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1.
Samples of topsoil together with reference samples of subsurface soil from a depth of 80–90 cm were collected in the central-northern part of the Zambian Copperbelt to distinguish lithogenic sources of metals from anthropogenic contamination of soils caused by fallout of dust from mining operations, flotation ore treatment plants, tailings dams, smelters and slag dumping grounds. The total sulphur, Cu and Co contents were found to be significantly higher in topsoil relative to subsurface soil over a large part of the surveyed area, and Zn, Pb, As and Hg contents showed a definite increase in the close neighbourhood of smelters and in the direction of prevailing winds. This indicates that the increase of these elements in the topsoil is due to anthropogenic activities. The areal extent and degree of anthropogenic contamination of topsoil can be expressed by an enrichment index (EI) based on the average ratio of the actual and median concentrations of the given contaminants. Although the contamination of soil by dust fallout decreases progressively with depth in the soil profile, in areas strongly affected by mining and mineral processing the anthropogenic contamination by sulphur and copper can be traced to a depth of 80–90 cm. In contrast, the concentration of elements such as Cr, Ni, and V, that show a direct correlation with the content of iron in the soils, increases in the subsurface soil relative to the topsoil. This is particularly evident in areas underlain by rocks of the Katanga Supergroup.  相似文献   

2.
We performed a series of experiments at high pressures and temperatures to determine the partitioning of a wide range of trace elements between ilmenite (Ilm), armalcolite (Arm) and anhydrous lunar silicate melt, to constrain geochemical models of the formation of titanium-rich melts in the Moon. Experiments were performed in graphite-lined platinum capsules at pressures and temperatures ranging from 1.1 to 2.3 GPa and 1300-1400 °C using a synthetic Ti-enriched Apollo ‘black glass’ composition in the CaO-FeO-MgO-Al2O3-TiO2-SiO2 system. Ilmenite-melt and armalcolite-melt partition coefficients (D) show highly incompatible values for the rare earth elements (REE) with the light REE more incompatible compared to the heavy REE ( 0.0020 ± 0.0010 to 0.069 ± 0.010 for ilmenite; 0.0048 ± 0.0023 to 0.041 ± 0.008 for armalcolite). D values for the high field strength elements vary from highly incompatible for Th, U and to a lesser extent W (for ilmenite: 0.0013 ± 0.0008, 0.0035 ± 0.0015 and 0.039 ± 0.005, and for armalcolite 0.008 ± 0.003, 0.0048 ± 0.0022 and 0.062 ± 0.03), to mildly incompatible for Nb, Ta, Zr, and Hf (e.g. 0.28 ± 0.05 and : 0.76 ± 0.07). Both minerals fractionate the high field strength elements with DTa/DNb and DHf/DZr between 1.3 and 1.6 for ilmenite and 1.3 and 1.4 for armalcolite. Armalcolite is slightly more efficient at fractionating Hf from W during lunar magma ocean crystallisation, with DHf/DW = 12-13 compared to 6.7-7.5 for ilmenite. The transition metals vary from mildly incompatible to compatible, with the highest compatibilities for Cr in ilmenite (D ∼ 7.5) and V in armalcolite (D ∼ 8.1). D values show no clear variation with pressure in the small range covered.Crystal lattice strain modelling of D values for di-, tri- and tetravalent trace elements shows that in ilmenite, divalent elements prefer to substitute for Fe while armalcolite data suggest REE replacing Mg. Tetravalent cations appear to preferentially substitute for Ti in both minerals, with the exception of Th and U that likely substitute for the larger Fe or Mg cations. Crystal lattice strain modelling is also used to identify and correct for very small (∼0.3 wt.%) melt contamination of trace element concentration determinations in crystals.Our results are used to model the Lu-Hf-Ti concentrations of lunar high-Ti mare basalts. The combination of their subchondritic Lu/Hf ratios and high TiO2 contents requires preferential dissolution of ilmenite or armalcolite from late-stage, lunar magma ocean cumulates into low-Ti partial melts of deeper pyroxene-rich cumulates.  相似文献   

3.
By using the axisymmetric finite elements static limit analysis formulation, proposed recently by the authors, the stability numbers (γH/co) for an unsupported vertical circular excavation in clays, whose cohesion increases with depth, have been determined under undrained condition; γ = unit weight, H = height of the excavation and co = cohesion along ground surface. The results are obtained for various values of H/b and m; where b = the radius of the excavation and m = a non-dimensional parameter which accounts for the rate of the increase of cohesion with depth. The values of the stability numbers increase continuously both with increases in H/b and m. The results obtained in this study compare well with those available in literature.  相似文献   

