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1.
The subsurface behaviour of 99Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)(aq) in pH 6-8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 × 10−9 atm O2). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 μmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)(aq) = 0.05-0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe-X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. 57Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O2·nH2O(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O2·nH2O(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit 99Tc remobilization upon the return of oxidizing conditions.  相似文献   

2.
Assessing the influence of CO2 on soil and aquifer geochemistry is a task of increasing interest when considering risk assessment for geologic carbon sequestration. Leakage and CO2 ascent can lead to soil acidification and mobilization of potentially toxic metals and metalloids due to desorption or dissolution reactions. We studied the CO2 influence on an Fe(III) (oxyhydr)oxide rich, gleyic Fluvisol sampled in close vicinity to a Czech mofette site and compared the short-term CO2 influence in laboratory experiments with observations on long-term influence at the natural site. Six week batch experiments with/without CO2 gas flow at 3 different temperatures and monitoring of liquid phase metal(loid) concentrations revealed two main short-term mobilization processes. Within 1 h to 1 d after CO2 addition, mobilization of weakly adsorbed metal cations occurred due to surface protonation, most pronounced for Mn (2.5–3.3 fold concentration increase, mobilization rates up to 278 ± 18 μg Mn kgsoil−1 d−1) and strongest at low temperatures. However, total metal(loid) mobilization by abiotic desorption was low. After 1–3 d significant Fe mobilization due to microbially-triggered Fe(III) (oxyhydr)oxide dissolution began and continued throughout the experiment (up to 111 ± 24 fold increase or up to 1.9 ± 0.6 mg Fe kgsoil−1 d−1). Rates increased at higher temperature and with a higher content of organic matter. The Fe(III) mineral dissolution was coupled to co-release of incorporated metal(loid)s, shown for As (up to 16 ± 7 fold, 11 ± 8 μg As kgsoil−1 d−1). At high organic matter content, re-immobilization due to resorption reactions could be observed for Cu. The already low pH (4.5–5.0) did not change significantly during Fe(III) reduction due to buffering from sorption and dissolution reactions, but a drop in redox potential (from > +500 mV to minimum +340 ± 20 mV) occurred due to oxygen depletion. We conclude that microbial processes following CO2 induction into a soil can contribute significantly to metal(loid) mobilization, especially at optimal microbial growth conditions (moderate temperature, high organic carbon content) and should be considered for carbon sequestration monitoring and risk assessment.  相似文献   

3.
The geochemistry of Se is largely controlled by that of iron, with which Se is closely affiliated in both oxidizing and reducing environments. In aerated waters the Se(IV) oxyanions, HSeO?3 and SeO2?3, are strongly adsorbed by hydrated surfaces of ferric oxides over the pH range 2–8; above pH8 adsorption decreases to complete desorption at pH 11. This adsorption immobilizes Se(IV) in neutral-to-acid waters and increases the range of oxidation potential over which Se(IV) is stable. During experimental aeration of aqueous Fe-S-Se systems, the stability field of Se(IV) is attained and elemental Se is slowly oxidized to this higher valence; oxidation potentials of the Se(VI) stability field were never reached, however, even by continued aeration of an alkaline system. Under reducing conditions, elemental Se either is incorporated within pyrite or forms the mineral ferroselite (FeSe2.Selenium geochemistry is summarized on an Eh-pH diagram, synthesized from equilibrium calculations, experimental work and reported geologic occurrences. A stability field for ferroselite, constructed for a Gibbs free-energy value of ?23.2 kcal/mole, is in accord both with its geologic occurrence and behavior and with conditions under which ferroselite has been synthesized. Traces on this diagram of Eh-pH variation show the behavior of selenium during oxidation of associated iron-sulfide minerals. Such considerations also demonstrate the manner in which selenium migrates, is deposited and is increasingly concentrated in roll-type sandstone uranium deposits, as well as the relative positions of the several forms of selenium within the deposit.  相似文献   

