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1.
Many studies have proposed that silicic acid and phosphate (PV) can displace arsenic sorbed to iron oxides leading to elevated As concentrations in aquatic systems. While surface complexation models are adept at quantifying sorption to synthetic oxides in laboratory systems their application to complex natural systems remains challenging. In this study we provide a systematic approach to developing a robust use of models for understanding AsV distribution in natural systems in which hydrated iron oxides are the main adsorptive phase. The Waikato River provides a useful laboratory for this work because it contains high H4SiO4, AsV and PV loadings due to geothermal and agricultural inputs. A 15 min oxalate extraction and a 48 h ethylenediaminetetraacetic acid (EDTA) extraction of river sediment contained the same ratios of As:Fe, P:Fe and Si:Fe. Both of these extracts target the poorly ordered iron oxide phases (typically ferrihydrite) and by following the release of elements over time in the EDTA extraction it was possible to demonstrate that the extracted As, P, and Si were associated with the ferrihydrite. This demonstrates for the first time that a single oxalate extraction can quantify ferrihydrite sorbed H4SiO4, As and PV and provides a basis to quantify the role of these ligands in inhibiting AsV sorption to sediments. The measured concentrations of ferrihydrite sorbed AsV, PV and H4SiO4 for the Waikato River suspended sediment allow for the informed selection of appropriate model parameters for applying the Diffuse Layer Model to the system. In this way it was possible to quantify the effect of the individual components in the river water on AsV sorption. This study provides an explanation for the observation that the proportion of sorbed As in the Waikato River is generally significantly lower than that observed in rivers closer to the world average concentrations. More generally the study provides a method to quantify the role of individual water chemistry components on AsV distribution in natural systems.  相似文献   

2.
Little research has been done to study the role of soil parameters in cobalt (Co) retention, release and the processes involved in calcareous soils of arid and semi-arid regions. We studied the Co sorption and desorption capacity of various calcareous soils using batch technique. The sorption and desorption behavior of Co varied greatly among the studied soils. The sorbed fraction ranged from 92.3% to 97.2% and from 51.0% to 71.8%, when 5 and 200 mg Co l−1, was added to the soil samples, respectively. Cobalt sorption curves were well fitted with Langmuir, Freundlich, and linear equations. The values of the distribution coefficients obtained from linear equation ranged from 9.5 l kg−1 to 23.4 l kg−1. Desorption experiments resulted in a Co recovery ranged from 3.6% to 11.4%, indicating a low desorption of Co from soils. The results of the geochemical modeling indicated that under low Co addition, the solutions were undersaturated with respect to Co(OH)2(am), Co(OH)2(c), Co3(PO4)2(s), CoCl2(s), CoHPO4(s), CoCl2·6H2O(s), and CoO(s), whereas under higher Co addition, the solutions were undersaturated with respect to Co(OH)2(am), CoCl2(s), CoCl2·6H2O(s), CoO(s), CoHPO4(s), and saturated with respect to Co3(PO4)2(s), and CoCO3(s). The hysteresis indices indicated that desorption of freshly sorbed Co with 0.01 M CaCl2 was hysteretic in all soils and low mobility and leaching potential of freshly sorbed Co can be expected from these calcareous soils. Statistical correlations revealed that Co sorption and desorption onto the soils were influenced by the presence of CaCO3 in soils. These findings suggested that calcareous soils are able to retain strongly Co in which the movement of Co in the soil profile would be negligible. Thus, little risk of groundwater contamination can be expected with Co in these calcareous soils.  相似文献   