4.
In this work, the inorganic chemical profiles of soil samples collected at different sites in the Salentum peninsula (Italy, Apulia region) are discussed. The samples were re-suspended in the laboratory, for PM10 sampling, using a ventilated wooden chamber and were then chemically analysed measuring the abundances of 17 elements. Different land use categories of soils (olive grove, arable land, vineyards, sand, and urban dust) were included in the 50 samples analysed: 45 collected in background areas and five collected in the urban area of Lecce. The objectives were to compare the chemical profiles of raw soil and re-suspended PM10 for different crustal sources and to estimate the potential improvements in the calculation of the enrichment factors of atmospheric PM10. The variability of elemental abundances in samples of the same category of soil collected in different zones was of the same order of magnitude as the differences observed between the various categories of soil. This allows the calculation of a weighted average composition of soil and urban dust and the corresponding weighted average composition of re-suspended PM10. In re-suspended PM10 from average background soil, all of the elements except Ca, Na, K and V have larger abundances with respect to raw soil. In urban dust, this is limited to Ca, V and Mg. The crustal enrichment factors (EFs) of atmospheric PM10 were evaluated by considering different reference elements and different reference tables. Results indicated that it is possible to apply a two-threshold (S1 and S2) scheme for the interpretation of EF, with thresholds derived from uncertainty in soil categories and from the choice of the reference element. A specific element is likely of crustal origin if EF < S1 and likely of anthropogenic origin if EF > S2. Between the two thresholds, the element can be considered of mixed origin. The thresholds vary according to the geological composition used in the evaluation of EF. If the average composition of local re-suspended soils is used, the thresholds are S1 = 2 and S2 = 4. If raw soil is used, the thresholds become S1 = 5 and S2 = 10. If the average upper-crust composition from literature data is used, the thresholds further increase to S1 = 10 and S2 = 20.  相似文献   

5.
Synthetic fluid inclusions in quartz were grown from cassiterite-saturated fluids in cold-seal pressure vessels at and subsequently analyzed by laser ablation-ICP-MS. Most inclusions were synthesized using a new technique that allows entrapment of fluid that had no immediate contact to the capsule walls, such that potential disequilibrium effects due to alloying could be avoided. Measured Sn solubilities increase with increasing ligand concentration in the fluid, ranging from 100 to 800 ppm in NaCl-bearing fluids (5-35 wt% NaCl), from 70 to 2000 ppm in HF-bearing fluids (0.5-3.2 m HF), and from 0.8 to 11 wt% in HCl-bearing fluids (0.5-4.4 m HCl). Two runs performed with the in-situ cracking method after 1 week of pre-equilibration demonstrate that the speed of hydrogen diffusion through the capsule wall relative to that of fluid inclusion formation is a critical factor in fO2-dependent solubility studies. Graphical evaluation of the solubility data suggests that Sn may have been dissolved as Sn(OH)Cl in the NaCl-bearing fluids, as Sn(OH)Cl and SnCl2 in the HCl-bearing fluids, and as SnF2 in the HF-bearing fluids. Experiments with NaF-bearing fluids produced an additional melt phase with an approximate composition of 53 wt% SiO2, 25 wt% H2O, 14 wt% NaF and 8 wt% SnO, which caused the composition of the coexisting fluid to be buffered at 0.5 wt% NaF and 150 ppm Sn. Fluorine-rich, peralkaline melts may therefore serve as important transport media for Sn in the final crystallization stages of tin granites. Based on the available cassiterite-solubility data in fluids and melts, in natural granite systems is estimated to be in the order of 0.1-4 (depending on their aluminosity), suggesting that Sn is not easily mobilized by magmatic-hydrothermal fluids. This interpretation is in accordance with the high degrees of Sn-enrichment commonly observed in highly fractionated melt inclusions. is primarily controlled by the HCl concentration in the fluid, which in turn is a function of the aluminum saturation index of the magma. Compared to HCl, the effect of fluorine on is subordinate.  相似文献   