4.
《Applied Geochemistry》2005,20(11):2082-2096
Calcite is an important component of many potential host rocks currently under consideration for the disposal of radioactive wastes. Even in the chemically disturbed zone formed around a cementitious repository, this mineral remains largely unaffected by the hyper-alkaline waters migrating out of the near field. Thus, due to its abundance and geochemical stability, calcite could play an important role in the retardation of radionuclides released from a repository for nuclear wastes. Actinides are an important class of elements present in almost all radioactive waste streams, and for this reason, investigations of their retention behaviour under representative chemical conditions are particularly relevant to assessing safe disposal in the long term. Organic ligands originating from the degradation of cellulosic materials in the repository or present as cement additives could possibly reduce the retardation of tri- and tetravalent actinides due to the formation of stable metal–ligand complexes in solution. In this study, isosaccharinic acid (ISA) and gluconic acid (GLU) have been taken as representatives of cellulose degradation products and concrete admixtures, respectively. Batch-type sorption experiments have been conducted to investigate the effect of ISA and GLU on the retardation of 152Eu, 241Am and 228Th by calcite. 152Eu and 241Am are representatives of the trivalent lanthanides and actinides, respectively, and 228Th is a representative of the tetravalent actinides.High ISA and GLU concentrations in solution were found to significantly affect the sorption of the radionuclides. Rd values for Eu(III) and Am(III) decreased significantly at ISA concentrations above 10−5 M and at GLU concentrations above 10−7 M. The critical concentration limits were similar for Th(IV), that is 2 × 10−5 M in the case of ISA and 10−6 M in the case of GLU. The effects of ISA and GLU on the immobilisation of Eu(III), Am(III) and Th(IV) were interpreted in terms of complex formation in solution. In the case of Eu(III) and Am(III) in ACW, the metal–ligand complexes were found to have a 1:1 stoichiometry. Complexation constants of these aqueous ISA and GLU complexes with Eu(III) and Am(III) were determined and discussed in connection with the presently unclear situation concerning the stability constant of the Eu(OH)30 species. In the case of Th(IV) in ACW, it was assumed that a Th(IV)–ISA–Ca complex and a Th(IV)–GLU–Ca complex are formed, both having a 1:2:1 stoichiometry. The complexation constants of these complexes were determined and compared with the literature data.Assuming maximum concentrations for ISA and GLU in the pore water of the disturbed zone of a cementitious repository based on representative near-field conditions ([ISA]aq = 3 × 10−6 M, [GLU]aq = 10−7 M), it is predicted that the formation of aqueous ISA and GLU complexes would not significantly affect Eu(III), Am(III) and Th(IV) sorption on calcite.  相似文献   

5.
This work deals with structural and geochemical (chemical and isotopic) analyses of calcite veins hosted in Carrara marbles in the Alpi Apuane, NW Tuscany, Italy. Geometric features and spatial distribution of veins provided estimations of stress ratio (Φ = (σ2 − σ3)/(σ1 − σ3)), driving stress ratio (R′ = (Pf − σ3)/(σ1 − σ3)) and fluid overpressure (Δsi = Pf − σ3) at the time of vein formation. The obtained values of Φ = 32 and R′ = 0.43 reveal that fluid pressure was higher than the intermediate principal stress at the time of veins formation, whereas the estimated Δsi ranging from 129 to 207 MPa indicates that veins formed under supra-hydrostatic to lithostatic pressure conditions. Carbon (δ13CV-PDB = 1.81–2.10‰ for veins and 1.95–2.51‰ for host marbles), oxygen (δ18OV-SMOW = 28.71–29.57‰ for veins and 28.90–29.36‰ for host marbles) and strontium (87Sr/86Sr = 0.707716–0.707985 for veins and 0.0707708–0.707900 for host marbles) isotope compositions in vein/host marble pairs were internally quite consistent. Combining our structural and geochemical data, a modeling approach was performed to investigate the compositional features and temperatures of calcite depositing fluids. The results of our studies give evidence that (1) pore-fluids in Carrara marble, consisting of metamorphic formation waters, were re-mobilized during veining event and migrated within the veins in closed system conditions, (2) veins formed after ductile folding phases and before high-angle brittle faulting events, at temperature and pressure around 250 °C and 210 MPa, and finally (3) about 12 g H2O/m3 marble are calculated to have been available as vein parental fluid at the time of vein formation.  相似文献   

