SORPTION OF INORGANIC PHOSPHATE BY IRON- AND ALUMINIUM- CONTAINING COMPONENTS

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.     

Relationships between phosphate sorption and iron oxides in Alfisols from a river terrace sequence of Mediterranean Spain

Phosphate sorption isotherms for samples of the A- and upper B-horizons of Alfisols situated on a sequence of terraces of the River Guadalquivir, southern Spain, showed that phosphate sorbed at an equilibrium concentration of 0.3 μg P ml^?1 was correlated with several soil properties. Crystalline Fe-oxides (goethite and hematite) appeared to be the most important P-sorbing components of the soil samples. Sorption was highly correlated with percent clay and with dithionite soluble Fe. This last property was as good a property to predict sorption as the specific surface of crystalline Fe-oxides (which was estimated by line profile analysis of the X-ray diffractograms), probably because the range of surface areas for goethite and hematite was relatively narrow in the samples and because of the limited accuracy of the method of line profile analysis.Well drained and imperfectly drained soils differed little in sorption properties. In imperfectly drained, hematite-free soils, chroma was correlated with sorption. This is promising for it would allow rapid field estimation of sorption.The sorption maximum, calculated from the fitted Langmuir isotherm, was about 1.7 μmol P m^?2 of Fe-oxides, a value similar to those reported in the literature for natural and synthetic oxides.     

Assessing the fixation and availability of sorbed phosphate in soil using an isotopic exchange method

An isotopic exchange method was used to characterize quantitatively the fixation and plant availability of phosphate previously sorbed by soils. In general, the exchangeability of the sorbed phosphate was much higher than its desorbability for both soils and clay minerals. Isotopic exchangeability of the sorbed phosphate increased with sorption saturation during the initial stage (15–60% saturation), but the increase was less with increasing saturation from 60–90% for all soils tested. Therefore a sorption saturation of 60% was recommended as the upper limit of P fertilization in terms of economical efficiency. For clay minerals, with increasing sorption saturation, the isotopic exchangeability of the sorbed P increased significantly for kaolinite and sesquioxides, but decreased for montmorillonite. Most of the phosphate sorbed by montmorillonite and kaolinite was found to be isotopically exchangeable, but only a small amount of the P sorbed by goethite could be exchanged. The P sorbed by Al oxide exhibited isotopic exchangeability between that of kaolinite and Fe oxide. The isotopically exchangeable phosphate pool could readily account for the P uptake of plants and the available P determined by some commonly used chemical methods, such as Olsen-P and Bray-P.     

Phosphate sorption in relation to aluminum and iron oxides of oxisols from Ghana

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 P_max (Langmuir P sorption capacity), which in turn, was significantly correlated with oxalate‐extractable aluminum (Al) (Al_o) and iron (Fe) (Fe_o) and related (not significantly) to the difference between dithionite‐citrate‐bicarbonate‐extractable Fe (Fe_d) and oxalate‐extractable Fe. Accordingly, P_max is fairly well predicted by the model of Borggaard: P_ca]e=0.211#lbÀl_o+0.115#lbFe_o+ 0.05#lb(Fe_d‐Fe_o)+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 P_max and P_calc 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).     

Retention of Ni,Zn and Cd by Si-associated goethite

Synthetic goethite used to study the effects of reaction time and temperature on the pH-dependent sorption of Ni, Zn and Cd was associated with amorphous silica. Ni interacted with dissolved Si and formed a Ni/Si precipitate on the goethite surface. Individual metals added at a concentration of 0.5 μmol g^?1 and sorbed during a reaction period of 504 hours (21 days) at 35°C were extracted by 0.7 M HNO₃ for 14 days. At the end of this period 11,28 and 40 percent of Ni, Cd and Zn, respectively, were not extracted whereas 20 percent of the total Fe content of the goethite and 39 percent of the associated Si were dissolved. During the sorption process metals became immobilized in the goethite particles. This effect can be related to a diffusion of metal ions into micropores. A total mobilization of sorbed metals can only be achieved by a complete dissolution of the goethite. The strong fixation of Ni, Zn and Cd by goethite suggests that additions of this Fe oxide could be used to ameliorate highly contaminated sludges or soils.     

Retention of cobalt by an oxisol in relation to the content of iron and manganese oxides

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.     

Irreversibility of sulfate sorption on goethite and hematite

Sulfate ion adsorption and desorption experiments carried out on synthetic goethite and hematite and natural hematite show adsorption to be a highly irreversible reaction. All oxides showed an increase in sulfate ion adsorption with decrease in pH. Only a small fraction of sorbed sulfate was desorbable after 48 hr, and only at a pH of 3. Extreme irreversibility of sulfate sorption on these common soil minerals suggests that adsorbed sulfate is more immobile in watersheds than previously considered and that recovery models which inherently assume reversibility may need to be modified.     

