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1.
UV femtosecond laser ablation coupled to MC-ICP-MS provides a promising in situ tool to investigate elemental and isotope ratios by non-matrix-matched calibration. In this study, we investigate Fe isotope composition in siliceous matrices including biotite, hornblende, garnet, fayalite and forsterite (San Carlos Olivine), and an oceanic Fe–Mn crust using the iron reference material IRMM-014 for calibration. To test the accuracy of the laser ablation data, Fe isotope compositions were obtained independently by solution ICP-MS after chromatographic separation of Fe. Sample materials with low Cr content, i.e. biotite, hornblende, fayalite and the Fe–Mn crust, reveal δ56/54Fe and δ57/54Fe values that agree with those from solution ICP-MS data within the measured precision. For high Cr concentration (54Cr/54Fe >0.0001), i.e. in the garnet and forsterite sample, δ56/54Fe and δ57/54Fe values were derived from 57Fe/56Fe ratios as correction of the isobaric interference of 54Cr on 54Fe is unsatisfactory. This approach provides accurate results for both minerals. Moreover, the garnet crystal exhibits isotopic zonation with differences of 0.3‰ in δ56/54Fe showing that substantial heterogeneities exist in high-temperature metamorphic minerals. Multiple analyses of homogeneous sample materials reveal a repeatability of 0.1‰ (2 SD) for δ56/54Fe and 0.2‰ (2 SD) for δ57/54Fe, respectively. This study adds to the observations of Horn et al. (2006) who have shown that the determination of Fe isotope ratios in various matrices including iron alloys, iron oxides and hydroxides, iron sulfide and iron carbonates can be performed with high accuracy and precision at high spatial resolution using UV femtosecond laser ablation ICP-MS. These results demonstrate that femtosecond laser ablation ICP-MS is a largely matrix-independent method, which provides a substantial advantage over commonly employed nanosecond laser ablation systems.  相似文献   

2.
Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fetotal and 84% of Mntotal). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m–2 d–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m–2 d–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m–2 d–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m–2 d–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm–3 d–1, respectively.  相似文献   

3.
We have detected micrometre-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using an UV femtosecond laser ablation system connected to a MC-ICP-MS. In the magnetite–carbonate–chert BIF from the Archean Old Wanderer Formation in the Shurugwi Greenstone Belt (Zimbabwe), magnetite shows neither intra- nor inter-layer trends giving overall uniform δ56Fe values of 0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual δ56Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and δ56Fe end member values are 0.4‰ for siderite and −0.7‰ for ankerite. The data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by Fe(III)-reducing bacteria; or more likely an abiotic reaction of organic carbon and Fe(III) during low-grade metamorphism. Si isotope composition of the Old Wanderer BIF also shows significant variations with δ30Si values that range between −1.0‰ and −2.6‰ for bulk layers. These isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal-rich waters. Interestingly, Fe and Si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures. Moreover, the changes of Fe and Si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal-rich water which govern the rates of Fe and Si precipitation and therefore also the development of layering. During periods of low hydrothermal activity, precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate–chert layers. During periods of intensive hydrothermal activity, precipitation rates of ferric oxyhydroxide were high, and subsequent diagenesis triggered only partial reduction, forming magnetite–carbonate–chert layers. We are confident that our micro-analytical technique is able to detect both the solute flux history into the sedimentary BIF precursor, and the BIF’s diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors.  相似文献   

4.
Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO42−, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO42− and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.  相似文献   

5.
Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H2SO4, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L−1, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO4–H+ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H+ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO4–H+ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H+ solutions.  相似文献   

6.
The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l− 1) and sulphates (up to 1190 mmol l− 1).The δ56Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ56Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ56Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ56Fesolid–water < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.  相似文献   