6.
《Applied Geochemistry》2006,21(10):1760-1780
Sulfide-rich mine tailings in Adak that are exposed to weathering cause acid mine drainage characterized by low pH (2–4) and high SO4 (up to 800 mg L−1). Surface water, sediment and soil samples collected in this study contain higher concentrations of As, Cu, Fe and Zn, compared to the target and/or intervention limits set by international regulatory agencies. In particular, high As concentrations in water (up to 2900 μg L−1) and sediment (up to 900 mg kg−1) are of concern. There is large variability in trace element concentrations, implying that both physical (grain size) and chemical factors (pH, secondary phases as sulfides, Al-oxides or clay minerals) play an important role in their distribution. The low pH keeps the trace elements dissolved, and they are transported farther downstream. Trace element partition coefficients are low (log Kd = 0.3–4.3), and saturation indices calculated with PHREEQC are <0 for common oxide and sulfidic minerals. The sediment and soil samples indicate an enhanced pollution index (up to 17), and high enrichment factors for trace elements (As up to 38,300; Zn up to 800). Finally, leaves collected from different plant types indicate bioaccumulation of several elements (As, Al, Cu, Fe and Zn). However, some of the plants growing in this area (e.g., Salix, Equisétum) are generally resistant to metal toxicity, and hence, liming and phytoremediation could be considered as potential on-site remediation methods.  相似文献   

7.
In the DI-A2 experiment several non-reactive and reactive tracers were injected as a pulse in a packed-off borehole in the Opalinus Clay. Unlike the previous DI-A1 test, the design of the Teflon filter in the injection borehole forced the water to flow through the filter and the open space between the filter and the borehole wall (the filter itself did not act as a diffusion barrier between the circulating solution and the rock). The decrease in tracer concentration in the liquid phase was monitored during a period of a year. Afterwards, the borehole section was overcored and the tracer profiles in the rock were analyzed. A main interest of this experiment was to understand the chemical behavior of sorbing tracers: Cs+ (stable), 85Sr2+, 60Co2+ and Eu3+ (stable). The complete dataset (except for Eu3+ because of strong sorption to experimental equipment) was analyzed in a previous study with a 2D diffusion–reaction model and the derived diffusion and sorption parameters were compared with laboratory data. As in DI-A1, a difference by a factor of about 2 for sorption (magnitude of the Freundlich isotherm) was obtained between in situ and laboratory batch sorption experiments.Recent experimental and modeling studies have shown equivalent Cs+ sorption on intact and disaggregated Opalinus Clay samples. In view of these developments, new modeling of Cs+ diffusion and retention in the DI-A2 experiment has been performed using CrunchFlow. The calculations include transport by diffusion and a multisite cation exchange model to account for the retention of Cs+. The new results show that upscaling of Cs+ sorption from laboratory to field is no longer required. However, a difference in sorption by a factor of about 2 is still explained by the use of different versions of the same cation exchange model (a small difference in the selectivity coefficient for one type of site). This uncertainty in sorption leads to an uncertainty in the effective diffusion coefficient (De) for Cs+, also by a factor of 2 (2–4 × 10−10 m2/s). Clearly, the values of De obtained are correlated with the strength of sorption in the model, with stronger sorption leading to larger De values. Discrimination between the two versions of the exchange model is not possible when using only the results of the in situ test. Additionally, during early times (t < 10 days) the drop in Cs+ concentration in the circulation system is slower than expected. Due to the experimental setup, this slow decrease in concentration cannot be caused by the filter in the contact between borehole and rock. Poor mixing in the circulation system could explain this effect.  相似文献   

