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1.
The effects of fertilizer applications on runoff loss of phosphorus   总被引：4，自引：0，他引：4  
The phosphorus index (PI) can be used to effectively identify areas with high risks of phosphorus losses. Manures and fertilizers are important source factors for the establishment of the PI system. An artificial precipitation experiment was performed to evaluate phosphorus losses with the applications of different types of fertilizers and manures. The results showed that the total phosphorus (TP) losses in runoff followed the order of ammonium phosphate monobasic (NH4H2PO4), ammonium hydrogen phosphate ((NH4)2HPO4), monobasic potassium phosphate (KH2PO4), chicken manure, and cattle manure with surface application of these fertilizers and manures. The order was slightly changed to NH4H2PO4, KH2PO4, (NH4)2HPO4, chicken manure, and cattle manure with incorporation application under the same rainfall condition. Both the methods and the rate of manure application can affect the amounts of phosphorus in water and particles of runoff. More than 90 % of TP in runoff were lost through suspended particles. Manure application had a significant contribution to the P load in runoff.  相似文献   

2.
In order to prepare iron phosphate by waste sludge, we report a method for effective utilization of the sludge obtained from the electrocoagulation treatment of source-separated urine. The sludge was dissolved with hydrochloric acid and pretreated with H2O2 and Na3PO4; finally, NaOH was added to precipitate iron phosphate from the solution. Thermal treatment of the precipitate at 750 °C in air yielded crystalline quartz-like anhydrous FePO4. The precipitate was characterized by a number of thermal techniques such as thermogravimetry/differential thermal analysis, scanning electron microscopy, and X-ray powder diffraction.  相似文献   

3.
《Applied Geochemistry》2006,21(7):1216-1225
The aim of the study was to determine whether the application of bulk industrial chemicals (potassium permanganate and water-soluble phosphate fertilizer) to partly oxidized, polyminerallic mine wastes can inhibit sulfide oxidation, and metal and metalloid mobility. The acid producing waste rocks were metal (Pb, Zn, Cu) and metalloid (As, Sb) rich and consisted of major quartz, dickite, illite, and sulfide minerals (e.g., galena, chalcopyrite, tetrahedrite, sphalerite, pyrite, arsenopyrite), as well as minor to trace amounts of pre- and post-mining oxidation products (e.g., hydrated Fe, Cu, Pb, and alkali mineral salts). SEM-EDS observations of treated waste material showed that metal, metal–alkali, and alkali phosphate coatings developed on all sulfides. The abundance of phosphate phases was dependant on the fertilizer type and the availability of metal and alkali cations in solution. In turn, the release of cations was dependent on the amount of sulfide oxidation induced by KMnO4 during the experiment and the dissolution of soluble sulfates. Mn, Ca, Fe, and Pb phosphates remained stable during H2O2 leaching, preventing acid generation and metal release. In contrast, the lack of complete phosphate coating on arsenopyrite allowed oxidation and leaching of As to proceed. The mobilized As did not form phosphate phases and consequently, As displayed the greatest release from the coated waste. Thus, the application of KMnO4 and the water-soluble phosphate fertilizer Trifos (Ca(H2PO4)2) to partly oxidized, polyminerallic mine wastes suppresses sulfide oxidation and is most effective in inhibiting Cu, Pb, and Zn (Sb) release. However, the technique appears ineffective in suppressing oxidation of arsenopyrite and preventing As leaching.  相似文献   

4.
The large range of stable oxygen isotope values of phosphate‐bearing minerals and dissolved phosphate of inorganic or organic origin requires the availability of in‐house produced calibrated silver phosphate of which isotopic ratios must closely bracket those of studied samples. We propose a simple protocol to synthesise Ag3PO4 in a wide range of oxygen isotope compositions based on the equilibrium isotopic fractionation factor and the kinetics and temperature of isotopic exchange in the phosphate–water system. Ag3PO4 crystals were obtained from KH2PO4 that was dissolved in water of known oxygen isotope composition. Isotopic exchange between dissolved phosphate and water took place at a desired and constant temperature into PYREX? tubes that were placed in a high precision oven for defined run‐times. Samples were withdrawn at desired times, quenched in cold water and precipitated as Ag3PO4. We provide a calculation sheet that computes the δ18O of precipitated Ag3PO4 as a function of time, temperature and δ18O of both reactants KH2PO4 and H2O at t = 0. Predicted oxygen isotope compositions of synthesised silver phosphate range from ?7 to +31‰ VSMOW for a temperature range comprised between 110 and 130 °C and a range of water δ18O from ?20 to +15‰ VSMOW.  相似文献   

