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1.
The amounts of inorganic P sorbed by a range of Fe- and Al- containing components varied appreciably and decreased in the order allophane > fresh Al gel > Fe gel pseudoboehmite > aged Al gel > dried Fe gel > Fe-coated kaolinite > haematite > goethite > akaganeite > gibbsite = ground kaolinite > dispersed kaolinite. Al gel sorbed 30 to 70 times more P than gibbsite, and Fe gel sorbed approximately 10 times more P than its crystalline analogues (haematite, goethite. and akaganeite). Despite large differences in the extent of P sorption, the form of the isotherm was essentially the same for each sorbent. The ability of freshly-prepared Al gel suspensions to sorb P decreased with ageing, a property not shown by Fe gel. Drying of Fe gel at 80°C, however, caused an approximately 4-fold decrease in P sorption. Precipitation of Fe gel (2% Fe) on the surface of kaolinite increased P sorption by a factor of 10. The occurrence of Fe gel as a coating apparently presents more sorption sites to solution per unit weight of Fe gel than Fe gel alone. A linear relationship (r= 0.98) was obtained between the amount OH? sorbed per unit increase in pH value (‘hydroxyl buffering’) and the overall P sorption maximum for each sorbent. Hydroxyl buffering provided a better index of P sorption potential than specific surface area. Except for the crystalline Fe sorbents, isotherms obtained by plotting fractional sorption saturation against final solution P concentration for the sorbents were essentially coincident with those for several contrasting soils. For crystalline Fe components a lower relative amount of weaker sorption, as opposed to chemisorption, of the overall sorption maximum was obtained. Differences in the extent of P sorption. however, appear to be primarily related to the number of functional M-OH groups presented at the solid-solution interface.  相似文献   

2.
Amounts of inorganic phosphate (P) sorbed by two unfertilized soils, during times less than required to reach equilibrium, were affected by the ionic strength and cation species of the matrix solution. For non-equilibrium conditions the amounts of P sorbed increased with increasing ionic strength and were greater with Ca2+ than Na+. For higher P additions, resulting in equilibrium solution P concentrations greater than 30 to 40μrnole 1?1, the effects of the matrix solution on P sorption were maintained at equilibrium, whereas at lower P additions the dependence of sorption on matrix solution composition was eliminated at equilibrium. Equilibrium sorption isotherms for each soil and matrix solution were described by three Langmuir equations, which corresponded to distinct concentration ranges or regions (I, II, and III) on the overall isotherm. The free energies of sorption (ΔG) for each region, were essentially independent of the soil matrix solution. The sorption maxima for regions I and II of the isotherm for a particular soil were also virtually independent of the matrix solution used. The sorption maximum for region III, however, was markedly dependent on the matrix solution, implying a potential-determining (p.d.) sorption mechanism.  相似文献   

3.
Abstract

A laboratory experiment was conducted to study kinetics of sorption of orthophosphate (OP) and pyrophosphate (PP) from dilute solutions by three ammoniated tropical soils. Milligrams of P sorbed by soil (?P) and shaking time (t) showed a linear relationship: ?P = a + b √t. The data suggested two diffusion — controlled processes during P sorption. In general, due to ammoniation, initial sorption rate of OP (in linear region I) increased while that of PP decreased. PP was sorbed more than OP. Sorption rate of OP and PP in linear region II showed a tendency to decrease with increasing ammoniation levels.  相似文献   

4.
MECHANISMS OF PHOSPHATE SORPTION BY SOILS AND HYDROUS FERRIC OXIDE GEL   总被引：5，自引：0，他引：5  
Data for the sorption of added inorganic phosphate (P) by contrasting soils and iron oxide gel were resolved by a method of successive approximation of the Langmuir sorption constants. Three distinct Langmuir equations described the overall isotherm irrespective of the experimental conditions used. Free energies of sorption (ΔG) for a particular region were similar for each soil and for iron oxide gel under all experimental conditions. In contrast, the sorption maximum for each region was influenced by the sorbent and experimental conditions. Because of the pronounced similarities in their P sorption characteristics iron oxide gel was used as a model surface for P sorption by soils. Three mechanisms for P sorption by iron oxide gel and by soils are proposed: (i) chemisorption at protonated surface sites, (ii) chemisorption by replacement of surface hydroxyls, and (iii) a more-physical sorption of P as a potential-determining ion.  相似文献   