8.
《Chemical Geology》2007,236(3-4):323-338
Serpentinized garnet peridotites from the Xugou peridotite body of the Sulu ultrahigh-pressure (UHP) metamorphic terrane, central eastern China, are refractory (olivines have Fo91.7–93.1), indicating their origin as residual mantle. Negative correlations between whole-rock MgO and TiO2, Al2O3, total Fe2O3 and CaO (r = − 0.90 to − 0.95) and positive correlations between whole-rock Al2O3 and CaO and incompatible elements [Li, V, Cu, Ga, Sr, Y, Zr, heavy rare earth elements (HREEs), Hf, Pb and U] (r = 0.69 to 0.98) likely reflect melt depletion trends. Four highly refractory samples were selected for Re–Os isotopic analysis. Although they show evidence of variable enrichment of incompatible elements during serpentinization/metasomatism, no correlations exist between 187Re/188Os or 187Os/188Os with either La or Re (r = 0.00 to 0.17). These results indicate that any Re addition was fairly recent and did not affect the Os isotopic composition significantly. The correlation between 187Os/188Os and 187Re/188Os ratios thus, most likely reflects an ancient melt extraction event.The TRD, TMA and errorchron ages of the Xugou peridotites are all similar, suggesting that these peridotites formed around 2.0 Ga ago. This age is similar to Os model ages of mantle peridotites from the Dabie terrane, but contrasts markedly with the Archean ages of the continental lithospheric mantle (CLM) beneath the eastern block of the North China craton (NCC). If we assume that the Dabie–Sulu belt formed by the Triassic collision of the Yangtze craton with the eastern block of NCC and that the Archean aged CLM of the latter persisted until the Triassic, the Paleoproterozoic ages suggest derivation of these Dabie–Sulu mantle peridotites from the Yangtze craton. A Yangtze craton origin is consistent with the existing tectonic model of the Dabie–Sulu UHP belt. Our results support the hypothesis that the crust and underlying lithospheric mantle of the Yangtze craton were subducted to depths of > 180–200 km to form the world's largest UHP belt.  相似文献   

9.
We collected groundwaters in and around a large (313 Mt at 1.08% Cu and 0.3% cutoff) undisturbed porphyry copper deposit (Spence) in the hyperarid Atacama Desert of northern Chile, which is buried beneath 30–180 m of Miocene piedmont gravels. Groundwaters within and down-flow of the Spence deposit have elevated Se (up to 800 μg/l), Re (up to 31 μg/l), Mo (up to 475 μg/l) and As (up to 278 μg/l) concentrations compared to up-flow waters (interpreted to represent regional groundwater flow). In contrast, Cu is only elevated (up to 2036 μg/l) in groundwaters recovered from within the deposit; Cu concentrations are low down gradient of the deposit. The differential behavior of the metals/metalloids occurs because the former group dissolves as anions, enhancing their mobility, whereas the base metals dissolve as cations and are lost from solution most likely through adsorption to clay surface exchange sites and through formation of secondary copper chlorides, carbonates, and oxides. Most groundwaters within and down-flow of the deposit have Eh–pH values around the FeII/FeIII phase boundary, limiting the impact of Fe-oxyhydroxides on oxyanions mobility. Se, Re, Mo, and As are all mobile (with filtered/unfiltered samples ～ 1) to the limit of sampling 2 km down gradient from the deposit. The increase in ore-related metals, metalloids, and sulfate and decrease in sulfate–S isotope ratios (from values similar to regional salars, + 4 to + 8‰ δ34SCDT to lower values closer to hypogene sulfides, + 1 to + 4‰ δ34SCDT) is consistent with active water–rock reactions between saline groundwaters and the Spence deposit. It is likely that hypogene and/or supergene sulfides are being oxidized under the present groundwater conditions and mineral saturation calculations suggest that secondary copper minerals (antlerite, atacamite, malachite) may also be actively forming, suggesting that supergene and exotic copper mineralization is possible even under the present hyperarid climate of the Atacama Desert.  相似文献   

10.
Significant amounts of sulfuric acid (H2SO4) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; RSi, RAl, RFe) increased with decreasing solution pH and increasing temperature. For example, the highest log RSi value was obtained at pH 1 and 45 °C (−9.07 mol g−1 s−1), while the lowest log RSi value was obtained at pH 4 and 25 °C (−11.20 mol g−1 s−1). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol−1 (pH 1) to 37.7 kJ mol−1 (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H2SO4/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.  相似文献   