DESORPTION AND ISOTOPIC EXCHANGE RELATIONSHIPS OF PHOSPHATE SORBED BY SOILS AND HYDROUS FERRIC OXIDE GEL

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.     

Development and evaluation of a kinetic model to describe phosphate sorption by hydrous ferric oxide gel

Isotherms for the sorption of inorganic phosphate (P) by hydrous ferric oxide gel (Fe gel) were described by a three-equation Langmuir sorption model. Each equation described sorption within a distinct concentration range or region (I, II, and III) of the overall isotherm. Regions I and II involved chemisorption, whereas region III involved a more physical sorption type. With increasing sorption time between 0.7 and 28.7 days, the extent of sorption in region I increased by more than 30%. In contrast, the extent of sorption in regions II and III remained essentially constant. An equation was developed, based on the change in the sorption maximum of region I (b_I) with increasing sorption time, which described the change in solution P concentration with time. The increase in b_I with time, evaluated by the closeness of fit of this relationship to experimental data, was found to depend on two factors: first, the extent to which P was chemisorbed, and this was affected by pH and ionic strength; second, the batch of Fe gel used. For two different levels of P addition, the proportion of sorbed P which remained extractable in 0.1M NaOH, decreased with increasing sorption time. After 30 days only 88% of the sorbed P remained NaOH-extractable. The data obtained indicated that the increasing chemisorption of P with increasing sorption time involves the diffusion of sorbed P into the bulk of the Fe gel particles. This concept is discussed in relation to mechanisms proposed by previous workers to explain the time-dependence of P sorption.     

The Contrasting Effect of Goethite and Hematite on Phosphate Sorption and Desorption by Terre Rosse

Phosphate sorption and desorption in soils are markedly influenced by iron oxides, although little is known on how the common iron oxides differ in their behaviour towards added phosphate. In this study, we investigated phosphate sorption and desorption in the clay fractions of 12 Terre Rosse that ranged widely in Fe oxide content, had very low contents of oxalate-extractable Fe oxides and different hematite/goethite ratios. Phosphate sorption at an equilibrium concentration of 1 mg P 1^?1 was correlated with the goethite but not with the hematite content of the clay fractions. When phosphate was desorbed by electro-ultrafiltration, the difference in desorption half-time between untreated and deferrified clays was positively correlated with the goethite but not with the hematite content. These results suggest that goethite is more active than hematite in phosphate sorption and retention by soils.     

Factors affecting phosphate sorption along a Mediterranean, dolomitic soil and vegetation chronosequence

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.     

Sorption and desorption of cobalt by soils and soil components

The sorption of Co by individual soil components was studied at solution Co concentrations that were within the range found in natural soil solutions. Soil-derived oxide materials sorbed by far the greatest amounts of Co although substantial amounts were also sorbed by organic materials (humic and fulvic acids). Clay minerals and non-pedogenic iron and manganese oxides sorbed relatively little Co. It is considered that clay minerals are unlikely to have a significant influence on the sorption of Co by whole soils. Cobalt sorbed by soil oxide material was not readily desorbed back into solution and, in addition, rapidly became non-isotopically exchangeable with solution Co. In contrast, Co was relatively easily desorbed from humic acid and a large proportion of the Co sorbed by humic acid remained isotopically exchangeable. Cobalt sorbed by montmorillonite was more easily desorbed than that sorbed by soil oxide but less easily than that sorbed by humic acid. Cobalt sorption isotherms for whole soils at low site coverage were essentially linear and the gradients of isotherms increased with pH. A comparison of isotherm gradients for whole soils and individual soil components supported the suggestion that Co sorption in whole soils is largely controlled by soil oxide materials.     

How do amorphous sesquioxides affect and contribute to butachlor retention in soils?

Purpose

Sorption and desorption of butachlor were simultaneously investigated on synthesized pure amorphous hydrated Fe oxides (AHOs Fe), and soils both with and without surface coating of AHOs Fe, with special interest towards how amorphous sesquioxides affect and contribute to butachlor retention in soils.

Materials and methods

The AHOs Fe was artificially synthesized pure materials. Two soils with contrasting physicochemical properties selected for study were black soil and latosol, belonging to permanent charged soil and variable charged soil, respectively. Both soils were further treated using AHOs Fe for detecting the differentiation from native soils regarding butachlor retention produced after the soils were surface-coated by AHOs Fe. A sorption experiment was conducted using a batch equilibrium technique, and desorption was carried out immediately following sorption by three sequential dilution. Hysteresis index (HI) values were calculated to investigate desorption hysteresis by developing desorption isotherms concentration dependent and time dependent, respectively.