5.
The surface of arsenopyrite was characterized after acidic, oxidative leaching in the presence of the bacterial species Thiobacillus ferrooxidans. Polished single-crystal grains of arsenopyrite were reacted for 1, 2, and 3 weeks with T. ferrooxidans suspended in a solution (pH 2.3) of essential salts (MgSO4·7H2O, [NH4]2SO4, KH2PO4, and KCl). Abiotic control experiments were conducted in identical solutions. Reaction between arsenopyrite and T. ferrooxidans in the essential salts solution produced a uniform solid FePO4 overlayer (∼0.2 μm thick) on the arsenopyrite surface within 1 week. The overlayer was detected visually by scanning electron microscopy (SEM) and chemically by X-ray photoelectron spectroscopy (XPS). It could not be distinguished by energy-dispersive X-ray analyses. No overlayer formed in the abiotic control. The uniform thickness and lateral continuity of the overlayer suggest an inorganic origin promoted by bacterial production of Fe3+. Iron released from arsenopyrite was oxidized by bacteria and subsequently precipitated with PO43− (from the essential salts), forming ferric phosphate. After 2 and 3 weeks, SEM images revealed a roughened arsenopyrite surface, and XPS depth profiles indicated a progressively thicker phosphate overlayer and continued oxidation, diffusion, and dissolution of arsenopyrite beneath the overlayer. After only 1 week, the cells were isolated from the arsenopyrite surface by the uniform overlayer. Therefore, bacteria need not be attached to arsenopyrite to promote rapid reaction, and the mechanism of alteration at the arsenopyrite surface must have been inorganic. Because the delicate overlayer did not prevent continued alteration of arsenopyrite, FePO4 may not be an effective barrier to oxidation in the tailings environment. The FePO4 coating has likely formed in other experiments using these bacteria but was not detected because analytical techniques were not sufficiently surface sensitive to identify a separate, compositionally distinct overlayer. Some previous experimental results thus may be misleading or inapplicable to the tailings environment.  相似文献   

6.
This study aims to compare the impact of oyster cultures on diagenetic processes and the phosphorus cycle in the sediments of the Aber Benoît and the Rivière d’Auray, estuary of Brittany, France. Our results showed clear evidence of the seasonal impact of oyster cultures on sediment characteristics (grain size and organic matter parameters) and the phosphorus cycle, especially in the Aber Benoît. At this site, seasonal variations in sulfide and Fe concentrations in pore waters, as well as Fe–P concentrations in the solid phase, highlighted a shift from a system governed by iron reduction (Reference) to a system governed by sulfate reduction (beneath oyster). This could be partly explained by the increase in labile organic matter (i.e., biodeposits) beneath oysters, whose mineralization by sulfate led to high sulfide concentrations in pore waters (up to 4,475 µmol l?1). In turn, sulfide caused an enhanced release of phosphate in the summer, as adsorption sites for phosphate decreased through the formation of iron–sulfide compounds (FeS and FeS2). In the Aber Benoît, dissolved Fe/PO4 ratios could be used as an indicator of phosphate release into oxic water. Low Fe/PO4 ratios in the summer indicated higher effluxes of phosphate toward the water column (up to 47 µmol m?2 h?1). At other periods, Fe/PO4 ratios higher than 2 mol/mol indicated very low phosphate fluxes. In contrast, in the Rivière d’Auray, the occurrence of macroalgae, stranding regularly all over the site, clearly masked the impact of oyster cultures on sediment properties and the phosphorus cycle and made the use of Fe/PO4 ratios more difficult in terms of indicators of phosphate release.  相似文献   

7.
The reactions of secondary lead orthophosphate with approximately 10?1 M sodium fluoride and sodium bromide solutions have been investigated at 25°C. Interpretation of the solubility data resulted in solubility product constants for fluoropyromorphite and bromopyromorphite of 10?71.6 and 10?78.1, respectively. According to these constants, the stability sequence for lead pyromorphites is Pb5(PO4)3Cl > Pb5(PO4)3Br > Pb5(PO4)3OH > Pb5(PO4)3F. The derived free energy data have been used to evaluate the respective stabilities of fluoro-pyromorphite and bromopyromorphite within the systems PbF2-PbO-P2O5-H2O and PbBr2-PbO-P2O5-H2O and to predict the equilibrium behavior of the Pb5(PO4)3F-Pb5(PO4)3OH solid solution under aqueous conditions.  相似文献   