11.
The A'gui Cu deposit is located in the eastern slope of the southern Great Xing'an Range (SGXR), and it is a vein-type Cu deposit spatially and temporally related to the Cretaceous monzogranite which intruded Pingshan Formation. Vein-type Cu orebodies are mainly hosted in the NE and nearly EW faults. Previous studies on the A'gui deposit mainly focused on geological exploration, and there was no study on its fluid evolution and genesis. Therefore, we carried out conducted fluid inclusion and stable isotope (C–H–O–S–Pb) analysis to study the fluid evolution, fluid and ore-forming material sources and genesis of the A'gui deposit. According to the field investigations and mineral crosscutting relationships, four paragenetic stages were identified: quartz–pyrite–chalcopyrite–pyrrhotite–arsenopyrite ± magnetite (Stage I), quartz–pyrite–chalcopyrite (Stage II), quartz–chalcopyrite ± pyrite–sphalerite–galena (Stage III) and carbonate ± quartz (Stage IV). From Stage I to Stage II, the assemblage of fluid inclusions (FIs) in quartz is characterized by the development of daughter mineral–bearing three–phase FIs (SL–type), vapour FIs (V–type), vapour–rich two–phase aqueous FIs (LV–type) and liquid–rich two–phase aqueous FIs (VL–type). Only VL–type FIs appeared in the Stage III quartz and Stage IV calcite. The homogenization temperatures of FIs in stages I, II, III and IV are 329–390 °C, 255–336 °C, 166–244 °C and 120–157 °C, with salinities of 3.37–45.33 wt%, 3.53–39.76 wt%, 4.17–7.86 wt% and 3.37–7.15 wt% NaCl eqv., respectively. The fluid inclusion type assemblage suggested that obvious fluid boiling occurred in the Stage I and Stage II. Fluid boiling may be the reason for the precipitation of useful minerals. According to the HO isotope analysis of stages I–II quartz (δ18OH2O = −2.1 to 3.2 ‰, δDV–SMOW = −128.4 ‰ to −110.6 ‰), the fluid was originally magmatic water. From Stage III to Stage IV (δ18OH2O = −12.3 to −2.3 ‰, δDV–SMOW = −129.6 ‰ to −104.2 ‰), the HO isotope value is obviously close to the meteoric water line, indicating that meteoric water is mixed with evolved magmatic solutions. The ore–forming fluid of the A'gui deposit represents a medium–high temperature NaCl-H2O magmatic hydrothermal system. The C isotope compositions (δCV–PDB = −5.74 ‰ to −4.76 ‰) in stage IV indicate that the C in the fluid was derived from a magmatic source and was affected by meteoric water. In addition, the measured S isotope compositions in stages I–III of the hydrothermal fluids (δ34SV–CDT = 2.2 to 3.7 ‰) indicate that S mainly comes from granitic magma. Further, the Pb isotope (206Pb/204Pb = 18.276–18.367, 207Pb/204Pb = 15.52–15.556, 208Pb/204Pb = 38.157–38.193) in stages I–III indicate that the ore-forming materials are derived from the mixture of mantle and orogenic material. In summary, this study showed the A'gui is a typical magmatic hydrothermal vein-type Cu deposit that related to Cretaceous monzogranite formed under the joint constraints of Mongolia-Okhotsk Ocean and Paleo-Pacific Ocean tectonic system. Fluid boiling and mixing are the main ore-forming mechanism.  相似文献   

12.
《Applied Geochemistry》2000,15(8):1203-1218
Ca6[Al(OH)6]2(CrO4)3·26H2O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca6[Al(OH)6]2(CrO4)3·26H2O⇌6Ca2++2Al(OH)−4+3CrO2−4+4OH−+26H2O varies with pH unless a CaCrO4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca2++CrO2−4=CaCrO4(aq) was obtained by minimizing the variance in the IAP for Ca6[Al(OH)6]2(CrO4)3·26H2O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log KSP) of Ca6[Al(OH)6]2(CrO4)3·26H2O at 25°C is −41.46±0.30. The temperature dependence of the log KSP is log KSP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG0r,298 and ΔH0r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol−1. the values of ΔC0P,r,298 and ΔS0r,298 are −1506±140 and −534±83 J mol−1 K−1. Using these values and published standard state partial molal quantities for constituent ions, ΔG0f,298=−15,131±19 kJ mol−1, ΔH0f,298=−17,330±8.6 kJ mol−1, ΔS0298=2.19±0.10 kJ mol−1 K−1, and ΔC0Pf,298=2.12±0.53 kJ mol−1 K−1, were calculated.  相似文献   