Results and discussion

The sorption capacity for butachlor increased in the order of AHOs Fe, uncoated soils, and soils with surface coating of AHOs Fe. The sorption capacity of both soils significantly increased after surface coating by AHOs Fe (p?<?0.01), with a bigger increase achieved by black soil (52.0 %) as compared with that by latosol (45.3 %). Desorption of butachlor was coincidently hysteretic on AHOs Fe, and soils both uncoated and coated, whereas variation in desorption hysteresis was different between AHOs Fe and soils with increasing butachlor sorption loading, indicating different sorption mechanisms were operative for AHOs Fe and soils across the entire butachlor concentration range. Hysteresis of butachlor desorption was weakened after the soils were surface coated by AHOs Fe, as suggested by the changed HI values.

Conclusions

With high specific surface area and highly reactive surfaces, the “active” AHOs Fe originally has a relatively high sorption capacity and affinity for butachlor. While in natural soils, where the inevitable association derived from soil organic matter (SOM) would restrain AHOs Fe from sequestrating butachlor directly, AHOs Fe may likely contribute in a mediator way by coordinating active sites both on and within SOM. This may enhance the availability of sorption domains both on and within soils, thereby achieved an enhanced but more reversible retention for butachlor in soils after their surfaces were coated by AHOs Fe. This study has extended the observations of the role of noncrystalline sesquioxides in retention of pesticides such as butachlor from pure clay mineral systems to natural soils.     

Phosphate desorption from the surface of soil mineral particles by a phosphate-solubilizing fungus

High phosphate (Pi) sorption in soils is a serious limiting factor for plant productivity and Pi fertilization efficiency, particularly in highly weathered and volcanic ash soils. In these soils, the sorbed Pi is so strongly held on the surfaces of reactive minerals that it is not available for plant root uptake. The use of phosphate-solubilizing microorganisms (PSM) capable of Pi desorption seems to be a complementary alternative in the management of these soils. The aim of this study was to evaluate the effectiveness of the soil fungus Mortierella sp., a known PSM, to desorb Pi from four soil minerals differing in their Pi sorption capacity. The fungus was effective in desorbing Pi from all tested minerals except from allophane, and its desorption depended on the production of oxalic acid. The effectiveness of the fungus to desorb Pi was ranked as montmorillonite > kaolinite > goethite > allophane. The quantity of desorbed Pi increased by increasing the amount of sorbed Pi. The Pi sorption capacity expressed as P_0.2 value (amount of P required to increase a solution P concentration up to 0.2 mg L^?1) was a good indicator of the effectiveness of Mortierella sp. to desorb Pi from soil minerals.     

Phosphorus availability and sorption under alternating waterlogged and drying conditions

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 (P_ac) 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 Fe_ac increased dramatically with waterlogging. Drying the waterlogged soils caused a rapid decrease in P_ac, Fe_ac and Mn_ac suggesting the Fe(OH)₂ may have been transformed into more stable forms [e.g., Fe(OH)₃]. Much of the changes in P_ac appeared to be due to changes in Fe_ac, with limited influence from Mn_ac. 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.     

Short-term controls over inorganic phosphorus during soil and ecosystem development

Geochemical sorption and biological demand control phosphorus (P) retention and availability in soils. Sorption and the biota predominantly utilize the same inorganic form of P, from the same soil pool, on the same time scale, and thus are likely to compete for P as it flows through the available pool. In tropical soils, P availability is typically quite low and soil geochemical reactivity can be quite high. We tested whether greater P sorption strength in tropical soils resulted in lower biological uptake of available P. Since the strength of soil sorption and biological demand for P change as ecosystems develop and soils age, we used soils from the two upper horizons from three sites along a 4.1 million-year-old tropical forest chronosequence in the Hawaiian archipelago. We evaluated the strength of geochemical sorption, microbial demand, and the partitioning of added available P into biological versus geochemical soil pools over 48 h using a ³²PO₄ tracer. Soil sorption strength was high and correlated with soil mineral content. The amount of added phosphate geochemically sorbed versus immobilized by microbes varied more between the organic and mineral soil horizons than among soil ages. Microbial activity was a good predictor of how much available P was partitioned into biological versus geochemical pools across all soils, while sorption capacity was not. This suggests that microbial demand was the predominant control over partitioning of available P despite changes in soil sorption strength.     