3.
Sorptive stabilization of organic matter by amorphous Al hydroxide   总被引：3，自引：0，他引：3  
Amorphous Al hydroxides (am-Al(OH)3) strongly sorb and by this means likely protect dissolved organic matter (OM) against microbial decay in soils. We carried out batch sorption experiments (pH 4.5; 40 mg organic C L−1) with OM extracted from organic horizons under a Norway spruce and a European beech forest. The stabilization of OM by sorption was analyzed by comparing the CO2 mineralized during the incubation of sorbed and non-sorbed OM. The mineralization of OM was evaluated based in terms of (i) the availability of the am-Al(OH)3, thus surface OM loadings, (ii) spectral properties of OM, and (iii) the presence of phosphate as a competitor for OM. This was done by varying the solid-to-solution ratio (SSR = 0.02-1.2 g L−1) during sorption. At low SSRs, hence limited am-Al(OH)3 availability, only small portions of dissolved OM were sorbed; for OM from Oa horizons, the mineralization of the sorbed fraction exceeded that of the original dissolved OM. The likely reason is competition with phosphate for sorption sites favouring the formation of weak mineral-organic bindings and the surface accumulation of N-rich, less aromatic and less complex OM. This small fraction controlled the mineralization of sorbed OM even at higher SSRs. At higher SSRs, i.e., with am-Al(OH)3 more available, competition of phosphate decreased and aromatic compounds were sorbed selectively, which resulted in pronounced resistance of sorbed OM against decay. The combined OC mineralization of sorbed and non-sorbed OM was 12-65% less than that of the original DOM. Sorbed OM contributed only little to the overall OC mineralization. Stabilization of OC increased in direct proportion to am-Al(OH)3 availability, despite constant aromatic C (∼30%). The strong stabilization at higher mineral availability is primarily governed by strong Al-OM bonds formed under less competitive conditions. Due to these strong bonds and the resulting strong stabilization, the surface loading, a proxy for the mineral’s occupation by OM, was not a factor in the mineralization of sorbed OM over a wide range of C sorption (0.2-1.1 mg C m−2). This study demonstrates that sorption to am-Al(OH)3 results in stabilization of OM. The mineral availability as well as the inorganic solution chemistry control sorptive interactions, thereby the properties of sorbed OM, and the stability of OM against microbial decay.  相似文献   

4.
Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg2+ and Ca2+ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.  相似文献   

5.
Hydration of organic coatings in soils is expected to affect the sorption of oxyanions onto hydrous Fe and Al oxides. We hypothesized that the hydration of polygalacturonate (PGA) coatings on alumina (Al2O3) increases their permeability for phosphate. Pure and PGA-coated alumina were equilibrated in deionized water for 2 and 170 h at pH 5 and 20 °C before studying (i) their porosity with N2 gas adsorption and 1H NMR relaxometry, (ii) structural changes of PGA-coatings with differential scanning calorimetry (DSC), and (iii) the kinetics of phosphate sorption and PGA desorption in batch experiments. Scanning electron micrographs revealed that PGA molecules formed three-dimensional networks with pores ranging in size from <10 to several hundred nanometers. Our NMR results showed that the water content of intraparticle alumina pores decreased upon PGA sorption, indicating a displacement of pore water by PGA. The amount of water in interparticle alumina pores increased strongly after PGA addition, however, and was attributed to water in pores of PGA and/or in pores at the PGA-alumina interface. The flexibility of PGA molecules and the fraction of a PGA gel phase increased within one week of hydration, implying restructuring of PGA. Hydration of PGA coatings increased the amount of phosphate defined as instantaneously sorbed by 84%, showing that restructuring of PGA enhanced the accessibility of phosphate to external alumina surfaces. Despite the fact that the efficacy of phosphate to displace PGA was higher after 170 h than after 2 h, a higher phosphate surface loading was required after 170 h to set off PGA desorption. Our findings imply that the number of PGA chain segments directly attached to the alumina surface decreased with time. We conclude that hydration/dehydration of polymeric surface coatings affects the sorption kinetics of oxyanions, and may thus control the sorption and transport of solutes in soils.  相似文献   

6.
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   

7.
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   

8.
Sequestration of organic carbon (OC) in environmental systems is critical to mitigating climate change. Organo-mineral associations, especially those with iron (Fe) oxides, drive the chemistry of OC sequestration and stability in soils. Short-range-ordered Fe oxides, such as ferrihydrite, demonstrate a high affinity for OC in binary systems. Calcium commonly co-associates with OC and Fe oxides in soils, though the bonding mechanism (e.g., cation bridging) and implications of the co-association for OC sequestration remain unresolved. We explored the effect of calcium (Ca2+) on the sorption of dissolved OC to 2-line ferrihydrite. Sorption experiments were conducted between leaf litter-extractable OC and ferrihydrite at pH 4 to 9 with different initial C/Fe molar ratios and Ca2+ concentrations. The extent of OC sorption to ferrihydrite in the presence of Ca2+ increased across all tested pH values, especially at pH ≥ 7. Sorbed OC concentration at pH 9 increased from 8.72 ± 0.16 to 13.3 ± 0.20 mmol OC g?1 ferrihydrite between treatments of no added Ca2+ and 30 mM Ca2+ addition. Batch experiments were paired with spectroscopic studies to probe the speciation of sorbed OC and elucidate the sorption mechanism. ATR-FTIR spectroscopy analysis revealed that carboxylic functional moieties were the primary sorbed OC species that were preferentially bound to ferrihydrite and suggested an increase in Fe-carboxylate ligand exchange in the presence of Ca at pH 9. Results from batch to spectroscopic experiments provide significant evidence for the enhancement of dissolved OC sequestration to 2-line ferrihydrite and suggest the formation of Fe–Ca-OC ternary complexes. Findings of this research will inform modeling of environmental C cycling and have the potential to influence strategies for managing land to minimize OM stabilization.  相似文献   