7.
On the south-eastern edge of Russia, the chemical composition of rainwater is controlled by sea salts, terrestrial material, as well as volcanic (Kuril islands volcanic area) and anthropogenic emissions, mostly in the southern part of the area. The predominant major ions of the Primorye, Sakhalin and the Kuril Islands rainwaters were respectively HCO3−–SO42−, Ca–Na, and of Cl–Na. Concentration of trace elements changes within 1–2 orders of magnitude but some difference in the distribution of the elements between continental and island rainwater is found. The concentration of the chemical elements in the particulate fraction varies from < 10% to 90% of the total concentration (dissolved + particulate) with the following distribution: Tl, Na, Ca, Sr, Zn, Cd (< 10%)–Be, Th, Bi, Rb, U, K, Sc (10–20%)–Cu, Mn, Mg, Mo, Se, Ba, Ni, As, Ag, Cs, Co, Y, Ga, V (20–50%)–Sb, Pb, Ge, Cr, Fe, Al (50–90%).The concentration of elements of the particulate fraction of the rainwater usually is significantly different from concentrations in the crust, including both higher and lower concentrations. The terrestrial contribution to dissolved elements was evaluated and follows the decreasing order: Fe > K, Mg, Ca > Ba, Sr > Na (65–1%). Close order was found for total (dissolved and solid) concentrations. Sea salt contribution to dissolved element concentration in the rainwater decrease in the following order: Cl, Mg > K, SO4 > Ca > HCO3−, Ba, Fe (78–0.1%). Calculation of anthropogenic and volcanic inputs for two ions (Cl− and SO42−) shows that anthropogenic inputs for the Vladivostok and Yuzno-Sakhalinsk cities can be evaluated as 15–20% of Cl− and up to 80–90% of SO42−. Volcanic components in the Kuril Islands, where anthropogenic inputs are absent, can reach up to 76% of SO42− and 36% of Cl−.  相似文献   

8.
Total suspended particulate samples (TSP) were collected and concentrations measured during seventeen months in the vicinity of a ceramic industrial area. A method of fractionating was applied to the samples in order to obtain two fractions corresponding to mineral particulate coming from dust emissions (Upper-F fraction) and to amorphous matter (carbon plus small amounts of S, Ca, Fe, etc) coming mainly from traffic and other combustion processes. Also for TSP samples several element concentrations were measured following two previous treatments: extraction of elements mainly associated with the soluble fraction of the samples (B, Fe, P, As, NO2–, NH4+, Cl–, F) and acid digestion for trace metals and elements mainly associated with the non-soluble fractions of the samples (Fe, As, Cd, Ni, Pb, Zn Ca). Seasonal differences and the influence of meteorological parameters (temperature, relative humidity, pressure and wind conditions) on the air pollution levels, particles as well as ions, were studied.Results show different seasonal and weekly evolution for mineral and amorphous carbonaceous particles because of the different origins in dust emissions or combustion processes respectively, and the different physical properties such as size grain. Of the ions analyzed Fe, Ca and Zn were clearly associated to mineral phases and consequently related to dust emissions, and NO2–, NH4+, P, Cl– were related to amorphous matter coming from combustion. Ni and Cd show lower levels than those reported as guideline values and the source is mainly related to the enrichment of these elements in clay materials. B and As content result in elevated concentrations, with the tendency to increase during cold months. The emission of these elements was associated with vaporization or volatilization during high temperature ceramic processes. The original gaseous state is influenced by temperature. In the winter the content for B and As is higher due to enhanced condensation of gas-phase boron onto particles, while in the summer the increase of air temperature results in elevated evaporation.  相似文献   

9.
Analysis of 3-m sediment cores revealed that profiles of carbon (C), sulfur (S), and iron (Fe) varied with relative distance from marine and terrestrial sediment sources in Tomales Bay California. Despite relatively high sedimentation rates throughout the bay (historically 3–30 mm yr−1), sulfate reduction of deposited organic matter led to free-sulfide accumulation in sediments only at the location farthest from terrestrial runoff, the source of reactive iron. Acid-volatile sulfide concentrations in all sediments (<10 μmol g−1) were low relative to concentrations of chromiumreducible sulfide (up to 400 μmol g−1 farthest from the reactive iron source). A calculated index of iron availability, used to describe sediment resistance to build-up of free sulfide, was lowest at this location. Recent, upward shifts in reactive Fe concentration and in the relative contribution of terrestrial orgnic carbon (measured as a shift in δ13C of bulk sediment organic matter) in all cores indicated that erosion and transport of sediments from the watershed surrounding Tomales Bay increased after European settlement in the 1850s.  相似文献   

10.
This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)9S8. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol–1, 20.52 J K–1 mol–1, and 6.99 × 10–6 m3 mol–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 102 T –1+8.41 x 10–7 T –1 P, where K = (Fe/Ni)octahedral /(Fe/Ni)tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol–1.  相似文献   