Use of the Kubelka—Munk theory to study the influence of iron oxides on soil colour

The Kubelka–Munk theory, which is commonly applied to ‘pigment mixtures’, adequately predicted the colour of mixtures of synthetic haematite, synthetic goethite and deferrated soil powders. The theory illustrated the higher pigmenting effect of haematite compared with goethite. In mixtures containing haematite the calculated colour coordinates could be combined into simple ‘redness’ indices that were highly correlated with haematite content and were not appreciably influenced by goethite. The theory was also applied to the study of the chromatic characteristics of 98 soils, differing widely in their origin but having an organic matter content <2% in which haematite or goethite was the dominant Fe oxide. The theory showed that the average ‘soil’ haematite and ‘soil’ goethite had colours similar to those of their synthetic counter-parts, whereas the rest of the soil components could be considered as an essentially ‘grey’ matrix. It was also useful in predicting the haematite and goethite contents of soils either from several reflectance measurements of soil-white standard mixtures or from the indices of redness developed for the synthetic mixtures.     

Effects of equilibrating salt solutions on phosphate sorption by soils

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.     

Rate of desorption of eight heavy metals from goethite and its implications for understanding the pathways for penetration

We compared rates of desorption of heavy metals from goethite, an important soil constituent, in order to understand the mechanisms of sorption and desorption better. Samples of goethite were reacted with salt solutions of heavy metals for 2 hours or for 8 weeks. The metals were Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb. Desorption was then induced by successive treatments with 0.7 m HNO₃ for up to 360 hours followed by complete dissolution of the goethite particles. After brief sorption (2 hours), a large proportion of the sorbed metals was desorbed by brief treatment (15 minutes) with HNO₃. This suggests that the metals were mainly sorbed on, or close to, external goethite surfaces. After longer sorption (8 weeks), even 360 hours of extraction with 0.7 m HNO₃ did not recover all of the sorbed metals. Complete dissolution of the goethite particles was necessary. This suggests that the eight heavy metals had penetrated the goethite particles deeply. When desorption was summarized using a pragmatic equation, it was only for brief sorption followed by brief desorption that indices of the rate of desorption were well correlated with measures of the rate of sorption as obtained in an earlier work. When desorption was described with a mechanistic model, observed desorption was often faster than predicted and the discrepancy was greatest with the shorter periods of desorption. The discrepancy was marked for Ni, Cr and Co. We think this was because large portions of these metals were incorporated into the goethite structure by lattice diffusion and were therefore held close to the surface. When the acid dissolved some of the goethite these metals were released. For long‐term desorption and for most metals, the ratio of observed to predicted desorption decreased with increasing ionic radius. We think that this reflects a changing balance between lattice and pore diffusion, with lattice diffusion more important for metals with radii near that of Fe (Cr, Co, Ni), and pore diffusion more important for the larger cations of Cd and Pb. Manganese was an exception. Desorption was at first faster than predicted but then declined to be close to predicted values. This suggests that Mn mostly penetrated more deeply by pore diffusion.     

高岭石,蒙脱石和针铁矿对泥炭腐殖酸的吸附和分离

Sorption of humic acid (HA) on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants (HOCs) and carbon sequestration in soils. The objective of our study is to determine the fractionation behavior of HA upon sorption on mineral surfaces with varying surface properties. HA was coated sequentially on kaolinite (1:1 clay), montmorillonite (2:1 clay), and goethite (iron oxide) for four times. The unadsorbed HA fractions were characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and solid state ¹³C nuclear magnetic resonance spectroscopy (NMR). The mineral-HA complexes were characterized by DRIFT. Polarity index [(N+O)/C] revealed higher polarity of the unadsorbed HA fractions after coating on kaolinite, reflecting that relatively higher polarity fractions of HA remain unadsorbed. Sorption of aliphatic alcohol fraction along with carbohydrate was prominent on kaolinite surface. DRIFT results of the unadsorbed HA fractions indicated more sorption of aliphatic moieties on both kaolinite and montmorillonite. DRIFT results of the unadsorbed HA fractions after sorption on kaolinite and goethite showed the sorption of the proteinaceous fractions of HA. The HA fractions obtained after coating on goethite showed significant sorption of carboxylic moieties. The results mentioned above comply reasonably well with the DRIFT spectra of the mineral-HA complexes. ¹³C NMR results showed higher sorption of anomeric C on kaolinite surface. Higher sorption of paraffinic fraction was observed on montmorillonite. NMR data inferred the sorption of carboxylic moieties on goethite surface. Overall, this study showed that aliphatic moieties of HA preferentially sorbed on kaolinite and montmorillonite, while carboxylic functional groups play a significant role in sorption of HA on goethite. The sorbed fractions of HA may modify the mineral surface properties, and thus, the interaction with organic contaminants.