Sorption of iron‐cyanide complexes on goethite investigated in long‐term experiments

The iron‐cyanide complexes ferrocyanide, [Fe^II(CN)₆]^4–, and ferricyanide, [Fe^III(CN)₆]^3–, are anthropogenic contaminants in soil. We investigated their sorption on goethite, α‐FeOOH, in batch experiments in a time range from 1 d to 1 yr, their desorption by phosphate and chloride as well as their surface complexes on goethite by Fourier‐transform infrared spectroscopy (FTIR). The sorption of both complexes continued over the whole time range. Percent desorption of ferricyanide by phosphate decreased, whereas that of ferrocyanide increased until it amounted to approximately 87% for both complexes. By FTIR spectroscopy inner‐sphere complexation of both complexes on the goethite surface was indicated. With both complexes, a Berlin‐Blue‐like layer (Fe₄[Fe(CN)₆]₃) was formed initially on the goethite surface which disappeared with increasing reaction time. After at least 30 d reaction time, ferricyanide was the only sorbed iron‐cyanide complex detected even when ferrocyanide was initially added. This resulted from slow oxidation of ferrocyanide, most probably by dissolved oxygen. Based on all results, we propose that ferricyanide forms monodentate inner‐sphere complexes on the goethite surface.     

Simple modelling of the sorption of iron‐cyanide complexes on ferrihydrite

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/(S_max‐S), where c is the solution concentration; S is the sorbed amount; S_max 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.     

Modeling ferricyanide adsorption on goethite: Basics and applications

Ferricyanide, [Fe^III(CN)₆]^3–, is an anthropogenic and potentially toxic contaminant in soil. Its adsorption on goethite has been previously studied, but not evaluated with a surface complexation model (SCM) considering the effects of pH and ionic strength. Therefore, we carried out batch experiments with ferricyanide and goethite suspensions with different ferricyanide concentrations (0.075 mM and 0.15 mM), ionic strengths (0.01 and 0.1 M), and pH (ranging from 4 to 7.4). Adsorption data were then interpreted with the 1‐pK Stern and the charge distribution model assuming monodentate inner‐sphere ferricyanide surface complexes on goethite (lg K = 10.6), which are known from infrared spectroscopy. Furthermore, we applied the SCM to ferricyanide adsorption in previous studies on ferricyanide adsorption in the presence of sulfate and on the solubility of Fe‐cyanide complexes in a suspension of a loess loam. The SCM correctly reflected ferricyanide adsorption in the batch experiments as well as the effects of pH and ionic strength. The SCM also described ferricyanide adsorption in the presence of sulfate, because the ferricyanide adsorption measured and that modeled were significantly correlated (R² = 0.80). Furthermore, we applied the SCM to a study on the solubility of Fe‐cyanide complexes in soil under varying redox conditions so that ferricyanide adsorption on goethite and precipitation of Fe‐cyanide complexes were considered. The actual ferricyanide concentrations were rather reflected when applying the SCM compared to those modeled in an approach in which exclusively precipitation was taken into account. We conclude that ferricyanide adsorption on goethite should be included into geochemical modeling approaches on the mobility of Fe‐cyanide complexes in subsoils.     

Interactions of ferricyanide with humic soils and charred straw

The iron‐cyanide complexes ferricyanide, [Fe^III(CN)₆]^3?, and ferrocyanide, [Fe^II(CN)₆]^4?, are anthropogenic contaminants in soil. We studied the interactions of ferricyanide with humic soils and charred straw (maize and rye, both charred at 300, 400 and 500°C) by batch experiments and Fourier transform infrared (FTIR) spectroscopy. All soil samples sorbed ferricyanide (up to 8.4 g kg^?1). Precipitation of a manganese ferrocyanide after reduction of ferricyanide in the moderately acidic to neutral soils was deduced from both FTIR spectroscopy (CN absorption bands at 2069–2065 cm^?1) and geochemical modelling. Ferricyanide was also adsorbed onto the charred straw. The amounts of iron‐cyanide complexes adsorbed increased with increasing charring temperature, with a maximum of 1.71 g kg^?1. An absorption band at 2083 cm^?1 indicated weakly adsorbed intermediates of the reduction of ferricyanide to ferrocyanide. This band disappeared in the samples charred at higher temperature, whereas a band at 2026 cm^?1 was present in all spectra and became intensified in the high‐temperature straw. We attribute this band to ferrocyanide forming inner‐sphere complexes, presumably with quinone species of the organic matter. The band at 2026 cm^?1 was also present in the spectra of the soils, indicating that soil organic matter also adsorbs ferrocyanide. However, in humic soils the main processes of ferricyanide interaction include reduction to ferrocyanide and precipitation as manganese ferrocyanide. Quantitatively, adsorption on highly aromatic substances plays only a less important role as compared with precipitation.     

