed nearly complete structural relaxation and the composition independence of the Mn–O distance are consistent with the Pauling model behavior of solid solutions, and agree with previous studies showing a high degree of relaxation around hetero-sized substituents in the calcite structure. Strain occurs through bond bending, which is facilitated by the exclusively corner-sharing topology of calcite. Observed distances from Mn to more distant neighbors show significant variation across the solid-solution series that resembles Vegard's law-type behavior but reflects averaging. The high degree of relaxation suggests modest enthalpies of mixing in the solution, consistent with calorimetric studies.  相似文献   

14.
The influence of citrate and phthalate on Co coprecipitation with calcite was investigated using a combination of batch experiments, Fourier-transform infra-red (FT-IR) spectroscopy, and thermogravimetric analysis (TGA) over a wide range of precipitation rates. Steady-state growth conditions (at constant [Ca], [Co], DIC, and pH) were generally achieved within 3-5 h, after which Co(II) partitioning into calcite was evaluated. Only minor differences are observed in the partition coefficient (Kd) trends with and without citrate and phthalate as a function of calcite precipitation rate except at very low rates. Slight inhibition of calcite growth is observed in the presence of citrate or phthalate, which can be attributed to adsorption at surface sites. TGA curves for samples coprecipitated with citrate show a significant mass loss between 375 and 550 °C, whereas the weight-loss curves for the Co-phthalate coprecipitates are indistinguishable from those of the organic-free Co coprecipitates. This indicates that citrate is incorporated into calcite during calcite crystallization, whereas phthalate is excluded. FT-IR spectra for the sample with citrate show a broad absorption in the range 3700-3100 cm−1, which is attributable to water molecules coordinated to citrate coprecipitated with calcite. The preferential incorporation of citrate over phthalate likely reflects differences in both aqueous speciation and conformation of the carboxylate groups. This new finding may provide new insight to the factors that control the behavior of macromolecules and their incorporation into the structure of calcium carbonate during biomineralization.  相似文献   

15.
Ionic conductivity of polycrystalline calcite containing varying amounts of PO 4 3? ions was measured in the pressure range of 1–6 GPa and at room temperature. Electrical conductivity increased with pressure corresponding to the phase transition of calcite I to calcite II. The conductivity in calcite III decreased exponentially with pressure. Calculated activation volumes of the conductivity varied with PO 4 3? content in the range of 0.94–5.34 cm3/mol. This variation corresponded to the lattice parameter change of calcite I due to PO 4 3? incorporation and indicated the contribution of CO 3 2? -vacancies associated with PO 4 3? ions to the conductivity.  相似文献   

16.
Present strategies for the long-term disposal of high-level nuclear wastes are based on the construction of repositories hundreds of meters below the earth surface. Although the surrounding host-rocks are relatively isolated from the light at the earth surface they are by no means lifeless. Microorganisms rule the deep part of the biosphere and it is well established that their activity can alter chemical and physical properties of these environments. Microbial processes can directly and indirectly affect radionuclide migration in multiple ways. Within 6th FP IP FUNMIG the interplay between microbial biofilms and radionuclides and the effect of microbially induced redox transformations of Fe on radionuclide mobility have been investigated. For the first time, formation of U(V) as a consequence of microbial U(VI) reduction in a multi-species biofilm was detected in vivo by combining laser fluorescence spectroscopy and confocal laser scanning microscopy. Furthermore, it was demonstrated that addition of U(VI) can lead to increased respiratory activity in a biofilm. Increased respiration in a biofilm can create microenvironments with lower redox potential, and hence induce reduction of radionuclides. Transient mobilization of U was observed in experiments with Fe oxides containing adsorbed U(VI) in which the activity of SO4-reducing organisms was mimicked by sulfide addition. Faster reaction of sulfide with Fe oxides compared to U(VI) reduction, and decreasing U(VI) adsorption due to the transformation of Fe oxides into FeS can explain the observed intermittent U mobilization. The presented research on microbe-radionuclide interactions performed within FUNMIG addresses only a few aspects of the potential role of microorganisms in the performance assessment of nuclear waste repositories. For this reason, additionally, this article provides a cursory overview of microbial processes which were not studied within the FUNMIG project but are relevant in the context of performance assessment. The following aspects are presented: (a) the occurrence and metabolic activity of microorganisms of several proposed types of host-rocks, (b) the potential importance of microorganisms in the near-field of nuclear waste repositories, (c) indirect effects of microbial processes on radionuclide mobility in the repository far-field, (d) binding of radionuclides to microbial biomass, (e) microbial redox transformations of radionuclides, and (f) the implementation of microbial processes in reactive transport models for radionuclide migration.  相似文献   