8.
 Selenium (Se), an animal toxicant and aquifer contaminant, occurs in coal mine environments of Wyoming. There is a paucity of information on solution-phase Se speciation in mine soils. The objectives of this study were to compare Se extraction efficiencies of various reagents and to characterize SeO2– 3 (selenite), SeO2– 4 (selenate) and organic Se components in these extracts. Forty coal mine soils were extracted using DI (deionized) water, hot water (0.1% CaCl2), AB-DTPA, NaOH, and KH2PO4. Each solution was analyzed for total dissolved Se, and inorganic and organic Se fractions. Both inorganic and organic Se fractions were detected in the soil extracts. The order of Se (total, inorganic, and organic) extraction efficiency for different reagents was DI water < hot water < AB-DTPA < NaOH < KH2PO4. The inorganic–organic Se ratios in DI water, hot water, AB-DTPA, NaOH, and KH2PO4 extracts were 60 : 40, 26 : 74, 61 : 39, 87 : 13, and 52 : 48, respectively, indicating predominance of inorganic Se in all but the hot water extract. Selenite was the dominant inorganic species in AB-DTPA and KH2PO4 extracts, while SeO2– 4 was the major Se species in the DI water, hot water, and NaOH extracts. Significant correlations (P<0.01) were observed among extractable inorganic Se [NaOH and KH2PO4 (r=0.95); hot water and AB-DTPA (r=0.89)], total soluble Se [DI water with hot water (r=0.98) and AB-DTPA (r=0.95)], and Se species [SeO2– 3 in AB-DTPA with SeO2– 4 in NaOH (r=0.94) and SeO2– 3 in KH2PO4 (r=0.88)]. These correlations are indicative of Se extraction efficiency, thermodynamically predicted chemical transformations (such as oxidation of SeO2– 3 to SeO2– 4), and probable interconversions between the organic and inorganic Se fractions (r=0.70 in KH2PO4 extracts); as a whole the correlations can be used as statistical validations of possible geochemical processes. Received: 21 August 1995 · Accepted: 16 October 1995  相似文献   

9.
The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O2/H2S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m−2 d−1.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O2/H2S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.  相似文献   

10.
Iron (III) oxides are ubiquitous in near-surface soils and sediments and interact strongly with dissolved phosphates via sorption, co-precipitation, mineral transformation and redox-cycling reactions. Iron oxide phases are thus, an important reservoir for dissolved phosphate, and phosphate bound to iron oxides may reflect dissolved phosphate sources as well as carry a history of the biogeochemical cycling of phosphorus (P). It has recently been demonstrated that dissolved inorganic phosphate (DIP) in rivers, lakes, estuaries and the open ocean can be used to distinguish different P sources and biological reaction pathways in the ratio of 18O/16O (δ18OP) in PO43−. Here we present results of experimental studies aimed at determining whether non-biological interactions between dissolved inorganic phosphate and solid iron oxides involve fractionation of oxygen isotopes in PO4. Determination of such fractionations is critical to any interpretation of δ18OP values of modern (e.g., hydrothermal iron oxide deposits, marine sediments, soils, groundwater systems) to ancient and extraterrestrial samples (e.g., BIF’s, Martian soils). Batch sorption experiments were performed using varied concentrations of synthetic ferrihydrite and isotopically-labeled dissolved ortho-phosphate at temperatures ranging from 4 to 95 °C. Mineral transformations and morphological changes were determined by X-Ray, Mössbauer spectroscopy and SEM image analyses.Our results show that isotopic fractionation between sorbed and aqueous phosphate occurs during the early phase of sorption with isotopically-light phosphate (P16O4) preferentially incorporated into sorbed/solid phases. This fractionation showed negligible temperature-dependence and gradually decreased as a result of O-isotope exchange between sorbed and aqueous-phase phosphate, to become insignificant at greater than ∼100 h of reaction. In high-temperature experiments, this exchange was very rapid resulting in negligible fractionation between sorbed and aqueous-phase phosphate at much shorter reaction times. Mineral transformation resulted in initial preferential desorption/loss of light phosphate (P16O4) to solution. However, the continual exchange between sorbed and aqueous PO4, concomitant with this mineralogical transformation resulted again in negligible fractionation between aqueous and sorbed PO4 at long reaction times (>2000 h). This finding is consistent with results obtained from natural marine samples. Therefore, 18O values of dissolved phosphate (DIP) in sea water may be preserved during its sorption to iron-oxide minerals such as hydrothermal plume particles, making marine iron oxides a potential new proxy for dissolved phosphate in the oceans.  相似文献   

