Redox potential measurements and Mössbauer spectrometry of Fe adsorbed onto Fe (oxyhydr)oxides

The redox properties of Fe^II adsorbed onto a series of Fe^III (oxyhydr)oxides (goethite, lepidocrocite, nano-sized ferric oxide hydrate (nano-FOH), and hydrous ferric oxide (HFO)) have been investigated by rest potential measurements at a platinum electrode, as a function of pH (−log₁₀[H⁺]) and surface coverage. Using the constant capacitance surface complexation model to describe Fe^II adsorption onto these substrates, theoretical values of the suspension redox potential (E_H) have been computed, under the assumption that Fe^II adsorption occurs at crystal growth sites of the substrate surface. Good agreement between calculated and experimental E_H values is observed for nano-FOH and HFO, however the redox potentials measured for lepidocrocite and goethite are significantly more oxidizing than predicted. Mössbauer spectroscopic analysis of ⁵⁷Fe^II adsorbed onto HFO and goethite shows that in both cases the adsorbed ⁵⁷Fe^II is incorporated into the crystal structure of the substrate, in broad agreement with the thermodynamic model, but is almost completely oxidized to ⁵⁷Fe^III. The mechanism by which the adsorbed ⁵⁷Fe^II is oxidized is not resolved in this work, but is thought to be due to electron transfer to the substrate, rather than a net oxidation of the suspension. The disagreement between experimental and calculated rest potential measurements in the goethite and lepidocrocite systems is thought to be due to the poor electrochemical equilibration of these suspensions with the platinum electrode, rather than a failure of the thermodynamic model. The model developed for the redox potential of adsorbed Fe^II allows direct assessment of the reactivity of this species towards oxidized pollutants.     

A revised scheme for the reactivity of iron (oxyhydr)oxide minerals towards dissolved sulfide

The reaction between dissolved sulfide and synthetic iron (oxyhydr)oxide minerals was studied in artificial seawater and 0.1 M NaCl at pH 7.5 and 25°C. Electron transfer between surface-complexed sulfide and solid-phase Fe(III) results in the oxidation of dissolved sulfide to elemental sulfur, and the subsequent dissolution of the surface-reduced Fe. Sulfide oxidation and Fe(II) dissolution kinetics were evaluated for freshly precipitated hydrous ferric oxide (HFO), lepidocrocite, goethite, magnetite, hematite, and Al-substituted lepidocrocite. Reaction kinetics were expressed in terms of an empirical rate equation of the form:

     

Mo isotope fractionation during adsorption to Fe (oxyhydr)oxides

Molybdenum (Mo) isotopes have great potential as a paleoredox indicator, but this potential is currently restricted by an incomplete understanding of isotope fractionations occurring during key (bio)geochemical processes. To address one such uncertainty we have investigated the isotopic fractionation of Mo during adsorption to a range of Fe (oxyhydr)oxides, under variable Mo/Fe-mineral ratios and pH. Our data confirm that Fe (oxyhydr)oxides can readily adsorb Mo, highlighting the potential importance of this removal pathway for the global Mo cycle. Furthermore, adsorption of Mo to Fe (oxyhydr)oxides is associated with preferential uptake of the lighter Mo isotopes. Fractionations between the solid and dissolved phase (Δ⁹⁸Mo) increase at higher pH, and also vary with mineralogy, increasing in the order magnetite (Δ⁹⁸Mo = 0.83 ± 0.60‰) < ferrihydrite (Δ⁹⁸Mo = 1.11 ± 0.15‰) < goethite (Δ⁹⁸Mo = 1.40 ± 0.48‰) < hematite (Δ⁹⁸Mo = 2.19 ± 0.54‰). Small differences in isotopic fractionation are also seen at varying Mo/Fe-mineral ratios for individual minerals. The observed isotopic behaviour is consistent with both fractionation during adsorption to the mineral surface (a function of vibrational energy) and adsorption of different Mo species/structures from solution. The different fractionation factors determined for different Fe (oxyhydr)oxides suggests that these minerals likely exert a major control on observed natural Mo isotope compositions during sediment deposition beneath suboxic through to anoxic (but non-sulfidic) bottom waters. Our results confirm that Mo isotopes can provide important information on the spatial extent of different paleoredox conditions, providing they are used in combination with other techniques for evaluating the local redox environment and the mineralogy of the depositing sediments.     