11.
Mg–Fe interdiffusion rates have been measured in wadsleyite aggregates at 16.0–17.0 GPa and 1230–1530 °C by the diffusion couple method. Oxygen fugacity was controlled using the NNO buffer, and water contents of wadsleyite were measured by infrared spectroscopy. Measured asymmetric diffusion profiles, analyzed using the Boltzmann–Matano equation, indicate that the diffusion rate increases with increasing iron concentration and decreasing grain size. In the case of wadsleyite containing 50–90 weight ppm H2O, the Mg–Fe interdiffusion coefficients at compositions of Mg/(Mg + Fe)=0.95 in the coarse-grained region (about 60 m) and 0.90 in the fine-grained region (about 6 m) were determined to be a DXmg = 0.95 (m2 s–1)=1.24 × 10–9 exp[–172 (kJ mol–1)/RT] and DXmg = 0.90 (m2 s–1)=1.77 × 10–9 exp[–143 (kJ mol–1)/RT], respectively. Grain-boundary diffusion rates were estimated to be about 4 orders of magnitude faster than the volume diffusion rate. Grain-boundary diffusion dominates when the grain size is less than a few tens of microns. Results for the nominally dry diffusion couple in the present study are roughly consistent with previous studies, taking into account differences in pressure and grain size, although water contents of samples were not clear in previous studies. We observed that the diffusivity is enhanced by about 1 order of magnitude in wadsleyite containing 300–2100 wt. ppm H2O at 1230 °C, which is almost identical to the enhancement associated with a 300 °C increase in temperature. It is still not conclusive that a jump in diffusivity exists between olivine and wadsleyite because water contents of olivine in previous diffusion studies and effects of water on the olivine diffusivity are uncertain.  相似文献   

12.
The local structural heterogeneity and energetic properties of 22 natural Mg–Fe cordierites, ideal formula (Mg,Fe)2Al4Si5O18·x(H2O,CO2), were investigated at length scales given by powder infrared spectroscopy (IR) and also by published electronic absorption spectra. The studied samples have iron mole fractions from XFe = 0.06 to 0.82 and cover most of the Mg–Fe cordierite binary. Variations in wavenumbers and line widths of the IR bands were determined as a function of composition. Most modes shift linearly to lower wavenumbers with increasing XFe, except those at high wavenumbers located between 900 and 1,200 cm-1. They are vibrations that have a large internal (Si,Al)O4 character and are not greatly affected by Mg–Fe exchange on the octahedral site. The lower wavenumber modes can be best characterized as lattice vibrations having mixed character. The systematics of the wavenumber shifts suggest small continuous variations in the "average" cordierite structure with Mg–Fe exchange and are consistent with an ideal volume of mixing, Vmix= 0, behavior (Boberski and Schreyer 1990). IR line broadening was measured using the autocorrelation function for three wavenumber regions in order to determine the range of structural heterogeneity between roughly 2 and 100 Å (0.2–10.0 nm) in the solid solution. In order to do this, an empirical correction was first made to account for the effect that small amounts of channel Na have on the phonon systematics. The results show that between 1,200 and 540 cm-1 the line widths of the IR bands broaden slightly and linearly with increasing XFe. Between 350 and 125 cm-1 nonlinear behavior was observed and it may be related to dynamic effects. These results suggest minimal excess elastic enthalpies of mixing for Mg–Fe cordierite solid solutions. Channel Na should affect measurably the thermodynamic properties of natural cordierites as evidenced by variations in the IR spectra of Na-containing samples. Occluded H2O (Class I) and CO2 should have little interaction with the framework and can be considered nearly "free" molecules. They should not give rise to measurable structural heterogeneity in the framework. The contribution of the crystal field stabilization energy (CFSE) of octahedral Fe2+ to the energetics of Mg–Fe cordierites was also investigated using published electronic absorption spectra (Khomenko et al. 2001). Two bands are observed between 8,000 and 10,500 cm-1 and they represent electronic dd-excitations of octahedral Fe2+ derived from the 5T2g 5Eg transition. They shift to higher wavenumbers with increasing XMg in cordierite. An analysis gives slightly asymmetric excess -CFSE across the Mg–Fe cordierite join with a maximum of about –550 J/mole towards iron-rich compositions.Editorial responsibility: J. Hoefs  相似文献   

13.
The present study aims to model iron speciation when interacting with natural organic matter. Experimental data for iron speciation were achieved with insolubilized humic acid as an organic matter analogue for 1.8 × 10− 3 M and 1.8 × 10− 4 M iron concentrations and 2–5 pH range. Combining EPR spectroscopy and chemical analysis allowed us to fit NICA-Donnan model parameters for both organic complexation of iron and oxides precipitation.  相似文献   