9.
Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides—collectively referred to as “oxides” hereafter—are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO2, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite Oi, Oe, and Oa horizon leachate (“O horizon leachate” hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOM–HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 × 102 μg C m?2), DOM desorption—assessed by 0.1 M NaH2PO4 extraction—is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 102 μg C m?2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM–HMO complexes may be more vulnerable to reductive dissolution than DOM–goethite complexes.  相似文献   

10.
Iron isotopes were used to investigate iron transformation processes during an in situ field experiment for removal of dissolved Fe from reduced groundwater. This experiment provided a unique setting for exploring Fe isotope fractionation in a natural system. Oxygen-containing water was injected at a test well into an aquifer containing Fe(II)-rich reduced water, leading to oxidation of Fe(II) and precipitation of Fe(III)(hydr)oxides. Subsequently, groundwater was extracted from the same well over a time period much longer than the injection time. Since the surrounding water is rich in Fe(II), the Fe(II) concentration in the extracted water increased over time. The increase was strongly retarded in comparison to a conservative tracer added to the injected solution, indicating that adsorption of Fe(II) onto the newly formed Fe(III)(hydr)oxides occurred. A series of injection-extraction (push-pull) cycles were performed at the same well. The δ57Fe/54Fe of pre-experiment background groundwater (−0.57 ± 0.17 ‰) was lighter than the sediment leach of Fe(III) (−0.24 ± 0.08 ‰), probably due to slight fractionation (only ∼0.3 ‰) during microbial mediated reductive dissolution of Fe(III)(hydr)oxides present in the aquifer. During the experiment, Fe(II) was adsorbed from native groundwater drawn into the oxidized zone and onto Fe(III)(hydr)oxides producing a very light groundwater component with δ57Fe/54Fe as low as −4 ‰, indicating that heavier Fe(II) is preferentially adsorbed to the newly formed Fe(III)(hydr)oxides surfaces. Iron concentrations increased with time of extraction, and δ57Fe/54Fe linearly correlated with Fe concentrations (R2 = 0.95). This pattern was reproducible over five individual cycles, indicating that the same process occurs during repeated injection/extraction cycles. We present a reactive transport model to explain the observed abiotic fractionation due to adsorption of Fe(II) on Fe(III)(hydr)oxides. The fractionation is probably caused by isotopic differences in the equilibrium sorption constants of the various isotopes (Kads) and not by sorption kinetics. A fractionation factor α57/54 of 1.001 fits the observed fractionation.  相似文献   

11.
 Acid mine drainage (AMD) occurs when sulfide minerals are exposed to an oxidizing environment. Most of the methods for preventing AMD are either short-term or high cost solutions. Coating with iron phosphate is a new technology for the abatement of AMD. It involves treating the sulfide with a coating solution composed of H2O2, KH2PO4, and sodium acetate as a buffer agent. The H2O2 oxidizes the sulfide surface and produces Fe3+ so that iron phosphate precipitates as a coating on the sulfide surface. Experiments performed under laboratory conditions prove that an iron phosphate coating can be established on pyrrhotite surfaces with optimal concentrations of the coating solution in the range of: 0.2M/0.01M H2O2, 0.2M KH2PO4, and 0.2M sodium acetate NaAc, depending on the experimental scale. Iron phosphate coating may be a long-term solution to the problem of AMD. The method would be easy to implement; the reagent cost, however, is not low enough, although it is lower than the conventional treatment with lime. Received: 30 March 1995 · Accepted: 6 September 1995  相似文献   