13.
In this study we experimentally determine phlogopite/melt partition coefficients of Ra and other trace elements in a lamproitic system. This work was achieved using an analytical technique (LA-ICP-MS) with low detection limits (~ 0.01 fg) permitting the measurement of the very low Ra concentrations feasible in experiments (~ 1 ppb). DRaphlogopite/melt was determined to 2.28 ± 0.44 and 2.84 ± 0.47 in two experiments, the ratio DRa/DBa is around 1.6. The compatibility of Ra in phlogopite results from an ionic radius being close to the apex of the lattice strain parabola for earth alkalis in the large XII-coordinated interlayer site of phlogopite. A re-evaluation of DRa and DRa/DBa for magmatic minerals containing appreciable Ra, yields DRamineral/melt ranging from ~ 2.6 for phlogopite down to 2–3 ? 10? 5 for pyroxenes, and DRa/DBamineral/melt from ~ 4 for leucite to 2 ? 10? 2 for orthopyroxene. The influence of melt composition on DRa/DBa is less than 10%. All investigated minerals have different DRa/DBa, strongly fractionating Ra from Ba. Thus, for magmatic systems, (226Ra)/Ba in the various minerals is not constant, these minerals do not form a straight line in the (226Ra)/Ba–(230Th)/Ba system at the time of crystallization and thus, there is no (226Ra)/Ba–(230Th)/Ba isochron at t0. 226Ra–230Th–Ba mineral dating is thus applicable only to model ages calculated from mineral–glass pairs with known DRa.  相似文献   

14.
《Applied Geochemistry》2005,20(1):193-205
Sorption and precipitation of Co(II) in simplified model systems related to the Hanford site high-level nuclear waste tank leakage were investigated through solution studies, geochemical modeling, and X-ray absorption fine structure (XAFS) spectroscopy. Studies of Co(II) sorption to pristine Hanford sediments (ERDF and Sub), which consist predominantly of quartz, plagioclase, and alkali feldspar, show an adsorption edge centered at pH ≈ 8.0 for both sediments studied, with sorption >99% above pH ≈ 9.0. Aqueous SiO2 resulting from dissolution of the sediments increased in concentration with increasing pH, though the systems remained undersaturated with respect to quartz. XAFS studies of Co(II) sorption to both sediment samples reveal the oxidation of Co(II) to Co(III), likely by dissolved O2, although this oxidation was incomplete in the Sub sediment samples. The authors propose that Fe(II) species, either in aqueous solution or at mineral surfaces, partially inhibited Co(II) oxidation in the Sub sediment samples, as these sediments contain significantly higher quantities of Fe(II)-bearing minerals which likely partially dissolved under the high-pH solution conditions. In alkaline solutions, Al precipitated as bayerite, gibbsite, or a mixture of the two at pH > 7; an amorphous gel formed at pH values less than 7. Aqueous Co concentrations were well below the solubility of known Co-bearing phases at low pH, suggesting that Co was removed from solution through an adsorption mechanism. At higher pH values, Co concentrations closely matched the solubility of a Co-bearing hydrotalcite-like solid. XAFS spectra of Co(II) sorbed to Al-hydroxide precipitates are similar to previously reported spectra for such hydrotalcite-like phases. The precipitation processes observed in this study can significantly reduce the environmental hazard posed by 60Co in the environment.  相似文献   

15.
The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al2O3 and TiO2, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al2O3 (<3 wt%), TiO2 (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al2O3 (>3 wt%), TiO2, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu1PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu1PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe3+/(Fe3+/Fe2+) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ13CV-PDB (−4.0‰ to −6.6‰) and δ18OV-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ13CV-PDB = −0.8‰ to + 3.1‰ and δ18OV-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu1PAAS and δ13CV-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO2, with the deeper water, from which the carbonate facies BIF formed, depleted in δ13C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe2+-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe2+-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.  相似文献   