Iron-cyanide complexes in soil under varying redox conditions: speciation, solubility and modelling

The distribution of iron‐cyanide complexes between ferrocyanide, [Fe^II(CN)₆]^4–, and ferricyanide, [Fe^III(CN)₆]^3–, in soils on contaminated sites depends on the redox potential, E_H. We carried out microcosm experiments in which ferrocyanide (20 mg l^?1) was added to an uncontaminated moderately acidic subsoil (pH 5.2), and varied the E_H of the soil suspension between 200 and 700 mV over up to 109 days. Ferrocyanide and ferricyanide were analysed by capillary isotachophoresis. At redox potentials ranging from 400 to 700 mV, small amounts of iron‐cyanide complexes were adsorbed, and ferrocyanide was almost completely oxidized to ferricyanide. Decreasing E_H to 200 mV led to nearly complete removal of iron‐cyanide complexes from solution, and the complexes were not mobilized after subsequent aeration (E_H > 350 mV). Under weakly to moderately reducing conditions (E_H ≈ 200 mV), iron‐cyanide complexes were removed from solution by precipitation, which occurred, presumably in the form of e.g. Fe₂[Fe^II(CN)₆], Fe₄[Fe^II(CN)₆]₃ or Mn₂[Fe^II(CN)₆], after reductive dissolution of Mn and Fe oxides. Four different sets of geochemical model calculations were carried out. The species distribution between ferrocyanide and ferricyanide in solution was predicted reliably under varying pH and redox conditions when iron‐cyanide complex concentrations and Fe concentrations, excluding Fe bound in iron‐cyanide complexes, were used in model calculations. In model calculations on the fate of iron‐cyanide complexes in soil, adsorption reactions must be considered, especially under oxidizing conditions. Otherwise, the calculated iron‐cyanide complex concentrations are larger than those actually measured.     

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.     

不同pH、电解质浓度条件下草酸对针铁矿吸附Cd(II)的影响及机制

用吸附平衡法研究了不同草酸浓度、体系pH对针铁矿 (G)吸附Cd2+的影响与机制以及电解质 (KNO3)浓度对针铁矿、草酸化针铁矿 (G+40 )吸附Cd2+的影响差别及原因。结果表明 ,低浓度草酸 (1mmolL-1 )促进Cd2+的吸附 ;高浓度草酸 (1mmolL-1/sup )抑制Cd2+的吸附。已吸附在针铁矿表面的草酸对Cd2+ 吸附的影响与液相中草酸的影响不同 ,这主要与草酸引起的针铁矿表面电荷性质的变化、草酸在固液两相间的分配、草酸与Cd2+的配合作用和竞争作用有关。电解质 (KNO3)浓度对针铁矿和草酸化针铁矿吸附Cd2+的影响明显不同 ,随KNO3 浓度的提高 ,针铁矿的Cd吸附率由 44.5%增至 95%以上 ,而草酸化针铁矿吸附率由 29%降至6.2% ,这主要决定于二者的电荷零点 (PZC)和体系pH变化的不同。     

Sorption Behavior of Ofloxacin to Kaolinite: Effects of pH,Ionic Strength,and Cu(II)

Sorption of antibiotics to clay minerals is a key process controlling their transport and fate in environment. In this study, the effects of pH, ionic strength, and Cu(II) on ofloxacin (OFL) sorption to kaolinite were investigated by batch sorption experiments. The results of sorption edge experiments suggested that OFL sorption to kaolinite was pH and ionic strength dependent. Cation exchange was a major contributor to the sorption of OFL⁺ to kaolinite. The decreased OFL sorption with increasing ionic strength indicated the formation of outer-sphere complexation. When solution pH was lower than 7.0, Cu-OFL complexes facilitated OFL sorption through electrostatic attraction or formation of kaolinite-Cu-OFL and kaolinite-OFL-Cu ternary surface complexes. However, existence of free Cu(II) cation in solution competed for sorption sites, and thus suppressed OFL sorption. When solution pH was higher than 7.0, Cu(II) existed as Cu(OH)₂, and the Cu-OFL complexes in aqueous phase and solid phase (precipitation) enhanced OFL removal efficiency from solution. The results imply that Cu(II) effects should be taken into account in the evaluation of OFL mobility in environment.     