11.
Oxidation of pyrite by hydrogen peroxide (H2O2) at millimolar levels has been studied from 4 to 150 °C in order to evaluate isotopic effects potentially associated with radiolytic oxidation of pyrite. Gaseous, aqueous, and solid phases were collected and measured following sealed-tube experiments that lasted from 1 to 14 days. The dominant gaseous product was molecular oxygen. No volatile sulfur species were recovered from any experiment. Sulfate was the only aqueous sulfur species detected in solution, with sulfite and thiosulfate below the detection limits. X-ray diffraction patterns and images from scanning electron microscopy reveal solid residues composed primarily of hydrated ferric iron sulfates and sporadic ferric-ferrous iron sulfates. Hematite was detected only in solid residue produced during high temperature experiments. Elemental sulfur and/or polysulfides are inferred to be form on reacting pyrite surface based on extraction with organic solvents. Pyrite oxidation by H2O2 increases in rate with increasing H2O2concentration, pyrite surface area, and temperature. Rates measured in sealed-tube experiments at 25°C, for H2O2 concentration of 2 × 10−3 M are 8.8 × 10−9 M/m2/sec, which are higher than previous estimates. A combination of reactive oxygen species from H2O2 decomposition products and reactive iron species from pyrite dissolution is inferred to aggressively oxidize the receding pyrite surface. Competing oxidants with temperature-dependent oxidation efficiencies results in multiple reaction mechanisms for different temperatures and surface conditions. Sulfur isotope values of remaining pyrite were unchanged during the experiments, but showed distinct enrichment of 34S in produced sulfate and depletion in elemental sulfur. The Δsulfate-pyrite and Δelemental sulfur-pyrite was +0.5 to +1.5‰ and was −0.2 to −1‰, respectively. Isotope data from high-temperature experiments indicate an additional 34S-depleted sulfur fraction, with up to 4‰ depletion of 34S, in the hematite. Sulfur isotope trends were not influenced by H2O2 concentration, temperature, or reaction time. Results of this study indicate that radiolytically produced oxidants, such as hydrogen peroxide and hydroxyl radicals, could efficiently oxidize pyrite in an otherwise oxygen-limited environment. Although H2O2 is generally regarded as being of minor geochemical significance on Earth, the H2O2 molecule plays a pivotal role in Martian atmospheric and soil chemistry. Additional experimental and field studies are needed to characterize sulfur and oxygen isotope systematics during radiolytical oxidation of metallic sulfides and elemental sulfur.  相似文献   

12.
High-resolution core level and valence band (VB) X-ray photoelectron spectra (XPS) of olivine [(Mg0.87Fe0.13)2SiO4], bronzite [(Mg0.8Fe0.2)2Si2O6] and diopside [Ca(Mg0.8Fe0.2)Si2O6] were collected before and after leaching in pH ∼2 solutions with the Kratos magnetic confinement charge compensation system which minimizes differential charge broadening. The leached samples yield Si 2p, Mg 2p, Ca 2p and O 1s XPS spectral linewidths and lineshapes similar to those collected from the respective pristine samples prior to leaching. As with previous XPS studies on crushed samples, our broadscan XPS spectra show evidence for initial, preferential leaching of cations (i.e., Ca2+ and Mg2+) from the near-surface of these minerals. The O 1s spectra of leached olivine and pyroxenes show an additional peak due to OH−, which arises from H+ exchange with near-surface cations (Ca2+ and Mg2+) via electrophilic attack of H+ on the M-O-Si moiety to produce the H2Mg(M1)SiO4(surf) complex at olivine surfaces, and two complexes, H2Mg(M1)Si2O6(surf) and H4Si2O6(surf) at diopside and enstatite surfaces. The olivine and pyroxene surface complexes H2Mg(M1)SiO4(surf) and H2Mg(M1)Si2O6(surf) have been proposed previously, but the second pyroxene surface complex H4Si2O6(surf) has not. Two electrophilic reactions occur in both olivine and pyroxene. For olivine, the more rapid attacks the M2-O-Si moiety producing H2Mg(M1)SiO4(surf); while the second attacks the M1-O-Si moiety ultimately producing H4SiO4 which is released to solution. For pyroxenes, the first electrophilic reaction produces H2Mg(M1)Si2O6(surf), while the second produces.H4Si2O6(surf). These two reactions are followed by a nucleophilic attack of H2O (or H3O+) on Si of H4Si2O6(surf). This reaction is responsible for rupture of the brigding oxygen bond of the Si-O-Si moiety and release of H4SiO4 to solution. The intensity of the OH− peak for the leached pyroxenes is about double the OH− intensity for the leached olivine, consistent with the equivalent of about a monolayer of the above surface complexes being formed in all three minerals.Valence band XPS spectra and density functional calculations demonstrate the remarkable insensitivity of the valence band to leaching of Ca2+ and Mg2+ from the surface layers. This insensitivity is due to a dearth of Ca and Mg valence electron density in the valence band: the Ca-O and Mg-O bonds are highly ionic, with metal-derived s orbital electrons taking on strong O 2p character. The valence band spectrum of leached olivine shows an additional very weak peak at about 13.5 eV, which is assigned to Si 3s valence orbitals in the surface complex H2Mg(M1)SiO4, as indicated by high quality density functional calculations on an olivine where Mg2+ in M2 is replaced by 2H+. The intensity of this new peak is consistent with formation of the equivalent of a monolayer of the surface complex.  相似文献   