16.
《Applied Geochemistry》2004,19(11):1785-1800
Historical Au-ore exploitation at the Chéni mine in the Massif Central, France, generated 525,000 tonnes of finely ground mill tailings deposited in a heap that has spread with time into three settling basins. The tailings, which are rich in quartz (80%), mica and clay minerals (10% of illite, smectite, kaolinite and chlorite), feldspars (5%) but poor in carbonates (<1%), also contain sulphides (around 5%, mainly pyrite and arsenopyrite). Arsenic content of the tailings is around 6 g kg. This paper describes the geochemistry of drainage waters, with special attention paid to in situ values of the three major redox couples, namely Fe(II)/Fe(III), As(III)/As(V) and S(IV)/S(VI). The water samples range from acidic and oxidized (pH 2.9, Eh +700 mV) to moderate pH and weakly reducing (pH 7.6, Eh 15 mV). The waters are rich in SO4 and Ca and have variable As (0.05–95 mg L−1) and Fe concentrations (0.07–141 mg L−1). Reduced As(III) species predominate over As(V) species (As(III)/As(V) up to 21), whereas oxidized forms of Fe and S are favoured (Fe(II)/Fe(III) up to 0.5, and S(IV)/S(VI) up to 1).Thermodynamic calculations were performed with the PHREEQC and EQ3NR codes based on a revised As database to evaluate saturation indices (SI) of the waters in relation to the main minerals and define which redox couples control the redox state of the system. The important role of carbonates, though only present in small amounts, explains the acid buffering generated by the oxidation of sulphides for waters in the pH 7–7.5 range. Measured Eh appears to fall between the calculated Eh of the Fe(II)/Fe(III) couple and that of the As(III)/As(V) couple, illustrating redox disequilibrium.  相似文献   

17.
Recently, 6-methyl branched glycerol dialkyl glycerol tetraethers (brGDGTs) were separated from 5-methyl brGDGTs, which are used in brGDGT-based proxies. Here we analyzed brGDGTs in 27 soil samples along the 400 mm isoline of mean annual precipitation in China by using tandem 2D liquid chromatography. The fractional abundance of 6-methyl brGDGTs showed a positive correlation with soil pH, while that of 5-methyl brGDGTs decreased with increasing soil pH. The abundance ratio of 6-/5-methyl brGDGTs, namely the isomerization of branched tetraethers (IBT), was calculated. The correlation of IBT with pH (pH = 6.33 − 1.28 × IBT; R2 0.89; root mean squared error, RMSE, 0.24) was much stronger than that of the traditionally used cyclization index of branched tetraethers (CBT) with pH (R2 0.52; RMSE 0.49) and comparable with that of CBT′ with pH (R2 0.88; RMSE 0.25). Compiling all available data from 319 soil samples resulted in a global calibration: pH = 6.53 − 1.55 × IBT (R2 0.72; RMSE 0.65), which has a better correlation than the CBT5ME-pH proxy (R2 0.63; RMSE 0.78), but a weaker correlation than the CBT′-pH proxy (R2 0.85; RMSE 0.52). Our result suggests that the IBT is a promising indicator for soil pH, particularly in cases when some compounds in the CBT′ index cannot be determined.  相似文献   

18.
《Applied Geochemistry》2006,21(3):515-527
Dissolved and particulate Hg fluxes in the Lot–Garonne–Gironde fluvial-estuarine system were obtained from observation of daily discharge and suspended particulate matter (SPM) concentrations. In addition to the measurements of the total dissolved (<0.45 μm) and particulate Hg (>0.45 μm), called HgTD and HgTP respectively, the dissolved inorganic Hg species (HgRD) were determined monthly. Geochemical background values for HgTP in sediments and SPM were similar to crustal values and to typical concentrations in SPM of non-contaminated river systems, respectively. The Riou Mort watershed already known as the origin of important historical polymetallic (e.g., Cd, Zn) pollution was identified as an important Hg point source. In the downstream Lot River, Hg concentrations were clearly higher than those in other moderately contaminated systems. The mean relative contribution of HgRD to HgTD in the Lot River and in the Garonne River was close to 25% and 50%, respectively, and showed no correlation with water discharge or SPM concentration. Depending on the origin and nature of SPM, HgTP concentrations were correlated or not with particulate organic C (POC). Maximum HgTP concentrations were measured in samples containing low POC concentrations and were attributed to sediment resuspension. In contrast, high POC concentrations (6–17%) during algal blooms were associated with low/moderate HgTP concentrations (<0.5 mg kg−1) at different sites, suggesting that Hg concentrations in fluvial phytoplankton may be limited by bioavailability of dissolved Hg and/or physiologically controlled Hg accumulation. Mercury was mostly (up to 98%) transported in the particulate phase with estimated annual Hg fluxes at the outlet of the Lot River system ranging from 35 to 530 kg a−1 for the past decade. The minimum anthropogenic component (58–84% of total Hg fluxes) could not be explained by present Riou Mort point source contributions, suggesting important Hg release from contaminated sediment as a major source and from downstream point sources (e.g., coal-fired power plants and/or metal processing industries). HgTP concentrations and fluxes were strongly related to hydrologic variations and were clearly increased by riverbed dredging during lock construction. Therefore, the estimated Hg stocks in the Lot River sediment (5–13 tons) represent an important potential Hg source for the downstream fluvial-estuarine system.  相似文献   