Adsorption of glycerophosphate on goethite (α‐FeOOH): A macroscopic and infrared spectroscopic study

Adsorption, desorption, and precipitation reactions at environmental interfaces govern the bioavailability, mobility, and fate of organic phosphates in terrestrial and aquatic environments. Glycerophosphate (GP) is a common environmental organic phosphate, however, surface adsorption reactions of GP on soil minerals have not been well understood. The adsorption characteristics of GP on goethite were studied using batch adsorption experiments, zeta (ζ) potential measurements, and in situ attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR). GP exhibited fast initial adsorption kinetics on goethite, followed by a slow adsorption. The maximum adsorption densities of GP on goethite were 2.00, 1.95, and 1.44 μmol m^?2 at pH 3, 5, and 7, respectively. Batch experiments showed decreased adsorption of GP with increasing pH from 3 to 10. Zeta potential measurements showed a remarkable decrease in the goethite isoelectric point upon GP adsorption (from 9.2 to 5.5), suggesting the formation of inner‐sphere surface complexes. In addition, the ATR‐FTIR spectra of GP sorbed on goethite were different from those of free GP at various pH values. These results suggested that GP was bound to goethite through the phosphate group by forming inner‐sphere surface complexes.     

Effect of soil microorganisms on the sorption of zinc and lead compounds by goethite

The objectives of this study were (1) to determine the effect of microorganisms during in‐vitro incubation on the amount of Zn and Pb from solution retained on goethite precipitated as coatings on a sand matrix and (2) to evaluate accumulation of heavy metals in the biomass of soil microorganisms in the fresh soil samples using an extractive approach. A mixture of colonies of cultivated microorganisms extracted from a Haplic Luvisol (Russia) and an Antropi‐urbic Regosol (Germany) were used to prepare the cell and the microbial‐debris suspensions. The concentrations of Zn and Pb in the studied solutions supplied with microbial suspensions and/or goethite coated sand were 0.1 mM (130.8 and 414 mg kg^–1 of sand, respectively). Exchangeable forms of metals were determined by extraction with 10 mL of 1.0 M KNO₃. Nonexchangeable forms of Zn and Pb were recovered using 40 mL of 0.3 M NH₂OH‐HCl in 1 M HNO₃. Concentrations of Pb increased in the solutions and decreased on the surface of the Fe‐mineral due to living microorganisms. In comparison to incubation of heavy‐metal solutions with goethite only, the absolute concentrations of nonexchangeable forms of metal were reduced by microbial suspension to a greater extent than those of the exchangeable forms, whereas the relative content of both fractions decreased by a factor of almost two. Sorption of Pb by goethite was inversely correlated with the concentration of organic C in the solution. Microorganisms clearly influenced the Zn sorption by goethite at concentrations of C_org > 400 mg L^–1. The amount of Zn retained was decreased primarily due to decreasing Zn portions in the exchangeable fraction. Microbial debris prepared by autoclaving reduced the Pb sorption by goethite similar to the results for living cells. Living microorganisms accumulated more Zn than did microbial debris. The data of this paper show that a direct determination of heavy‐metal accumulation in soil microorganisms by extraction with 2.0 M KCl as well as by extraction with 1 M CH₃COONH₄ at the natural pH of the soils after chloroform fumigation of fresh soils samples with different concentrations of organic C was not possible.     

Speciation and calcium competition effects on cadmium sorption by sandy soil at various pHs

The effects of Ca competition, ionic strength, inorganic complexation and pH on cadmium adsorption by a sandy soil were studied. Sorption of Cd was measured using four different electrolytes CaCl₂, Ca(NO₃)₂, NaNO₃ and NaCl at a constant ionic strength (I) of 0.003 M at three different pHs, at variable Ca/Na ratio with a constant ionic strength of 0.03 and at variable ionic strengths between 0.003 and 0.3 M for two different pHs for Ca(NO₃)₂ and NaNO₃. The measured Cd sorption isotherms were non-linear. In the case of Cl as electrolyte anion, 13% of the Cd in solution is complexed at I= 0.003 (0.002 M Cl) and 91% of Cd is complexed at I= 0.3 (0.2 M Cl). If NO₃ is the anion, none of Cd is complexed at I= 0.003 and 11% at I= 0.3. The Cd complexes do not adsorb significantly. Calcium competition, at an ionic strength of 0.03, reduced the Cd adsorption by 60–80% compared with the case that Na is the cation. Increasing the ionic strength from 0.003 to 0.3 decreased Cd sorption by 60% for Ca(NO₃)₂ and 25% for NaNO₃ due to a decrease of the activity coefficient, increase of inorganic complexation and increase of Ca competition. A decrease of one pH unit reduces Cd sorption of about 75%. Sorption of Cd by soil could be described adequately with the three-species Freundlich (3SF) equation in which pH, complexation, Ca competition and ionic strength effects were taken into account.     