5.
TIME-DEPENDENT SORPTION OF PHOSPHATE BY SOILS AND HYDROUS FERRIC OXIDES   总被引：7，自引：0，他引：7  
The sorption of inorganic phosphate (P) by soils and hydrous ferric oxides was studied at times up to 192h. An initially rapid decrease in solution P concentration was followed by a much slower decrease between 48 and 192h with soils, Fe gel. and natural goethite, whereas synthetic goethite gave a well-defined equilibrium condition after only 48h. Resolution of the sorption isotherms showed that the increase in P sorption with time involved an appreciable shift of P from a more-physically sorbed form to a chemisorbed form. This was supported by chemical fractionation which showed that NaOH-extractable P was fairly constant with increasing sorption time, whereas the additional sorbed P was extracted by citrate-dithionite-bicarbonate from soils, and by HC1 from Fe gel and natural goethite. These sorbents contained short-range (amorphous) material, whereas synthetic goethite, from which all sorbed P was NaOH –extractable. did not. It is proposed that the time-dependent sorption of P and the associated shift of P to chemisorbed forms, involves the diffusion of P into “structurally porous”, short-range order material.  相似文献   

6.
The sorption of Pb(II), Cr(III) and Cr(VI) from aqueous solution using alum-derived water treatment sludge was investigated using the batch adsorption technique. Samples of sludge from two separate water treatment plants were used (one where alum was used alone and one where it was used in combination with activated C). The sorption characteristics of the two samples were generally very similar. Sorption isotherm data for all three ions fitted equally well to both Freundlich and Langmuir equations. Maximum sorption capacity and indices of sorption intensity both followed the order: Cr(III)?>?Pb(II)?>?Cr(VI). Kinetic data correlated well with a pseudo-second-order kinetic model suggesting the process involved was chemisorption. Sorption was pH-dependant with percentage sorption of Cr(III) and Pb(II) increasing from <30% to 100% between pH?3 and 6 whilst that of Cr(VI) declined greatly between pH?5 and 8. HNO3 at a concentration of 0.1?M was effective at removing sorbed Cr(III) and Pb(II) from the sludge surfaces and regeneration was successful for eight sorption/removal cycles. It was concluded that water treatment sludge is a suitable material from which to develop a low-cost adsorbent for removal of Cr and Pb from wastewater streams.  相似文献   

7.
Abstract

The study aims at determining the cobalt retention properties of various soil components. Therefore, cobalt (Co) sorptions and extractions were carried out using an Oxisol sample before (untreated) and after successive removal of organic matter and active manganese (Mn) oxides (H2O2‐treated) and iron (Fe) oxides (H2O2+CBD‐treated). A synthetic goethite was included for comparison. Sorption of the four sorbents was determined over a range of Co concentrations (initially 10‐8 M to 10‐4 M), pH values (3 to 8) and reaction times (2 hours to 504 hours). The Co species sorbed was Co(ll), since oxygen exclusion during sorption had no effect on the amount sorbed. The pH‐dependent sorption curve (sorption edge) was shifted to lower pH at decreasing initial Co concentration and increasing reaction time. The displacements, in particular of the sorption edges corresponding to the lowest initial Co concentrations, to successively higher pH following removal of Mn oxides, organic matter and Fe oxides could be attributed to sorption onto sites of decreasing Co affinity [Mn oxides (and organic matter) > Fe oxides > kaolinite]. Extractions of sorbed Co at pH 5.5–7.5 with 2 M HCI showed that the extractability decreased with increasing sorption time and decreasing initial Co concentration. The untreated and H2O2‐treated soil samples retained sorbed Co at least as firmly as the synthetic goethite, whereas the H2O2+CBD‐treated sample (kaolinite) was clearly less effective. The results emphasized the importance of the soil Mn and Fe oxides for Co retention in soils but also the necessity of taken interior sorption sites into consideration.  相似文献   

8.
In order to understand the sorption phenomena of I on Andosols, one of the most typical soils in Japan, radiotracer experiments were carried out using I? (iodide), IO3 ? (iodate), and for comparison, Cl?(chloride) by the batch method, with special emphasis on the influence of solution pH and concentration of the respective ions. Kanuma soil composed of allophane, one of the main consistent minerals in most Andosols, was also examined regarding sorption. The sorption of I? and Cl? on Kanuma soil increased with decreasing pH and the sorptions were expressed by Henry isotherms. This indicated that these anions were electrostatically adsorbed on the positive charges which appeared on the surface of Kanuma soil. Sorption of Cl? onto Andosol could also be explained by electrostatic adsorption. Both I? and IO3 ? were readily sorbed on Andosol from water even under weakly alkaline conditions. The adsorption isotherm of IO3 ? on Andosol almost overlapped with that on Kanuma soil, suggesting that the high IO3 ? sorption on Andosol was caused by the high adsorbability of IO3 ?on allophane and/or sesquioxides of Fe and Al. However, the high I? sorption on Andosol could not be explained analogously.  相似文献   