14.
Complete chemical analyses of the inner and outer portions of zoned phlogopite indicate differences in concentrations of 15 major and minor constituents. Concentrations of aluminium, sodium and zinc increase while those of other oxides decrease in the rim. Distribution coefficients of major and minor oxides between the rim and the core (KDoxr–c) indicate a slight decrease for Si, Fe2+, Mg, K and Sr (0.99–0.9); a greater decrease for Rb and water (0.86–0.83), and a significant decrease for Ti, Fe3+, Mn, Ni, and F (0.50–0.71).Physical and structural properties of the phlogopite portions from the core and the rim are similar, but phlogopite in the core contains exsolved rutile needles and fine-grained mica specks (0.5%) which cause white appearance of the core in reflected light.The zoned phlogopite provides an example of considerable anionic and cationic variations within a single crystal. It is of mineralogical and petrological interest because, unlike in most silicates, the concentrations of its iron and magnesium exhibit the same trend and an opposite trend to that of aluminium. Aluminium increases from 14% to 18%, and replaces Si, Ti, Mg, and Fe thus indicating its geochemical importance during late stages of crystallization.  相似文献   

15.
Concentrations of Au, Ag, As, Cd and Sb in aquatic bryophytes collected from the Dolgellau Mineral Belt, North Wales, U.K. are reported. One aquatic liverwort, Scapania undulata (L) Dum. and two mosses, Fontinalis squamosa Hedw. and Racomitrium aciculare (Hedw.) Brid. were collected from sites upstream and downstream of the recently reopened Gwynfyndd Au mine. There was little inter-species variation in metal contents for these three bryophytes, but Scapania undulata appeared the most sensitive to changes in water concentrations of Ag, As and Sb. Gold concentrations varied little between the contaminated and control sites. Concentrations in the range < 4–18 ng Aug g−1 D.W. were typical background levels, while bryophytes collected immediately below the mine contained 6–45 ng Au g−1. Silver and Sb both showed more pronounced ( 5–10 fold) elevations above control concentrations in samples collected downstream of the mine. Background concentrations for these elements were 5–85 ng Ag g−1 and 0.15–1.3 μg Sb g−1.Arsenic concentrations downstream of the mine (160–1080 μg g−1) greatly exceeded the background range of 9–32 μg g−1. It is suggested, therefore, that As may be an ideal ‘pathfinder’ element when prospecting for auriferous deposits using aquatic bryophytes.  相似文献   

16.
A series of laboratory batch experiments was conducted to evaluate the potential for treatment of acid mine drainage (AMD) using organic C (OC) mixtures amended by zero-valent Fe (Fe0). Modest increases in SO4 reduction rates (SRRs) of up to 15% were achieved by augmenting OC materials with 5 and 10 dry wt% Fe0. However, OC was essential for supporting SO4 reducing bacteria (SRB) and therefore SO4 reduction. This observation suggests a general absence of autotrophic SRB which can utilize H2 as an electron donor. Sulfate reduction rates (SRRs), calculated using a mass-based approach, ranged from −12.9 to −14.9 nmol L−1 d−1  g−1 OC. Elevated populations of SRB, iron reducing bacteria (IRB), and acid producing (fermentative) bacteria (APB) were present in all mixtures containing OC. Effective removal of Fe (91.6–97.6%), Zn (>99.9%), Cd (>99.9%), Ni (>99.9%), Co (>99.9%), and Pb (>95%) was observed in all reactive mixtures containing OC. Abiotic metal removal was achieved with Fe0 only, however Fe, Co and Mn removal was less effective in the absence of OC. Secondary disordered mackinawite [Fe1+xS] was observed in field-emission scanning electron microscopy (FE-SEM) backscatter electron micrographs of mixtures that generated SO4 reduction. Energy dispersive X-ray (EDX) spectroscopy revealed that Fe–S precipitates were Fe-rich for mixtures containing OC and Fe0, and S-rich in the absence of Fe0 amendment. Sulfur K-edges determined by synchrotron-radiation based bulk X-ray absorption near-edge structure (XANES) spectroscopy indicate solid-phase S was in a reduced form in all mixtures containing OC. Pre-edge peaks on XANES spectra suggest tetragonal S coordination, which is consistent with the presence of an Fe–S phase such as mackinawite. The addition of Fe0 enhanced AMD remediation over the duration of these experiments, however long-term evaluation is required to identify optimal Fe0 and OC mixtures.  相似文献   