Cyanide in paper de‐inking sludge used as a soil amendment

Paper de‐inking sludge is processed during the recycling of paper, and is sometimes used as a soil amendment. In this study the effect of a compost application on the cyanide (CN) status in soils of a public park was investigated. The compost was a mixture of chipped limbs and paper de‐inking sludge. Furthermore, the cyanide solubility was studied by conducting batch experiments with different pH levels. Total cyanide in the amended soils ranged from 540 to 740 mg CN kg^—1, and water soluble cyanide from 170 to 370 μg CN l^—1 as determined by means of an aqueous extract. Easily‐liberatable cyanides, which include the toxic free cyanide (HCN and CN^—) and weak metal‐cyanide complexes, were not present in the soil. From this result and the fact that iron blue pigments are used during paper printing, it can be inferred that cyanides occurring here were exclusively stable iron‐cyanide complexes [Fe(CN)₆]. With increasing pH the solubility of cyanide increased. In contrast to soils of coking plants, in which cyanide occur as Berlin blue, Fe₄[Fe(CN)₆]₃, the cyanide solubility in the paper de‐inking sludge amended soils was substantially lower, especially in the neutral and alkaline range. Thus, cyanides in paper de‐inking sludge could be present as sparingly soluble metal‐cyanide compounds with the general formula A₂B[Fe^II(CN)₆] with A = K⁺, Na⁺ and B = Ca²⁺ or divalent transition metals and B₂[Fe^II(CN)₆] with B = divalent transition metals. Pollution exposure by the pathways soil → human, and soil → air → human can be neglected. However, since leaching of iron‐cyanide complexes into the ground water cannot be excluded, and since they are decomposed to HCN when exposed to day light, environmental hazards by the pathway soil → ground water → surface water are possible. This is the risk arising from paper de‐inking sludge applications to soils.     

Effects of pH,solid/solution ratio,ionic strength,and organic acids on Pb and Cd sorption on kaolinite

Potentiometric and ion-selective electrode titrations together with batch sorption/desorption experiments, were performed to explain the aqueous and surface complexation reactions between kaolinite, Pb, Cd and three organic acids. Variables included pH, ionic strength, metal concentration, kaolinite concentration and time. The organic acids used were p-hydroxybenzoic acid, o-toluic acid, and 2,4-dinitrophenol. Titrations were used to derive previously unavailable aqueous conditional stability constants for the organometallic complexes. Batch results showed that aqueous lead-organic complexation reduced sorption of Pb by kaolinite. Cadmium behavior was similar, except for 2,4-dinitrophenol, where Cd sorption was increased. Metal sorption increased with increasing pH and decreasing ionic strength. Distribution ratios (K _d 's) decreased with increasing solid/solution ratio. The subsurface transport of lead and cadmium may be enhanced via complex interactions with organic wastes or their degradation products and sorbent mineral surfaces.

     

Removal of Cu2+ and Cd2+ from Aqueous Solution by Bentonite Clay Modified with Binary Mixture of Goethite and Humic Acid

Pre-modification of bentonite clay with goethite, humic acid, and a binary mixture of goethite and humic acid reagents increased its cation exchange capacity from 95 to 105.32, 120.4, and 125.8 meq/100 g of bentonite clay, respectively. The effective pre-modification of bentonite clay with goethite, humic acid, and goethite–humic acid reagents was confirmed from their Fourier transform infrared spectra which suggested that modification was effective on the AlAlOH and Si–O sites for goethite and humic acid modification and AlAlOH for goethite–humic acid modification. The presence of 0.001 M NaNO₃ electrolyte increased the adsorption capacity of bentonite clay. Temperature was observed to favor the adsorption of Cu²⁺ and Cd²⁺ onto both the raw and modified bentonite clay samples. The goethite–humic acid-modified bentonite gave the best adsorption capacity of ≈10 and 16 mg/g at 30 and 50°C, respectively, for both metal ions. The inner sphere complexation mechanism was suggested for the adsorption of both metal ions onto the modified adsorbents. Modifying bentonite clay with a binary mixture of goethite and humic acid reduced the selectivity of bentonite clay for either Cu²⁺ or Cd²⁺. Preadsorbed goethite and humic acid on bentonite clay will further reduce the mobility of heavy metal ions in soils and in aquatic environments.     