9.
The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO4 2– and PO4 3–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K f was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.  相似文献   

10.
Phosphate (P) sorption and the concomitant release of sulphate (SO,), silicate (Si) and hydroxyl ion (OH) were determined on three allophanic soils from Spain, at different P concentrations. P effectively replaced SO4, Si and OH. However, at every stage of P sorption, the molar ratios of the total amounts of anions released (SO4+ Si + OH) to that of the sorbed P were low. The amount of added P affected the relative proportions of SO4, Si and OH exchanged. At low concentrations of P, phosphate sorption was accompanied mostly by release of the adsorbed SO4 with some Si. As more P was sorbed an increasing displacement of OH was also observed.  相似文献   

11.
Abstract

Several equilibrating salt solutions have been used in the studies of P sorption by soils and sediments. This study was conducted to evaluate the effects of 10 salt solutions on estimation of P sorption by soils. Results obtained showed that, when the equilibrating solution was made to contain 0.01M with respect to CaCl2, Ca(NO3)2, CaSO4, MgCl2, KCl, LiCl, Nacl, or KHCO3, the amount of P sorbed by soil always exceeded the amount sorbed from the soil‐water system. In comparison with the amount of P sorbed from water, 0.01M NaHCO3 reduced P sorption by soils. Use of THAM buffer (0.05M pH 7.0) to control the pH increased P sorption by some soils and decreased P sorption by others, relative to that sorbed from the soil‐water system. The results indicated that inclusion of salts in the equilibrating solution for P‐sorption studies should be avoided, especially in studies related to water quality.  相似文献   

12.
Abstract

The effect of alternating waterlogged and drying conditions on phosphorus (P) availability and sorption was studied in three soils of contrasting chemical and physical properties. Soils were treated with two levels of P (0 and 50 mg kg‐1; P0 and P50), waterlogged for 21 days, then allowed to dry at room temperature for 14 days. The availability of P, iron (Fe), and manganese (Mn) over the waterlogged and drying periods was determined by shaking samples of each soil with 1M NaOAc (pH 3). Increasing concentrations of 1M NaOAc (pH 3) extractable P (Pac) over the waterlogged period was attributed to solubilization of Fe(OH)3 materials under reducing conditions with the release of sorbed and occluded P. The released P appeared to be resorbed by freshly precipitated amorphous Fe(OH)2 material since earlier studies showed that water soluble P concentrations in these soils were reduced to negligible levels under waterlogged conditions. The Fe(OH)2 material remained readily extractable with 1M NaOAc (pH 3) since Feac increased dramatically with waterlogging. Drying the waterlogged soils caused a rapid decrease in Pac, Feac and Mnac suggesting the Fe(OH)2 may have been transformed into more stable forms [e.g., Fe(OH)3]. Much of the changes in Pac appeared to be due to changes in Feac, with limited influence from Mnac. and mineralization of organic P. Phosphate sorption isotherms were determined using the standard batch technique for air‐dry, waterlogged (with and without ponded water), and waterlogged/dried conditions. Sorption isotherms were not affected by waterlogging and subsequent drying. Most soils sorbed all of the added phosphate irrespective of moisture treatment.  相似文献   

13.
Thin film A.S.V. was used to study the specific sorption of Cd, Pb and Cu by hydrous oxides (Mn, Fe, and Al) or clay mineral suspensions from acetate buffer solutions containing 10 to 100 μg L?1 of each metal ion. The amount sorbed varied with system pH (range 3 to 9), substrate crystal form, the ratio of adsorbent to absorbate present, and the metal ion involved. Uptake by hydrous Mn(IV) oxide was near total over the whole pH range. With other particulates the pH required for onset of sorption varied with solid phase composition, with uptake subsequently increasing steadily with increasing pH. In general, affinity and relative uptake values followed the sequences Pb > Cu > Cd and Mn(IV) oxides > Fe(III) oxides > A1(OH)3 > clays > iron ores. The solid phases loaded with sorbed metal were equilibrated with a range of extractant solutions used in soil/sediment studies, and the results confirmed that chemi-sorption was the main retention process. Significant release was achieved using extractants that attacked the substrate or formed stable complexes with the metal ion.  相似文献   