13.
Pore water profiles of total-CO2, pH, PO3?4, NO?3 plus NO?2, SO2?4, S2?, Fe2+ and Mn2+ have been obtained in cores from pelagic sediments of the eastern equatorial Atlantic under waters of moderate to high productivity. These profiles reveal that oxidants are consumed in order of decreasing energy production per mole of organic carbon oxidized (O2 > manganese oxides ~ nitrate > iron oxides > sulfate). Total CO2 concentrations reflect organic regeneration and calcite dissolution. Phosphate profiles are consistent with organic regeneration and with the effects of release and uptake during inorganic reactions. Nitrate profiles reflect organic regeneration and nitrate reduction, while dissolved iron and manganese profiles suggest reduction of the solid oxide phases, upward fluxes of dissolved metals and subsequent entrapment in the sediment column. Sulfate values are constant and sulfide is absent, reflecting the absence of strongly anoxic conditions.  相似文献   

14.
The effects of Na2SiO3, Na3PO4, Na4P2O7, (NaPO3)6, quebracho, tannic acid and S 808 (sulphonated product of rough phenantrene) on the floatability of the following five pure minerals: scheelite, calcite, fluorite, garnet and quartz, with sodium oleate as collector were investigated in detail as well as the role of pH on these effects. The results obtained indicate that Na4P2O7 and (NaPO3)6 were effective modifiers for the selective flotation of scheelite. The results of the batch flotation tests on mixtures of these minerals showed that the recovery of scheelite from scheelite-silicate mixtures (31% WO3) with (NaPO3)6 or Na4P2O7 increased by 20% as compared with sodium silicate and the WO3 grade of the concentrate by 5%. At room temperature, the scheelite-calcium mineral mixtures could not be separated with sodium silicate. In the separation of these mixtures with the phosphate modifiers, a concentrate grade of 47–60% WO3 was obtained at 70–90% recovery. This showed that the flowsheet of the selective flotation of scheelite with phosphate modifiers may replace the conventional Petrov's process.  相似文献   

15.
Ophiolitic metabasite host rocks of the Whalesback cupriferous iron sulfide deposit, Notre Dame Bay, Newfoundland, have undergone extensive redistribution of alkalis and lime. Such alteration (hydrothermal alteration, halmyrolysis) occurred before Acadian deformation and chlorite-zone greenschist facies metamorphism. The pyritic ores occur in chloritized rocks within such altered metabasites. Areas of intense chloritization, usually associated with silicification and minor sericitization, represent a more advanced stage of alteration. The most striking bulk chemical change in the ore zone is the almost complete leaching of sodium and calcium from the host metabasites. Increases in iron and sulfur contents and erratic enrichment in potassium are also characteristic. No significant changes are shown by SiO2, Al2O3, TiO2, MgO and MnO. Though subsequently metamorphosed to the chlorite zone of the greenschist facies, wall-rock alteration appears to have originally been chemically similar to that observed in the Cypriot cupriferous iron sulfide ores except for high CO2 associated with hydrothermal activity in the Whalesback area.  相似文献   