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.     

Observations and modelling of the reactions of 10 metals with goethite: adsorption and diffusion processes

A sample of goethite was mixed for periods which ranged from 2 hours to 8 weeks with solutions of dilute nitrate salts of Pb, Hg, Cd, Zn, Cu, Ni, Co, Mn, Cr and Al. The amount of sorption after each period was measured for an appropriate pH range for each metal. The sorption behaviour was characterized both by using characteristics of the sorption curves such as the pH at which half of the added metal was sorbed (pH₅₀) and by fitting a model in which sorption was mainly characterized by an affinity constant and by a diffusion constant. Initial sorption, whether characterized by the pH₅₀ or by the affinity constant, was closely correlated with the appropriate dissociation constants of the metals. The greater the affinity of the metals for hydroxide ions, the greater their affinity for the goethite surface. The metals differed in the rate at which they continued to react with the goethite. Lead had the slowest continuing reaction, cobalt the fastest. The continuing reaction was due to diffusion into the particles. It was characterized by the fitted diffusion constant and by the change with time in the pH₅₀. For seven of the eight divalent metals, these were correlated with the ionic radius of the metals: the larger the radius, the slower the reaction. For Al and Cr, rates were slower than would be expected from the ionic radii and we suggest this shows that these ions react as the larger M(OH)²⁺ ions. The behaviour of Ni was consistent with oxidation of the surface species and diffusion of Ni(OH)²⁺ ions. The continuing reaction was similar to that observed when metal ions react with soils and suggests that their reaction with iron oxides is important in soils. The results also show that studies in which sorption is measured at only one period of reaction are incomplete and the application of equilibrium models to such results is misleading.     

Characterizing heavy-metal adsorption on oxides and oxyhydroxides

Adsorption of Cu(II), Zn(II), Co(II) and Cd(II) on three different substrates: goethite, alumina and silica, was investigated over the pH range from 3.5 to 10. The consistent variation in the pH at which 50% of the metal is adsorbed (pH₅₀) indicates that the identity of the adsorbing ion is the principal factor determining the pH range over which adsorption occurs. However, the nature of the substrate does play a lesser role. The proton coefficient, χ, ranged from about 0.5 to 1.8, and was correlated with the difference between pH₅₀ and the pH for 50% precipitation. It is suggested that for most metal-substrate systems, for which χ is about 1, MOH⁺ plays a dominant role in adsorption. Increasing the substrate concentration decreased pH₅₀ for adsorption of metals on goethite, but there was little change in χ. The change in pH₅₀ was inversely related to χ. While the effect of the nature and concentration of the background electrolyte on Cu(II), Zn(II) and Co(II) adsorption depended on the substrate, increased ionic strength was found to decrease Cd(II) adsorption on all substrates.     

Dissolved organic matter sorption on sub soils and minerals studied by 13C-NMR and DRIFT spectroscopy

Sorption on the mineral matrix is an important process restricting the movement of dissolved organic matter (DOM) in soils. In this study, we aimed to identify the chemical structures responsible for the retention of DOM by sorption experiments with total DOM and acidic humic substances (AHS), containing humic and fulvic acids, on soil samples and minerals (goethite, ferrihydrite, and amorphous Al(OH)₃). The AHS remaining in solution after sorption were studied by ¹³C nuclear magnetic resonance (NMR) analysis, and total DOM and AHS for bed on the surfaces of minerals by diffuse reflectance Fourier-transform infrared (DRIFT) spectroscopy. The soil samples were taken from strongly sorbing Bw horizons of two Inceptisols rich in pedogenetic Fe (29 and 35 g kg ^?1) and containing little C (7 and 22 g kg^?1). The ¹³C-NMR spectra showed that sorption causes a preferential removal of aromatic and carboxyl C from the solution, whereas alkyl-C accumulates in the solution. No change was observed for O-alkyl C. The DRIFT spectra of sorbed total DOM and AHS showed a relative increase of the band intensity of carboxyl groups compared to DOM in the initial solution, confirming the importance of those groups for the sorption to mineral surfaces. The spectra also indicated reactions of carboxyl groups with metals at the mineral surfaces. The extent to which the carboxyl groups are bound depended on the surface coverage with DOM and the type of mineral.     

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.