12.
This work assessed both the fractionation and the seasonal mobility variations of Ga and In in systems impacted by acidic thermal waters. This was accomplished by performing thermodynamic calculations using the PHREEQC algorithm and by assessing the activity of acidophilic iron-oxidizing bacteria. The pH of the Kusatsu thermal waters in Gunma Prefecture, central Japan, is rapidly increased following the addition of a lime suspension. After an abrupt pH increase, under which conditions free ions of Ga and In and their complexes with Cl? and SO42? exist only in negligible quantities, the majority of dissolved Ga and In is removed by sorption onto suspended hydrous ferric oxides (HFOs). These HFOs are then transported to an artificial lake without significant sedimentation along the river. Subsequently, the suspended HFOs settle out and are added to sediments without significant fractionation between Ga and In. The Tamagawa thermal waters in Akita Prefecture, northeast Japan, are also treated with lime. However, complete neutralization requires mixing with some tributary streams, leading to a gradual downstream increase in pH. Dissolved Ga is, in general, sorbed by HFOs in upstream areas, leading to wide dispersal of Ga across the entire watershed. In comparison, In is transported to the lake inlet predominantly as a Cl? complex species without significant removal along the river, with the majority being precipitated in an artificial lake, where Cl? concentrations are too low to form stable complex species with In, and thus, dissolved In is sorbed by HFOs. As a result, In is effectively concentrated within downstream lakebed sediments, whereas Ga is dispersed along the river. Seasonal variations in Ga mobility within the Tamagawa field between snowmelt and low-flow seasons are primarily controlled by pH, because hydrolysis reactions of these metals, which are related to sorption reactions, tend to occur in the upstream regions in the snowmelt season. However, under warmer conditions, HFO formation preferably occurs due to the activity of acidophilic iron-oxidizing bacteria. Thus, under similar pH variations, dissolved Ga is more effectively removed by HFOs during warmer seasons. On the contrary, because HFOs are abundantly formed in low-flow season, even under colder conditions, before In hydrolysis reaction starts to occur, In mobility is less affected by water temperature and then bacterial activity.  相似文献   

13.
Phosphate sorption and desorption experiments were conducted with four ferruginous soils (alfisols) of Eastern India, in view of the low native phosphate concentrations in tropical Indian soils. From the P-isotherm curve, standard P requirement (SPR) of the soils was determined. Phosphate sorption data were fitted to both Langmuir and Freundlich equations and mean sorption maximum values obtained for the different soil series were in the decreasing order as Matimahal > Anandapur > Mrigindih > Kashipur. The fraction of added P sorbed followed the same trend as SPR, P sorption maximum (Pmax), phosphate affinity constant (K), maximum phosphate buffering capacity (MPBC), Freundlich constant K′ and phosphate desorption values. Phosphate sorption maximum was significantly correlated with MPBC, Freundlich 1/n, SPR, clay and different forms of Fe and Al. The value of K (bonding energy) was significantly correlated with MPBC, Freundlich K′ and pyrophosphate extractable Fe and Al. The MPBC was significantly correlated with Freundlich K′, Freundlich constant 1/n, clay, oxalate and dithionite extractable, amorphous and crystalline form of Fe and Al. Freundlich K′ was significantly correlated with Freundlich 1/n, pHwater, clay, dithionite extractable and crystalline form of Fe and Al. The results suggested that the soils having higher amount of extractable and reactive Fe and Al shared higher P sorbtion capacity and such soils may need higher levels of P application  相似文献   

14.
《Applied Geochemistry》2003,18(5):693-710
In experiments of 7 days duration using voltammetric and radiotracer measurement techniques, the role of different particle types in the sorption of dissolved metal species in a disturbed deep-sea bottom seawater system were investigated. Resuspension of oxic to suboxic surface sediment into the bottom water in the deep sea (either by natural events or industrial activities like Mn nodule mining) has been shown to be followed quickly by scavenging of dissolved heavy metals, e.g. released from interstitial water, on the resuspended particles. Compared to other deep-sea particles (like clay minerals, calcite and apatite), Mn and Fe oxides and oxyhydroxides were found to be by far the most important phases in scavenging many dissolved heavy metals. Only Pb was sorbed strongly on all particles used, with highest affinity to carbonate fluorapatite. Caesium+ was significantly scavenged only by clay minerals like illite. The sorption experiments support a simple electrostatic model: Hydrated cations and labile cationic chloro-complexes in seawater like Mn2+, MnCl+, Co2+, Ni2+, Cu2+, Zn2+, Ba2+, and PbCl+, are preferentially adsorbed or ion-exchanged on the negatively charged surfaces of Mn oxides. In contrast, oxyanions and neutrally or negatively charged complexes like HVO42−, MoO42−, HAsO42−, UO2(CO3)22−, and PbCO30 associate with neutral to slightly positive amphoteric Fe oxyhydroxide particles. Metals forming strong chloro-complexes in seawater like Cd (CdCl20), are less readily sorbed by oxides than others. A comparison of the results of voltammetric and radiotracer techniques revealed that after fast sorption within the first hour, isotopic exchange dominated reactions on MnO2-rich particles in the following days. This was especially pronounced for Mn and Co which are bound to the Mn oxide surface via a redox transformation.  相似文献   