6.
Tellurium isotope data acquired by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) are presented for sequential acid leachates of the carbonaceous chondrites Orgueil, Murchison, and Allende. Tellurium isotopes are produced by a broad range of nucleosynthetic pathways and they are therefore of particular interest given the isotopic anomalies previously identified for other elements in these meteorites. In addition, the data provide new constraints on the initial solar system abundance of the r-process nuclide 126Sn, which decays to 126Te with a half-life of 234,500 years. The 126Te/128Te ratios of all leachates were found to be identical, within uncertainty, despite variations in 124Sn/128Te of between about 0.002 and 1.4. The data define a 126Sn/124Sn ratio of <7.7 × 10−5 at the time of last isotopic closure, consistent with the value of <18 × 10−5 previously reported for bulk carbonaceous chondrites. How close this is to the initial 126Sn/124Sn ratio of the solar system depends on when the investigated samples last experienced redistribution of Sn and Te. No clear evidence is found for nucleosynthetic anomalies in the abundances of p-, s-, and r-process nuclides. The largest effect detected in this study is a small excess of the r-process nuclide 130Te in a nitric acid leachate of Murchison. This fraction displays an anomalous ε130Te of +3.5 ± 2.5. Although barely resolvable given the analytical uncertainties, this is consistent with the presence of a small excess r-process component or an s-process deficit. The general absence of anomalies contrasts with previous results obtained for K, Cr, Zr, Mo, and Ba isotopes in similar leachates, which display nucleosynthetic anomalies of up to 3.8%. The reason for this discrepancy is unclear but it may reflect volatility and more efficient mixing of Te in the solar nebula.  相似文献   

7.
The Nasirabad manganese occurrence is located to the south of the Neyriz in the Fars province. Structurally and lithologically, this occurrence lies in the southwest part of the Zagros Thrust Belt and was deposited as Mn-nodules and interconnected ore-bearing interlayer's with radiolarite cherts in the vicinity of the Neyriz ophiolites. The present work deals with the geology and geochemistry of the Nasirabad manganese occurrence with a discussion of its genesis. High Mn/Fe (average 18.85) and high Ba (average 28,830 ppm) with low Pb (2.0 ppm) and LREE > HREE, Lan/Ndn (average 4.5), Dyn/Ybn (average 1.2) and negative Eu anomaly suggest distal hydrothermal source. The Co/Zn (average 2.2), Ce/La ratio (average 0.67) and trace element discrimination diagrams indicate hydrothermal–hydrogenous processes. Y/Ho ratio (average 24.85) and strong positive correlation coefficient between major oxides and some high field strength elements (HFSE) like; TiO2 vs Fe2O3 (r = 0.98), Al2O3 vs Zr (r = 0.97), Al2O3 vs Fe2O3 (r = 0.98), Zr vs K2O (r = 0.98), Nb vs TiO2 (r = 0.92), Th vs Fe2O3 (r = 0.76), Th vs MgO (r = 0.86) reveal the presence of volcaniclastics and (or) terrigenous detritals of mafic composition being deposited into the depositional basin. It seems that intermittent interlayering of mafic detrital material derived from volcanic eruption of the Neyriz island arc directly affected the physicochemical conditions of hydrothermal ore precipitation in this basin and consequently the Nasirabad manganese ores represent hydrothermal–hydrogenous geochemical characteristics. The Nasirabad is an example of non-sulphidic, oxic Mn-mineralization. Similar trend between the enrichment and depletion of some bioessential elements (e.g., Mn, As, Ba, Sr, Co, Ce) might have been resulted from selective sequestering of metal ions by microbial processes and hence hydrogenous characteristics may also be the result of biogenetic processes. Moreover the high dilution of distal hydrothermal exhalations by sea water cannot be ruled out.  相似文献   

8.
Trace element partitioning between apatite and silicate melts   总被引：7，自引：0，他引：7  
We present new experimental apatite/melt trace element partition coefficients for a large number of trace elements (Cs, Rb, Ba, La, Ce, Pr, Sm, Gd, Lu, Y, Sr, Zr, Hf, Nb, Ta, U, Pb, and Th). The experiments were conducted at pressures of 1.0 GPa and temperatures of 1250 °C. The rare earth elements (La, Ce, Pr, Sm, Gd, and Lu), Y, and Sr are compatible in apatite, whereas the larger lithophile elements (Cs, Rb, and Ba) are strongly incompatible. Other trace elements such as U, Th, and Pb have partition coefficients close to unity. In all experiments we found DHf > DZr, DTa ≈ DNb, and DBa > DRb > DCs. The experiments reveal a strong influence of melt composition on REE partition coefficients. With increasing polymerisation of the melt, apatite/melt partition coefficients for the rare earth elements increase for about an order of magnitude. We also present some results in fluorine-rich and water-rich systems, respectively, but no significant influence of either H2O or F on the partitioning was found. Furthermore, we also present experimentally determined partition coefficients in close-to natural compositions which should be directly applicable to magmatic processes.  相似文献   