Ni isotope fractionation during coprecipitation of Fe(III)(oxyhydr)oxides in Si solutions

The dramatic decline in aqueous Ni concentrations in the Archean oceans during the Great Oxygenation Event is evident in declining solid phase Ni concentrations in Banded Iron Formations (BIFs) at the time. Several experiments have been performed to identify the main removal mechanisms of Ni from seawater into BIFs, whereby adsorption of Ni onto ferrihydrites has shown to be an efficient process. Ni isotopic measurements have shown limited isotopic fraction during this process, however, most experiments have been conducted in simple solutions containing varying proportions of dissolved Fe and Ni as NO₃ salts, as opposed to Cl salts which are dominant in seawater. Further, Archean oceans were, before the advent of siliceous eukaryotes, likely saturated with amorphous Si as seen in the interlayered chert layers within BIFs. Despite Si being shown to greatly affect the Ni elemental partitioning onto ferrihydrite solids, no studies have been made on the effects of Si on the Ni isotope fractionation. Here we report results of multiple coprecipitation experiments where ferrihydrite precipitated in mixed solutions with Ni and Si. Ni concentrations in the experiments ranged between 200 and 4000 nM for fixed concentrations of Si at either 0, 0.67 or 2.2 mM. The results show that Si at these concentrations has a limited effect on the Ni isotope fractionation during coprecipitation of ferrihydrite. At 0.67 mM, the saturation concentration of cristobalite, the isotopic fractionation factors between the precipitating solid and experimental fluid are identical to experiments not containing Si (0.34 ± 0.17‰). At 2.2 mM Si, and the saturation concentration of amorphous silica, however, the Ni isotopic composition of the ferrihydrite solids deviate to more negative values and show a larger variation than at low or no Si, and some samples show fractionation of up to 0.5‰. Despite this seemingly more unstable fractionation behaviour, the combined results indicate that even at as high concentrations of Si as 2.2 mM, the δ⁶⁰Ni values of the forming ferrihydrites does not change much. The results of our study implicate that Si may not be a major factor in fractionating stable Ni isotopes, which would make it easier to interpret future BIF record and reconstruct Archean ocean chemistry.     

氧化铁矿物对五氯苯酚表面吸附实验及其反应模式

批量法实验研究表明,五氯苯酚 (PCP)在合成的针铁矿、纤铁矿和赤铁矿表面吸附的浓度等温线为饱和型特征,可用 Langmuir公式拟合,而 pH吸附等温线为峰型曲线,峰值在 pH≈ 5. 矿物表面化合态和 PCP溶液离子化合态分析与计算表明, PCP在氧化铁矿物表面存在两种吸附反应模式,即表面静电吸附反应和表面络合吸附反应,表面静电吸附反应常数比表面络合吸附反应常数高 1～ 2个数量级.并进一步从反应机制上证明了憎水型可离解有机化合物 (HIOCs)在矿物表面吸附的模式与趋向性.     

Sorption of selenium(VI) onto anatase: Macroscopic and microscopic characterization

The sorption of selenium(VI) onto pure anatase, a polymorph of titanium dioxide, was investigated. At the macroscopic level, batch experiments and electrophoretic mobility measurements were performed. Selenium(VI) retention was found to be pH-dependent, i.e. sorption of selenium(VI) decreases with increasing pH (pH range 3.5-11). Selenium(VI) sorption dependence on the ionic strength was also evidenced, i.e. sorption increases while the ionic strength decreases. Electrophoretic mobility measurements showed that selenium(VI) sorption had no effect on the isoelectric point of anatase. At the microscopic level, XPS (X-ray Photoelectron Spectroscopy) measurements evidenced the absence of reduction of selenium(VI) during the sorption process. Furthermore, the nature of the sorbed surface species at the anatase/liquid interface was elucidated using Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) spectroscopy. The spectroscopic results strongly suggested the formation of outer-sphere complexes on the whole pH range, in agreement with batch sorption experiments and electrophoretic mobility findings.     