15.
Microbial dissimilatory iron reduction (DIR) has been identified as a mechanism for production of aqueous Fe(II) that has low 56Fe/54Fe ratios in modern and ancient suboxic environments that contain ferric oxides or hydroxides. These studies suggest that DIR could have played an important role in producing distinct Fe isotope compositions in Precambrian banded iron formations or other marine sedimentary rocks. However, the applicability of experimental studies of Fe isotope fractionation produced by DIR in geochemically simple systems to ancient marine environments remains unclear. Here we report Fe isotope fractionations produced during dissimilatory microbial reduction of hematite by Geobacter sulfurreducens in the presence and absence of dissolved Si at neutral and alkaline pH. Hematite reduction was significantly decreased by Si at alkaline (but not neutral) pH, presumably due to Si polymerization at the hematite surface. The presence of Si altered Fe isotope fractionation factors between aqueous Fe(II) or sorbed Fe(II) and reactive Fe(III), reflecting changes in bonding environment of the reactive Fe(III) component at the oxide surface. Despite these changes in isotopic fractionations, our results demonstrate that microbial Fe(III) oxide reduction produces Fe(II) with negative δ56Fe values under conditions of variable pH and dissolved Si, similar to the large inventory of negative δ56Fe in Neoarchean and Paleoproterozoic age marine sedimentary rocks.  相似文献   

16.
Phosphomonoesters are an important source of dissolved inorganic orthophosphate (PO4 or Pi), the preferred form of P utilized by microbiota and aquatic plants in marine and freshwater ecosystems. Two enzymes involved in phosphomonoester metabolism and commonly detected in natural waters (alkaline phosphatase and 5′-nucleotidase) have been studied to determine the oxygen isotope signature of Pi-regeneration from phosphomonoesters by enzymatic degradation. Oxygen (O) isotope ratios of water and Pi released from phosphomonoesters during enzyme hydrolysis experiments demonstrate that released Pi incorporates one oxygen atom from water. The isotopic fractionation between this incorporated water O and ambient water O is −30 (±8)‰ for alkaline phosphatase and −10 (±1)‰ for 5′-nucleotidase, with very weak dependence on temperature. The result of these enzyme-specific isotopic fractionations at one of the four O sites in PO4 is that the δ18O value of Pi regenerated by 5′-nucleotidase is 5‰ higher than Pi regenerated by alkaline phosphatase from the same phosphomonoester substrate. The δ18O value of regenerated Pi also reflects inheritance of 75% of O from the phosphomonoester substrate, thus making the δ18O of phosphomonoester-derived Pi a potential tracer of organophosphorous compound sources. Phosphomonoesterase-regenerated Pi has a distinct phosphate oxygen isotope signature that is different and distinguishable from that of biologically recycled and subsequently equilibrated Pi and Pi regenerated from photooxidation of organic matter. The δ18O value of regenerated Pi will correlate positively with the δ18O value of bulk water and the fractionation, α, between regenerated Pi and water, αregen Pi-water, should converge toward equilibrium αPi-water values with increased biological cycling of Pi.  相似文献   