9.
Synthesis, characterization and thermochemistry of a Pb-jarosite   总被引：1，自引：0，他引：1  
The enthalpy of formation from the elements of a well-characterized synthetic Pb-jarosite sample corresponding to the chemical formula (H3O)0.74Pb0.13Fe2.92(SO4)2(OH)5.76(H2O)0.24 was measured by high temperature oxide melt solution calorimetry. This value ( = −3695.9 ± 9.7 kJ/mol) is the first direct measurement of the heat of formation for a lead-containing jarosite. Comparison to the thermochemical properties of hydronium jarosite and plumbojarosite end-members strongly suggests the existence of a negative enthalpy of mixing possibly related to the nonrandom distribution of Pb2+ ions within the jarosite structure. Based on these considerations, the following thermodynamic data are proposed as the recommended values for the enthalpy of formation from the elements of the ideal stoichiometric plumbojarosite Pb0.5Fe3(SO4)2(OH)6:  = −3118.1 ± 4.6 kJ/mol,  = −3603.6 ± 4.6 kJ/mol and S° = 376.6 ± 4.5 J/(mol K). These data should prove helpful for the calculation of phase diagrams of the Pb-Fe-SO4-H2O system and for estimating the solubility product of pure plumbojarosite. For illustration, the evolution of the estimated solubility product of ideal plumbojarosite as a function of temperature in the range 5-45 °C was computed (Log(Ksp) ranging from −24.3 to −26.2). An Eh-pH diagram is also presented.  相似文献   

10.
Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ66Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ66Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ66Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe2O4)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ66Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ66Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ66Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.  相似文献   

11.
The solubility of ZnS(cr) was measured at 100 °C, 150 bars in sulfide solutions as a function of sulfur concentration (m(Stotal) = 0.02-0.15) and acidity (pHt = 2-11). The experiments were conducted using a Ti flow-through hydrothermal reactor enabling the sampling of large volumes of solutions at experimental conditions, with the subsequent concentration and determination of trace quantities of Zn. Prior to the experiments, a long-term in situ conditioning of the solid phase was performed in order to attain the reproducible Zn concentrations (i.e. solubilities). The ZnS(cr) solubility product was monitored in the course of the experiment. The following species were found to account for Zn speciation in solution: Zn2+ (pHt < 3), (pHt 3-4.5), (pHt 5-8), and ZnS(HS)− (pHt > 8) (pHt predominance regions are given for m(Stotal) = 0.1). Solubility data collected in this study at pHt > 3 were combined with the ZnS(cr) solubility product determined at lower pH to yield the following equilibrium constants (t = 100 °C, P = 150 bars):
  相似文献   

12.
New geochemical data on cosmic spherules (187 major element, 76 trace element, and 10 oxygen isotope compositions) and 273 analyses from the literature were used to assess the chemical diversity observed among glass cosmic spherules with chondritic composition. Three chemical groups of glass spherules are identified: normal chondritic spherules, CAT-like spherules (where CAT refers to Ca-Al-Ti-rich spherules), and high Ca-Al spherules. The transition from normal to high Ca-Al spherules occurs through a progressive enrichment in refractory major elements (on average from 2.3 wt.% to 7.0 wt.% for CaO, 2.8 wt.% to 7.2 wt.% for Al2O3, and 0.14 wt.% to 0.31 wt.% for TiO2) and refractory trace elements (from 6.2 μg/g to 19.3 μg/g for Zr and 1.6CI-4.3CI for Rare Earth Elements-REEs) relative to moderately refractory elements (Mg, Si) and volatile elements (Rb, Na, Zn, Pb). Based on a comparison with experimental works from the literature, these chemical groups are thought to record progressive heating and evaporation during atmospheric entry. The evaporative mass losses evaluated for the high Ca-Al group (80-90%) supersede those of the CAT spherules which up to now have been considered as the most heated class of stony cosmic spherules. However, glass cosmic spherules still retain isotopic and elemental evidence of their source and precursor mineralogy. Four out of the 10 normal and high Ca-Al spherules analysed for oxygen isotopes are related to ordinary chondrites (δ18O = 13.2-17.3‰ and δ17O = 7.6-9.2‰). They are systematically enriched in Ni and Co (Ni = 24-500 μg/g) with respect to spherules related to carbonaceous chondrites (Ni < 1.2 μg/g, δ18O = 13.1-28.0‰ and δ17O = 5.1-14.0‰). REE abundances in cosmic spherules, which are not fractionated according to parent body or atmospheric entry heating, can then be used to unravel the precursor mineralogy. Spherules with flat REE pattern close to unity when normalized to CI are the most abundant in our dataset (54%) and likely derive from homogeneous, fine-grained chondritic precursors. Other REE patterns fall into no more than five categories, a surprising reproducibility in view of the mineralogical heterogeneity of chondritic lithologies at the micrometeorite scale.  相似文献   