Retention behaviour of humic substances onto mineral surfaces and consequences upon thorium (IV) mobility: case of iron oxides

The influence of humic acids (HA) on the retention of Th(IV) onto the surface of Fe oxides has been investigated. Thorium (IV) is here considered as an analogue of tetravalent radionuclides (Zr, Hf, U, Np, Pu). Hematite (α–Fe₂O₃) and gœthite (α–FeOOH) have been chosen as model phases because of their widespread presence in the earth's crust. Retention experiments were performed by batch procedure at constant ionic strength and varying pH in the range 2–10; the HA concentration varied in the range 1–100 mg l⁻¹. Compared with the former data obtained on the retention of Th(IV) with the same hematite sample free of HA, the study of a ternary system (i.e. hematite–HA–Th), clearly shows the influence of HA on the retention mechanisms of Th(IV) even in neutral to slightly alkaline medium. In particular, it is illustrated that the retention of Th(IV) onto Fe oxides closely depends upon the ratio between humic and surface (Fe oxide) sites. This ratio has to be greater than a critical value in order to impede the sorption of Th(IV).     

Sorptive stabilization of organic matter in soils by hydrous iron oxides

Strong correlations between iron oxides (FeOx) and organic matter (OM) in soils have implied the importance of the former in stabilizing the latter. One mechanism thought to be important in this stabilization is sorption. We tested this possibility by reductively dissolving FeOx in a wide variety of soils and measuring the organic carbon (OC) that was solubilized. The OC dissolved from non-FeOx phases via anion exchange was corrected for by parallel control extractions. The resultant pool, reductively soluble OC, made up a minor amount of total soil OC in all but one of these soils, indicating that simple sorption reactions do not stabilize the bulk of soil OC in most mineral soils. OC:Fe ratios in the extracts from 2/3 of these soils were less than 0.22 (wt/wt), consistent with a sorbed state for this OC and showing that OC sorption by FeOx in these soils is limited by the amount of FeOx. The remaining soils had low pH and high OM concentrations; their higher OC:Fe ratios indicate inclusion of precipitated organo-Fe complexes in the extracts, which are likely only partially extracted by our method. The high volumetric ratios of OM to FeOx found in correlations between them from the literature are inconsistent with a dominant sorption control and point instead to stabilization to other mechanisms such as organo-Fe complexes or ternary associations among FeOx, OM and other minerals.     

Sorption of ferric iron from ferrioxamine B to synthetic and biogenic layer type manganese oxides

Siderophores are biogenic chelating agents produced in terrestrial and marine environments that increase the bioavailability of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but scant information appears to be available about the potential roles of layer type manganese oxides, which are relatively abundant in soils and the oligotrophic marine water column. To probe the effects of layer type manganese oxides on the stability of aqueous Fe-siderophore complexes, we studied the sorption of ferrioxamine B [Fe(III)HDFOB⁺, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] to two synthetic birnessites [layer type Mn(III,IV) oxides] and a biogenic birnessite produced by Pseudomonas putida GB-1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB⁺ at pH 8. Analysis of Fe K-edge EXAFS spectra indicated that a dominant fraction of Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to the mineral structure at multiple sites, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that layer type manganese oxides, including biogenic minerals, may sequester iron from soluble ferric complexes. We conclude that the sorption of iron-siderophore complexes may play a significant role in the bioavailability and biogeochemical cycling of iron in marine and terrestrial environments.     