14.
Phosphate sorption by calcareous soils has been studied mainly on heavily fertilized agricultural soils and soils with calcite as the main carbonate mineral. We examined factors affecting phosphate adsorption in the soils of a semi-arid, mediterranean, dolomitic, soil and vegetation chrono-sequence in southeastern Spain. The youngest soils are highly eroded, Sandy Regosols (Typic Xerorthents) under gorse-scrubland vegetation. These have small P sorption capacities, large Mg-Ca carbonate contents but small amounts of Fe and Al oxides. Small total P (HNO3/HClO4 digestion) concentrations (30–130 μg P g?1), of which up to 90% is Ca-bound (HCl-extractable), are typical of these young soils. P sorption markedly increased when Ca2+ was added to the solution. The fractionation of previously sorbed P indicates that the fate of most of this extra-sorbed P is the labile-P fraction sorbed on to (carbonate) surfaces and the apatite-like fraction (NaHCO3-extractable and HCl-extractable fractions). At the other extreme, older more-intensively weathered, sandy-clay-loam rendzinas (Entic Haploxerolls), supporting dense mature garrigue, have a much greater P adsorption capacity and larger clay and Fe and Al oxide concentrations. They have more total P (ca 400 μg P g?1), much of it in occluded form (residual fraction). These soils show no significant differences in P sorption whether or not CaCl2 was used as a background electrolyte. Considering the overall variations within the chronosequence, dithionite extractable Fe and Al are the properties best correlated with P sorption. This support the general finding that crystalline Fe-oxides (e.g. goethite and haematite) appear to be the most important P-sorbing component for soils in the Mediterranean region, rather than amorphous Fe-oxides (e.g. ferrihydrite) as is reported for more mesic areas. Stepwise multiple regression and fractionation data, however, suggest that, provided the soil solution is rich in Ca2+, carbonate may also be a significant contributing factor to P sorption, especially in the youngest of these dolomitic soils.  相似文献   

15.
Abstract

Phosphate (P) sorption characteristics of six natural Ghanaian Oxisols, selected because of their hydrological and topographical suitability for agriculture, were evaluated. Availability of P appears to be adequate for half of the soils as suggested by the Bray P1 test and determination of the standard P requirement (SPR), i.e., the amount of P sorbed at a concentration of 0.2 ppm P (6.46 μM). The SPR was found to be very closely related to Pmax (Langmuir P sorption capacity), which in turn, was significantly correlated with oxalate‐extractable aluminum (Al) (Alo) and iron (Fe) (Feo) and related (not significantly) to the difference between dithionite‐citrate‐bicarbonate‐extractable Fe (Fed) and oxalate‐extractable Fe. Accordingly, Pmax is fairly well predicted by the model of Borggaard: Pca]e=0.211#lbÀlo+0.115#lbFeo+ 0.05#lb(Fed‐Feo)+0.3, except for one soil strongly enriched in Fe oxides, mainly goethite. This goethite was found by X‐ray diffraction analysis to consist of crystals larger than normally found for pedogenic Fe oxides. The difference between Pmax and Pcalc for this soil could, therefore, be attributed to the occurrence of these large Fe oxide crystals, because P sorption will decrease with increasing crystal size (decreasing specific surface area).  相似文献   

16.
The sorption of the iron‐cyanide complexes ferricyanide, [Fe(CN)6]3—, and ferrocyanide, [Fe(CN)6]4—, on ferrihydrite was investigated in batch experiments including the effects of pH (pH 3.5 to 8) and ionic strength (0.001 to 0.1 M). The pH‐dependent sorption data were evaluated with a model approach by Barrow (1999): c = a exp(bS)S/(Smax‐S), where c is the solution concentration; S is the sorbed amount; Smax is maximum sorption; b is a parameter; and a is a parameter at constant pH. Ferricyanide sorption was negatively affected by increasing ionic strength, ferrocyanide sorption not at all. More ferricyanide than ferrocyanide was sorbed in the acidic range. In the neutral range the opposite was true. Fitting the pH‐dependent sorption to the model resulted in a strong correlation for both iron‐cyanide complexes with a common sorption maximum of 1.6 μmol m—2. Only little negative charge was conveyed to the ferrihydrite surface by sorption of iron‐cyanide complexes. The sorption of iron‐cyanide complexes on ferrihydrite is weaker than that on goethite, as a comparison of the model calculations shows. This may be caused by the lower relative amount of high‐affinity sites present on the ferrihydrite surface.  相似文献   