13.
Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO2 = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (DPb ∼ 6 ∗ mCl, DZn ∼ 8 ∗ mCl, DAg ∼ 4 ∗ mCl, DFe ∼ 1.4 ∗ mCl, where mCl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of DMo ∼ 20, DB ∼ 15, DAs ∼ 13, DSb ∼ 8, DBi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (DCu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (DSn = 0.3-42, DW = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.  相似文献   

14.
We have carried out a comparative Rb-Sr, Sm-Nd and Lu-Hf isotopic study of a progressively deformed hercynian leucogranite from the French Massif Central, belonging to the La Marche ductile shear zone, in order to investigate the respective perturbation of these geochronometers with fluid induced deformation. The one-meter wide outcrop presents a strongly deformed and mylonitized zone at the center, and an asymmetric deformation pattern with a higher deformation gradient on the northern side of the zone. Ten samples have been carefully collected every 10 cm North and South away from the strongest deformed mylonitic zone. They have been analyzed for a complete major, trace element data set, oxygen isotopes, Rb-Sr, Sm-Nd and Lu-Hf isotopic systematics.We show that most of major and trace elements except SiO2, alkaline elements (K2O, Rb), and some metal transition elements (Cu), are progressively depleted with increasing deformation. This depletion includes REE + Y, but also HFS elements (Ti, Hf, Zr, Nb) which are commonly considered as immobile elements during upper level processes. Variations in elemental ratios with deformation, e.g. decrease in LREE/MREE- HREE, Nd/Hf, Th/Sr, increase in Rb/Sr, U/Th and constant Sr/Nd, lead to propose the following order of element mobility: U ? Th > Sr = Nd ? Hf + HREE. We conclude in agreement with previous tectonic and metallogenic studies that trace element patterns across the shear zone result from circulation of oxidizing F-rich hydrothermal fluids associated with deformation. A temperature of the fluid of 470-480 °C can be deduced from the δ18O equilibrium between quartz-muscovite pairs.Elemental fractionation induces perturbation of the Rb-Sr geochronometer. The well-defined 87Rb/86Sr-87Sr/86Sr correlation gives an apparent age of 294 ± 19 Ma, slightly younger than the 323 ± 4 Ma age of leucogranites in this area. This apparent age is interpreted as dating event of intense deformation and fluid circulation associated with mass transfer, and exhumation of the ductile crust shortly after the leucogranite emplacement. Sm-Nd and Lu-Hf isochron-type diagrams do not define any correlation, because of the low fractionated Sm/Nd and Lu/Hf ratios. Isotopic data demonstrate that only the Lu-Hf geochronometer system is not affected by fluid circulation and gives reliable TDM age (1.29 ± 0.03 Ga) and εHf signatures. By contrast, the Sm-Nd geochronometer system gives erroneous old TDM ages of 2.84-4 Ga. There is no positive εNd-εHf correlation, because of decreasing εNd values with deformation at constant εHf values. However, εNd-εHf values remain in the broad εNd-εHf terrestrial array, which strongly indicates that fluid-induced fractionation can contribute to the width of the terrestrial array. The strong εHf negative values of the leucogranite are similar to metasedimentary granulitic xenoliths from the French Massif Central and confirm the generation of the leucogranite by several episodes of reworking of the lower crust.  相似文献   