19.
Whole rock elemental and Sr–Nd isotope geochemistry and in situ K-feldspar Pb isotope geochemistry were used to identify the sources involved in the genesis of Neoproterozoic granites from the Embu Terrane, Ribeira Belt, SE Brazil. Granite magmatism spanned over 200 Ma (810–580 Ma), and is dominated by crust-derived relatively low-T (850–750 °C, zircon saturation) biotite granites to biotite-muscovite granites. Two Cryogenian plutons show the least negative εNdt (−8 to −10) and highest mg# (30–40) of the whole set. Their compositions are strongly contrasted, implying distinct sources for the peraluminous (ASI ∼ 1.2) ∼660 Ma Serra do Quebra-Cangalha batholith (metasedimentary rocks from relatively young upper crust with high Rb/Sr and low Th/U) and the metaluminous (ASI = 0.96–1.00) ∼ 630 Ma Santa Catarina Granite. Although not typical, the geochemical signature of these granites may reflect a continental margin arc environment, and they could be products of a prolonged period of oceanic plate consumption started at ∼810 Ma. The predominant Ediacaran (595–580 Ma) plutons have a spread of compositions from biotite granites with SiO2 as low as ∼65% (e.g., Itapeti, Mauá, Sabaúna and Lagoinha granites) to fractionated muscovite granites (Mogi das Cruzes, Santa Branca and Guacuri granites; up to ∼75% SiO2). εNdT are characteristically negative (−12 to −18), with corresponding Nd TDM indicating sources with Paleoproterozoic mean crustal ages (2.0–2.5 Ga). The Guacuri and Santa Branca muscovite granites have the more negative εNdt, highest 87Sr/86Srt (0.714–0.717) and lowest 208Pb/206Pb and 207Pb/206Pb, consistent with an old metasedimentary source with low time-integrated Rb/Sr. However, a positive Nd–Sr isotope correlation is suggested by data from the other granites, and would be consistent with mixing between an older source predominant in the Mauá granite and a younger, high Rb/Sr source that is more abundant in the Lagoinha granite sample. The Ediacaran granites are coeval with profuse granite magmatism attributed to continental arc magmatism in northern Ribeira and Araçuaí belts. However, their evolved compositions with low mg# and dominantly peraluminous character are unlike those of magmatic arc granites, and they are more likely products of post-collisional magmatism or correspond to an inner belt of crust-derived granites.  相似文献   

20.
Varying pertechnetate (Tc(VII)) doses were reduced to Tc(IV) in the presence and absence of Gorleben humic substances with the aid of magnetite, a reducing Fe(II)-containing surface. In absence of humic substances dissolved Tc(IV) concentrations are over-saturated with respect to the known TcO2 · nH2O solubility and increase with increasing Tc(VII) dose due to the formation of a range of mononuclear to colloidal Tc(IV) species. In presence of dissolved humic substances, the Tc solubility is enhanced due to the additional interaction of dissolved Tc(IV) species with humic substances. Both in the absence and the presence of dissolved humic substances a sorption mechanism controls the distribution of the range of mononuclear to colloidal Tc(IV) species between the solid and the liquid phase. The proposed reaction mechanism between Tc(IV) and HS is represented by Σ[TcO(OH)2]n+HS = [TcO(OH)2]n − HS in which Σ[TcO(OH)2]n stands for the sum of monomeric and polynuclear (colloidal) Tc(IV) species present in the equilibrium solution. A log K-value of 2.9 (±0.3) was quantified from a modified Schubert approach which is based on the competition of HS and magnetite for all dissolved Tc(IV) species and was found independent of Tc–HS loading, Tc–magnetite loading and pH.  相似文献   

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