17.
Iron and Mn oxides and associated radionuclides in soils and sediments from the radioactive waste burial grounds at Oak Ridge National Laboratory have been selectively extracted using wet chemical techniques. Product-moment-correlation analyses have demonstrated that 60Co and various actinides, principally 244Cm, 241Am and 238Pu are dominantly associated with Mn oxides. Correlation coefficients between these radionuclides and Fe oxides and organic C are generally very low. The important role of Mn oxides in radionuclide adsorption is attributed to their unique surface and colloidal properties. The data illustrate the importance of the Mn oxide component of soils and sediments in controlling transition metal and actinide solubility.These results suggest two major implications for the disposal of radioactive waste. First, in order to minimize future 60Co and actinide mobilization from disposal sites, a chemical environment in which Mn oxides are least soluble should be maintained. Second, the liberal use of Mn oxides in waste management operations might improve long-term retention of these radionuclides. Deep-sea Mn modules, which may in the future be mined for their trace metal contents, could serve as a ready supply of Mn oxide for waste disposal applications.  相似文献   

18.
Much interest has been generated in assessing the possible risks of contamination for humans and marine life resulting from the dumping of nuclear waste in Arctic Seas by the former Soviet Union. Models are being used to predict the transport of radionuclides released from the dumping grounds. A key parameter in these models is the partition coefficient representing the uptake potential of marine sediments and seawater for radioactive contaminants. Partition coefficients are dependent upon the independent variables of sediment concentration and the sediment/water radionuclide distribution coefficients. Modelers must use estimated average values for the independent variables because data for these variables are lacking for the Arctic environment. In this note, we illustrate the differences between assuming that partition coefficients can be computed solely from the average values of the independent variables vs. exact probability distributions, and illustrate the technique for one of the radioactive contaminants,137Cs. In general, errors in the sediment partition coefficient can be as high as 67% using average values; for137Cs. the error is about 37%.  相似文献   

19.
The partitioning of Sr between calcite, dolomite and liquids is essentially independent of temperature between 150° and 350° C. The partition coefficients corrected for number of cation sites are b calc=0.096 and b dol= 0.048 for 1 mol cations/6 mol H2O liquid. Upon dilution the partition coefficients increase, but their ratio stays constant at about 2∶1. This ratio is due to the fact that calcite has twice as many Ca-sites for Sr-substitution as dolomite. The 2∶1 relationship is also observed in natural calcite and dolomite which have undergone diagenesis. The temperature independence of partitioning is caused by the relatively small thermal expansion of calcite and dolomite. Thermal expansion between 25° and 400° C was found to follow the equations V calc=7.0·10−4 T(°C)+36.95 and V dol=6.9·10−4 T(°C)+32.24, V: cm3/mol. Therefore calcite and dolomite cannot serve as a temperature indicator. To have an ideal geothermometer a mineral pair with high and low thermal expansion is required. Literature date demonstrate that wurtzite, sphalerite, and galena are such minerals.  相似文献   

20.
《Applied Geochemistry》1993,8(6):605-616
The Cigar Lake U deposit is located in northern Saskatchewan in the eastern part of the Athabasca Sandstone Basin, and consists of a high-grade ore body (up to 55% U) located at a depth of ∼430 m. As part of a study to evaluate the analog features of this deposit with respect to a disposal vault for waste nuclear fuel, colloids (1–450 nm) and suspended particles (450nm) in groundwater have been investigated to evaluate their effect on element transport through the U deposit. Tangential-flow ultrafiltration was used to concentrate particles from 501 groundwater samples in order to characterize the size distribution, concentration, composition and natural radionuclide content of particles in representative parts of the U deposit. Although Cigar Lake groundwaters contain particles in all sizes ranging from 10 nm to slightly larger than 20 μm, most samples contained a relatively high concentration of colloids in the 100–400 nm size range. Particle compositions are similar to the composition of minerals in the sandstones and ore body, suggesting that particles in groundwater are generated by the erosion of fracture-lining minerals. As a result, particle concentrations in groundwater are affected by the integrity of the host rock. In some piezometers the high initial concentrations of suspended particles, which may have been drilling artifacts, decreased during the collection of the first 350 1. Although colloid concentrations fluctuated during sampling, there are no indications that these concentrations will be permanently reduced by continued groundwater pumping. The observed colloid and suspended particle concentrations in the deep groundwaters are too low to have a significant impact on radionuclide migration, provided that radionuclide sorption is reversible. If radionuclides are irreversibly sorbed to particles they cannot sorb to the host rock and their migration can only be evaluated with an understanding of particle mobility. The data for dissolved and particulate U, Th and Ra were used to calculate field-derived distribution ratios (Rd) between particles and groundwater. The wide range of observed Rd values indicates that these radionuclides in particulate form are not in equilibrium with groundwater. U-series isotope data indicated that most of the U and Ra on particles was derived from groundwater. Some particles could have retained their U for as long as 8000 a. The U and Ra contents of particles in the ore and surrounding clay zones are significantly higher than in particles from sandstone, suggesting that the clay has been an effective barrier to particle migration.  相似文献   

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