15.
Os equilibrium solubilities were determined at 1350 °C over a wide range of oxygen fugacities (−12 < log fO2 < −7) applying the mechanically assisted equilibration technique (MAE) at 105 Pa (= 1 bar). Os concentrations in the glass samples were analysed using ID-NTIMS. Additional LA-ICP-MS and SEM analyses were performed to detect, visualize and analyse the nature and chemistry of “nanonuggets.” Os solubilities determined range at a constant temperature of 1350 °C from 0.63 ± 0.04 to 37.4 ± 1.16 ppb depending on oxygen fugacity. At the highest oxygen fugacities, Os3+ can be confirmed as the main oxidation state of Os. At low oxygen fugacities (below log fO2 = −8), samples are contaminated by nanonuggets which, despite the MAE technique, were still not removed entirely from the melt. However, the present results indicate that applying MAE technology does reduce the amount of nanonuggets present significantly, resulting in the lowest Os solubility results reported to date under these experimental conditions, and extending the experimentally accessible range of fO2 for these studies to lower values. Calculated metal/silicate melt partition coefficients are therefore higher compared to previous studies, making Os more siderophile. Neglecting the as yet unknown temperature dependence of the Os metal/silicate melt partition coefficient, extrapolation of the obtained Os solubilities to conditions for core-mantle equilibrium, results in a , while metallic alloy/silicate melt partition coefficients range from 1.4 × 106 to 8.6 × 107, in agreement with earlier findings. Therefore remains too high by 2-4 orders of magnitude to explain the Os abundance in the Earth’s mantle as result of core-mantle equilibrium during core formation.  相似文献   

16.
The volatization of Rhenium (Re) from melts of natural basalt, dacite and a synthetic composition in the CaO-MgO-Al2O3-SiO2 system has been investigated at 0.1 MPa and 1250-1350 °C over a range of fO2 conditions from log fO2 = −10 to −0.68. Experiments were conducted using open top Pt crucibles doped with Re and Yb. Analysis of quenched glasses by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) normal to the melt/gas interface showed concentration profiles for Re, to which a semi-infinite one-dimensional diffusion model could be applied to extract diffusion coefficients (D). The results show Re diffusivity in basalt at 1300 °C in air is log DRe = −7.2 ± 0.3 cm2/s and increases to log DRe = −6.6 ± 0.3 cm2/s when trace amounts of Cl were added to the starting material. At fO2 conditions below the nickel-nickel oxide (NNO) buffer Re diffusivity decreases to and to in dacitic melt. In the CMAS composition, . The diffusivity of Re is comparable to Ar and CO2 in basalt at 500 MPa favoring its release as a volatile. Our results support the contention that subaerial degassing is the cause of lower Re concentrations in arc-type and ocean island basalts compared to mid-ocean ridge basalts.  相似文献   

17.
Micro-Raman spectroscopy, even though a very promising technique, is not still routinely applied to analyse H2O in silicate glasses. The accuracy of Raman water determinations critically depends on the capability to predict and take into account both the matrix effects (bulk glass composition) and the analytical conditions on band intensities. On the other hand, micro-Fourier transform infrared spectroscopy is commonly used to measure the hydrous absorbing species (e.g., hydroxyl OH− and molecular H2O) in natural glasses, but requires critical assumptions for the study of crystal-hosted glasses. Here, we quantify for the first time the matrix effect of Raman external calibration procedures for the quantification of the total H2O content (H2OT = OH− + H2Om) in natural silicate glasses. The procedures are based on the calibration of either the absolute (external calibration) or scaled (parameterisation) intensity of the 3550 cm−1 band. A total of 67 mafic (basanite, basalt) and intermediate (andesite) glasses hosted in olivines, having between 0.2 and 4.8 wt% of H2O, was analysed. Our new dataset demonstrates, for given water content, the height (intensity) of Raman H2OT band depends on glass density, reflectance and water environment. Hence this matrix effect must be considered in the quantification of H2O by Raman spectroscopy irrespective of the procedure, whereas the parameterisation mainly helps to predict and verify the self-consistency of the Raman results. In addition, to validate the capability of the micro-Raman to accurately determine the H2O content of multicomponent aluminosilicate glasses, a subset of 23 glasses was analysed by both micro-Raman and micro-FTIR spectroscopy using the band at 3550 cm−1. We provide new FTIR absorptivity coefficients (ε3550) for basalt (62.80 ± 0.8 L mol−1 cm−1) and basanite (43.96 ± 0.6 L mol−1 cm−1). These values, together with an exhaustive review of literature data, confirm the non-linear decline of the FTIR absorptivity coefficient (ε3550) as the glass depolymerisation increases. We demonstrate the good agreement between micro-FTIR and micro-Raman determination of H2O in silicate glasses when the matrix effects are properly considered.  相似文献   