17.
Sorption of added inorganic phosphate (P) was irreversible in four contrasting soils and hydrous ferric oxide gel during 16 h desorption after 40 h sorption at the same (iso)pH. Irreversibility increased with increasing time of desorption above 30 h. When the amount of P which was chemisorbed during the sorption step was subtracted from the amount desorbed, the latter fell on the isotherm describing the more-physical, potential-determining sorption. No pH change occurred during desorption and net negative charge decreased by 1 equivalent per mole P desorbed. These results suggested that only more-physically sorbed P was desorbed at the iso-pH. The more-physically sorbed P was also reversible with respect to changes in the ionic strength and cation species of the desorbing solution. The isotopic exchangeability of the more-physically sorbed P was at least ten times greater than that of chemisorbed P. With increasing sorption time, both the ease of desorption and exchangeability of sorbed P decreased. Subsequent to desorption, the exchangeability of the remaining sorbed P also decreased. These observations are interpreted in terms of the concurrent changes in the amounts of chemisorbed and more-physically sorbed P.  相似文献   

18.
A model of P-sorption kinetics was developed, that accounts for the dependency of reaction rate on concentration, sorbed P content, sorption maximum and time. The sorption phenomena predicted by the model agree with available observations in the literature. The model was tested with batch experiments for 17 acid top– and subsoils. The experiments revealed a significant correlation between the sorption maximum, Fm, and the sum of amorphous iron and aluminium in soils. Plotting the dimensionless P–sorption ratio, F(c, t)/Fm, which may be interpreted as the fractional saturation of the sorption capacity of a soil, against the natural logarithm of the exposure variable, I, gave S–shaped curves. Different parts of the S–shaped curve can be experimentally assessed, depending on the initial fractional saturation of the P–sorption capacity of soils. Apart from this dependency, one set of parameter values sufficed to describe the sorption kinetics of 10 different sandy top– and subsoils. For non–sandy soils, the parameter values differed and depended on the initial P content. The model enables extrapolation to long times, which is necessary for applications to field conditions.  相似文献   

19.
Knowledge of phosphorus(P) sorption dynamics across different soil types could direct agronomic and environmental management of P. The objective of this study was to predict P isotherm parameters for a national soil population using data of routine laboratory tests. Langmuir and Freundlich sorption parameters were calculated from two different ranges(0–25 and 0–50 mg P L~(-1)) using an archive of representative agricultural soil types from Ireland.Multiple linear regression(MLR) identified labile forms of aluminium(Al) and iron(Fe), organic matter(OM), cation exchange capacity(CEC), and clay as significant drivers. Langmuir and Freundlich sorption capacities, Freundlich affinity constant, and Langmuir buffer capacity were predicted reliably, with R~2 of independent validation 0.9. Sorption isotherm parameters were predicted from P sorbed at a single concentration of 50 mg P L~(-1)(S_(50)). An MLR prediction of P sorption maximum in the 0–50 mg P L~(-1) range was achieved, to an accurate standard, using S_(50), OM, and Mehlich-3 Fe(R~2 of independent calibration and validation being 0.91 and 0.95, respectively). Using Giles' four shapes of isotherms(C, L, H, and S), L non-strict-and C-shaped isotherm curves accounted for 64% and 27% of the soils, respectively. Hierarchical clustering identified a separation of isotherm curves influenced by two ranges of Mehlich-3 Al. Soils with a low range of Mehlich-3 Al(2.5–698 mg kg~(-1)) had no incidence of rapid sorption(C shape). Single point indices, Al, or available soil data make the regression approach a feasible way of predicting Langmuir parameters that could be included with standard agronomic soil P testing.  相似文献   

20.
The hydrous oxides of Mn, Fe, and Al avidly sorbed Sb from μM Sb(OH), solutions, with uptake levelling off as initial Sb concentration increased. Capacity values decreased along the sequence MnOOH > Al(OH)3 > FeOOH. The amount sorbed by each substrate decreased gradually at pH values > 6. Addition of 0.4M CH3COONa to the aqueous phase (to minimise retention of weakly bound Sb) had little effect on MnOOH uptake capacity (～160 mmol, kg?1 at pH < 7) but retention dropped rapidly at higher pH. With the other two substrates (pH 6–7) the calculated capacity values for specific Sb sorption were ～ 45 mmol kg?1 FeOOH and ～ 33 mmol kg? Al(OH)3; about a third of the total capacity values. On these substrates specific Sb sorption tended to peak in the pH 7 to 8 region. The pH response pattern was modified using Sb tartrate sorbate solutions. Factors influencing Sb sorption included substrate surface charge, chemical form of Sb and surface interactions. Formation of a sparingly soluble metal coating was indicated by the uptake plateaus observed when increasing amounts of solid were added to Sb solutions containing acetate.  相似文献   

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