17.
For a period of 2 a, pore water composition in a heavily contaminated river floodplain soil was monitored in situ. Pore water samples were collected 12 times over all seasons in a profile ranging from aerobic to sulphidic redox conditions, and As, Cd, Cr, Cu, Pb, Zn, Mn, Fe, Ca, Cl, SO4, DOC, IOC and pH were determined. The variability of pH, IOC, DOC and Ca was found to be rather small during the year and within the profile (rsd < 0.04, 0.16, 0.24 and 0.22, respectively). The temporal variability of the metal and As concentrations was small, too, whereas changes with depth were distinct. Under sulphidic conditions, concentrations were below 1 μg L−1 (Cd, Cu, Pb) or 10 μg L−1 (Zn, As). The data set was compared with results from a geochemical model that was fully parameterised from literature data and included equilibrium speciation, sorption and mineral dissolution. The general pattern of the solid–solution partitioning of Cd, Cu, Zn and As in the profile was predicted well by mechanistic geochemical modelling on the basis of solid phase composition. Metals strongly bound to organic matter such as Cd and Cu were predicted better than metals mainly present within a mineral. Detailed information regarding the presence of colloidal Fe and Mn in pore water might improve the prediction of the solid–solution partitioning of a number of metals. The study also indicates that the chemical behaviour of Pb is still not understood sufficiently.  相似文献   

18.
Soil samples collected from various places in and around Mysore were analyzed for the total trace elements such as Fe, Mn, Cu, Zn, Pb, and Cd. The results of the analysis indicate that the concentration of lead and cadmium in soils is below 2.5 g ml–1 and 0.2 g ml–1, respectively, which are the minimum detection levels, whereas the concentration of iron, manganese, copper, and zinc in most of the samples is within the global average ranges of 3%, 500–1000 g g–1, 15–40 g g–1, and 50–100 g g–1, respectively. The investigated area has the presence of gneisses and schists, in which partly there are igneous intrusions and pegmatitic intrusions. There are amphibolite enclaves in gneisses that account for the higher concentration of trace elements. The lower concentration may be attributed to the presence of silicic type of rock.  相似文献   

19.
We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K d (X Fe carb X Mg ol /X Fe ol X Mg carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W FeMg ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO3 a W FeMg carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K d substantially enabling us to calculate W CaMg carb -W CaFe carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO2(CMS)–CO2 system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO2. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.  相似文献   

20.
The redox ratio of iron is used as an indicator of solution properties of silicate liquids in the system (SiO–Al2O3–K2O–FeO–Fe2O3–P2O5). Glasses containing 80–85 mol% SiO2 with 1 mol% Fe2O3 and compositions covering a range of K2O/Al2O3 were synthesized at 1400°C in air (fixed fO2). Variations in the ratio FeO/FeO1.5 resulting from the addition of P2O5 are used to determine the solution behavior of phosphorus and its interactions with other cations in the silicate melt. In 80 mol% SiO2 peralkaline melts the redox ratio, expressed as FeO/FeO1.5, is unchanged relative to the reference curve with the addition of 3 mol% P2O5. Yet, the iron redox ratio in the 85 mol% SiO2 potassium aluminosilicate melts is decreased relative to phosphorus-free liquids even for small amounts of P2O5 (0.5 mol%). The redox ratio in peraluminous melts is decreased relative to phosphorus- free liquids at P2O5 concentrations of 3 mol%. In peraluminous liquids, complexing of both Fe+3–O–P+5 and Al+3–O–P+5 occur. The activity coefficient of Fe+3 is decreased because more ferric iron can be accommodated than in phosphorus-free liquids. In peralkaline melts, there is no evidence that P+5 is removing K+ from either Al+3 or Fe+3 species. In chargebalanced melts with 3 mol% Fe2O3 and very high P2O5 concentrations, phosphorus removes K+ from K–O–Fe+3 complexes resulting in a redox increase. P2O5 should be accommodated easily in peraluminous rhyolitic liquids and phosphate saturation may be suppressed relative to metaluminous rhyolites. In peralkaline melts, phosphate solubility may increase as a result of phosphorus complexing with alkalis. The complexing stoichiometry may be variable, however, and the relative influence of peralkalinity versus temperature on phosphate solubility in rhyolitic melts deserves greater attention.  相似文献   

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