18.
This paper presents the results of a study on the geochemistry of waters circulating in the mineralised area of the south-eastern sector of Mt. Peloritani (north-eastern Sicily, Italy), aimed at basic understanding of the geochemical processes influencing their chemical composition. Chemico-physical parameters and data on 26 major and minor chemical elements are reported for 103 water samples. Water chemistry is mainly dominated by dissolution of carbonates and hydrolysis of aluminosilicate minerals. Total dissolved salts (TDS) range from 80 to 1398 mg/L. All the waters exhibit EH characteristic of an oxygenated environment. Excluding two samples, which show very high H+ activity (pH = 3.0 and 2.7), all the waters have pH values in the range 6.2–8.6. Cluster analysis based on major ion contents defined three main chemical water types, reflecting different hydrochemical processes. The first, group I, has low salinity (average TDS = 118 ± 30 mg/L) and abundance orders (meq/L) Na > Ca ≈ Mg > K and Cl ≈ HCO3 > SO4. With increased water–rock interaction, waters in groups II and III become more saline, changing composition towards SO4–Cl-alkaline earth and HCO3-alkaline earth types. Weathering of carbonate minerals causes waters to become saturated with respect to calcite and dolomite, whereas the incongruent dissolution of aluminosilicate minerals causes the solution to reach equilibrium with kaolinite and to form smectites. Trace element geochemistry in the analysed waters reflects interactions between waters and existing mineralisation, with elemental concentrations showing highly variable values, and higher concentrations of As, Pb, Sb and Zn near known mineralisation. Lead–Zn and As–Sb statistical associations, probably distinguishing interactions with different mineralogical phase paragenesis, were revealed by factor analysis. The main aqueous chemical forms of trace elements predicted by chemical speciation calculations are also reported. As most of the analysed spring waters provide the main source of freshwater for domestic purposes, attention should be given to As and Sb, whose concentrations exceed the recommended limits.  相似文献   

19.
Surface alteration-layers often coat minerals in acid-mine drainage systems and the characterization of their chemical composition is required to understand the uptake or release of potentially toxic elements. Samples with micrometer-thick rock coatings were collected from bedrock in contact with three acidic tailings ponds and a small lake, all located within the Copper Cliff mine tailings disposal area in Sudbury, Ontario, Canada. Distribution and concentration of trace-metals in the rock coatings were characterized with Laser-Ablation Inductively-Coupled Plasma Mass Spectroscopy and Micro X-ray Fluorescence Spectroscopy. The rock coatings are composed of goethite, ferrihydrite, schwertmannite, jarosite and amorphous silica. The latter phase is a product of the non-stoichiometric weathering of the underlying siliceous rock. Layers within the coatings are distinguished on the basis of their atomic Fe:Si ratios: FeOx coatings have Fe:Si > 4:1, Si-FeOx coatings have Fe:Si = 4:1 to 1:1 and SiOx coatings have Si > Fe. Iron-rich coatings (FeOx) in contact with acidic tailings ponds (pH < 3.5) have lower trace-metal concentrations than their Si-rich counterparts, whereas FeOx in contact with lake water at near neutral pH have similar trace-metal concentrations than Si-FeOx and SiOx, most likely the result of higher adsorption rates of metals at near neutral pH conditions. High trace-metal concentrations in Si-FeOx and SiOx are explained by the presence of jarosite-group minerals, which formed within Si-rich alteration layers through mixing of leached alkaline cations and trace elements from the underlying rock and Fe3+-sulfate solutions from the pond. Calculated enrichment factors for trace metals and metalloids in the coatings (relative to the pond) indicate that the mobility for Pb, As, Cr and Cu in the upper part of tailings ponds is commonly lower than the mobility for Zn, Mn, Co and Ni. The environmental significance of these findings is discussed in terms of the attenuation of trace metals in the coatings and the widespread occurrences of silica gels and jarosite-group minerals.  相似文献   

20.
Microbial SO42− reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL−1) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L−1 synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As4S4) and As2S3(am) were undersaturated throughout the experiment. Orpiment (As2S3) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS2) and greigite (Fe3S4) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na2S4) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO42− reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.  相似文献   

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