17.
The solubility behavior of phosphorus in glasses and melts in the system Na2O-Al2O3-SiO2-P2O5 has been examined as a function of temperature and Al2O3 content with microRaman spectroscopy. The Al2O3 was added (2, 4, 5, 6, and 8 mol% Al2O3) to melts with 80 mol% SiO2 and ∼2 mol% P2O5. The compositions range from peralkaline, via meta-aluminous to peraluminous. Raman spectra were obtained of both the phosphorus-free and phosphorous-bearing glasses and melts between 25 and 1218 °C. The Raman spectrum of Al-free, P-bearing glass exhibits a characteristic strong band near 940 cm−1 assigned to P=O stretching in orthophosphate complexes together with a weaker band near 1000 cm−1 assigned P2O7 complexes. With increasing Al content, the proportion of P2O7 initially increases relative to PO4 and is joined by AlPO4 complexes which exhibit a characteristic P-O stretch mode slightly above 1100 cm−1. The latter complex appears to dominate in meta-aluminosilicate glass and is the only phosphate complex in peraluminous glasses. When P-bearing peralkaline silicate and aluminosilicate glasses are transformed to supercooled melts, there is a rapid decrease in PO4/P2O7 so that in the molten state, PO4 units are barely discernible. The P2O7/AlPO4 abundance ratio in peralkaline compositions increases with increasing temperature. This decrease in PO4/P2O7 with increasing temperature results in depolymerization of the silicate melts. Dissolved P2O5 in peraluminous glass and melts forms AlPO4 complexes only. This solution mechanism has no discernible influence on the aluminosilicate melt structure. There is no effect of temperature on this solution mechanism. Received: 7 October 1997 / Accepted: 11 May 1998  相似文献   

18.
The sorption of Cu(II) and Pb(II) to kaolinite-fulvic acid colloids was investigated by potentiometric titrations. To assess the possible interactions between kaolinite and fulvic acid during metal sorption, experimental sorption isotherms were compared with predictions based on a linear additivity model (LAM). Suspensions of 5 g L−1 kaolinite and 0.03 g L−1 fulvic acid in 0.01 M NaNO3 were titrated with Cu and Pb solutions, respectively. The suspension pH was kept constant at pH 4, 6, or 8. The free ion activities of Cu2+ and Pb2+ were monitored in the titration vessel using ion selective electrodes. Total dissolved concentrations of metals (by ICP-MS) and fulvic acid (by UV-absorption) were determined in samples taken after each titration step. The amounts of metals sorbed to the solid phase, comprised of kaolinite plus surface-bound fulvic acid, were calculated by difference. Compared to pure kaolinite, addition of fulvic acid to the clay strongly increased metal sorption to the solid phase. This effect was more pronounced at pH 4 and 6 than at pH 8, because more fulvic acid was sorbed to the kaolinite surface under acidic conditions. Addition of Pb enhanced the sorption of fulvic acid onto kaolinite at pH 6 and 8, but not at pH 4. Addition of Cu had no effect on the sorption of fulvic acid onto kaolinite. In the LAM, metal sorption to the kaolinite surface was predicted by a two-site, 1-pK basic Stern model and metal sorption to the fulvic acid was calculated with the NICA-Donnan model, respectively. The LAM provided good predictions of Cu sorption to the kaolinite-fulvic acid colloids over the entire range in pH and free Cu2+ ion activity (10−12 to 10−5). The sorption of Pb was slightly underestimated by the LAM under most conditions. A fractionation of the fulvic acid during sorption to kaolinite was observed, but this could not explain the observed deviations of the LAM predictions from the experimental Pb sorption isotherms.  相似文献   

19.
Behavior of Uranium in the Yellow River Plume (Yellow River Estuary)   总被引：2，自引：0，他引：2  
The Yellow River (Huanghe) is the second largest river in China and is known for its high turbidity. It also has remarkably high levels of dissolved uranium (U) concentrations (up to 38 nmol 1-1). To examine the mixing behavior of dissolved U between river water and seawater, surface water samples were collected along a salinity gradient from the Yellow River plume during September 2004 and were measured for dissolved U concentration,234U:238U activity ratio, phosphate (PO4 3–), and suspended particulate matter. Laboratory experiments were also conducted to simulate the mixing process in the Yellow River plume using unfiltered Yellow River water and filtered seawater. The results showed a nonconservative behavior for dissolved U at salinities < 20 with an addition of U to the plume waters estimated at about 1.4 X 105 mol yr–1. A similarity between variations in dissolved U and PO4 3– with salinity was also found. There are two major mechanisms, desorption from suspended sediments and diffusion from interstitial waters of bottom sediments, that may cause the elevated concentrations of dissolved U and PO4 3– in mid-salinity waters. Mixing experiments indicate that desorption seems more responsible for the elevated dissolved U concentrations, whereas diffusion influences more the enrichment of PO4 3–.  相似文献   

20.
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   

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