16.
The effects of phosphate speciation on both rates of isotopic exchange and oxygen isotope equilibrium fractionation factors between aqueous phosphate and water were examined over the temperature range 70 to 180°C. Exchange between phosphate and water is much faster at low pH than at high pH, an observation that is similar to what has been observed in the analogous sulfate-water system. Oxygen isotope fractionations between protonated species like H3PO4 and H2PO4− that are dominant at relatively low pH and species like PO43− and ion pairs like KHPO4− that are dominant at relatively high pH, range between 5 and 8‰ at the temperatures of the experiments. In aqueous phosphate systems at equilibrium, 18O/16O ratios increase with increasing degree of protonation of phosphate. This effect can be explained in part by the relative magnitudes of the dissociation constants of the protonated species. Under equilibrium conditions, carbonate in solution or in solid phases concentrates 18O relative to orthophosphate in solution or in solid phases at all temperatures, supporting the traditional view that biogenic phosphate is precipitated in near oxygen isotope equilibrium with body/ambient aqueous fluids with no attendant vital effects.  相似文献   

17.
This study investigated the effect of cations and anions on the sorption and desorption of iron (Fe) and manganese (Mn) in six surface calcareous soil samples from Western Iran. Six 10 mM electrolyte background solutions were used in the study, i.e., KCl, KNO3, KH2PO4, Ca(NO3)2, NaNO3, and NH4NO3. NH4NO3 and NaNO3 increased the soil retention of Fe and Mn, whereas Ca(NO3)2 decreased the soil retention of Fe and Mn. Iron and Mn sorption was decreased by NO3 ? compared with H2PO4 ? or Cl?. The Freundlich equation adequately described Fe and Mn adsorption, with all background electrolytes. The Freundlich distribution coefficient (K F) decreased in the order H2PO4 ? > Cl? > NO3 ? for Mn and H2PO4 ? > NO3 ? > Cl? for Fe. The highest sorption reversibility was for Fe and Mn in competition with a Ca2+ background, indicating the high mobility of these two cations. A MINTEQ speciation solubility model showed that Fe and Mn speciation was considerably affected by the electrolyte background used. Saturation indices indicated that all ion background solutions were saturated with respect to siderite and vivianite at low and high Fe concentrations. All ion background solutions were saturated with respect to MnCO3(am), MnHPO4, and rhodochrosite at low and high Mn concentrations. The hysteresis indices (HI) obtained for the different ion backgrounds were regressed on soil properties indicating that silt, clay, sand, and electrical conductivity (EC) were the most important soil properties influencing Fe adsorption, while cation exchange capacity (CEC), organic matter (OM), and Mn-DTPA affected Mn adsorption in these soils.  相似文献   

18.
A phase of Ca3 (PO4)2, synthesized at 12GPa and 2300° C, is structurally analyzed by the single crystal X-ray diffraction method. This Ca3(PO4)2 is found to be a dense polymorph of tricalcium phosphate isostructural with Ba3 (PO4)2 and named γ-Ca3 (PO4)2. In the structure of Ca3 (PO4)2, a phosphorus atom is tetrahedrally coordinated by oxygen atoms and calcium atoms occupy two types of large metal sites. The Ca(1) site has twelve oxygen neighbours with the mean bond length of 2.739 Å while the other Ca(2) site is coordinated by ten oxygen atoms with the mean Ca-O distance of 2.588Å. The structure is characterized by the translationally interconnected polyhedral sequence PO4-Ca(2)O10-Ca (1)O12-Ca (2)O10-PO4 in the direction of the c axis. This dense phase of Ca3(PO4)2 with two large metal sites may be an important host for very large lithophile elements in the deep upper mantle of the earth.  相似文献   

19.
Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 °C to 25 °C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars.Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl2·4H2O, FeCl2·6H2O, FeSO4·H2O, FeSO4·7H2O, FeCO3, and Fe(OH)3] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO4, Fe-HCO3, H-Fe-Cl, and H-Fe-SO4.We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO3), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification.What began as a dilute Mg-Fe-HCO3 dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO4-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O2(g)], but later caused oxidation of iron [high O2(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses.  相似文献   

20.
The thermochemical study of natural hydrous calcium and iron phosphate, anapaite Ca2Fe(PO4)2 · 4H2O (Kerch iron ore deposit, Crimea, Russia), was carried out using high-temperature melt solution calorimetry with a Tian-Kalvet microcalorimeter. The enthalpy of formation of the mineral from elements was obtained to be Δ f Hel°(298.15 K) =–4812 ± 16 kJ/mol. The values of the standard entropy and the Gibbs energy of anapaite formation are S°(298.15 K) = 404.2 J/K mol and Δ f Gel°(298.15 K) =–4352 ± 16 kJ/mol, respectively.  相似文献   

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