The behaviour of dissolved organic material,iron and manganese in estuarine mixing

Fractionation by ultra-filtration of the dissolved organic material (DOM) in the River Beaulieu, with typical concentrations of dissolved organic carbon (DOC) of 7–8 mg C/l, showed it to be mainly in the nominal molecular weight range of 10³–10⁵, with 16–23% of the total DOC in the fraction > 10⁵. The molecular weight distribution of DOM in the more alkaline River Test (average DOC, 2 mg C/l) was similar. In the River Beaulieu water, containing 136–314 βg Fe/l in ‘dissolved’ forms, 90% or more of this Fe was in the nominal molecular weight fraction > 10⁵. Experiments showed that DOM of nominal molecular weight <10⁵ could stabilize Fe(III) in ‘dissolved’ forms. The concentrations of ‘dissolved’ Fe in the river water probably reflect the presence of colloidal Fe stabilized by organic material and this process may influence the apparent molecular weight of the DOM. Dissolved. Mn (100–136 βg/l) in the River Beaulieu was mainly in true solution, probably as Mn(II), with some 30% in forms of molecular weight greater than ca 10⁴.During mi xing in the Beaulieu Estuary, DOC and dissolved Mn behave essentially conservatively. This contrasts with the removal of a large fraction of the dissolved Fe (Holliday and LISS, 1976, Est. Coastal Mar. Sci. 4, 349–353). Concentrations of lattice-held Fe and Mn in suspended particulate material were essentially uniform in the estuary, at 3.2 and 0.012%, respectively, whereas the non-lattice held fractions decreased markedly with increase in salinity. For Mn the decrease was linear and could be most simply accounted for by the physical mixing of riverborne and marine participates, although the possibility that some desorption occurs is not excluded. The non-linear decrease in the concentration of non-lattice held Fe in particulates reflected the more complex situation in which physical mixing is accompanied by removal of material from the ‘dissolved’ fraction.     

Sorption behavior of nine chromium (III) organic complexes in soil

Sorption data were obtained with a Matawan soil and the following chromium (III) organic complexes: chromium (III) ascorbate, chromium (III) glutamate, chromium (III) histidine, chromium (III) mandelate, chromium (III) citrate, chromium (III) cysteine, chromium (III) serine, chromium (III) pyruvate and chromium (III) oxalate. The influence of pH (2–12), ionic strength (0.005–1 M) and concentration of sorbate (1–10 mg/L) on the extent of sorption was evaluated. The pH value did not influence the percent sorption at environmentally relevant pH 7. Ionic strength between 0.005 and 0.01 M KNO₃ did not influence the sorption. Sorption and desorption data obtained at pH 7, 0.01 M KNO₃ and 1–10 mg/L for each chromium (III) organic complex were analyzed using Freundlich and Langmuir models. The Freundlich model provided good fits for all of the chromium (III) organic complexes. Sorption data for chromium (III) glutamate, chromium (III) pyruvate, chromium (III) oxalate, chromium (III) cysteine, chromium (III) ascorbate and chromium (III) citrate were described well by the Langmuir model. Estimates for the saturated sorption capacities were 141, 70.9, 36.5, 35.5, 28.6 and 4.4 μg/g, respectively. It was not possible to desorb significant amounts of the previously sorbed chromium (III) organic complexes. At the same pH, ionic strength and solid:liquid ratio, the order of the observed sorption to the Matawan soil from highest to lowest was chromium (III) mandelate, chromium (III) glutamate, chromium (III) histidine, chromium (III) cysteine, chromium (III) serine, chromium (III) pyruvate, chromium (III) oxalate, chromium (III) ascorbate and chromium (III) citrate.     

Contributions from glacially derived sediment to the global iron (oxyhydr)oxide cycle: Implications for iron delivery to the oceans

Estimates of glacial sediment delivery to the oceans have been derived from fluxes of meltwater runoff and iceberg calving, and their sediment loads. The combined total (2900 Tg yr⁻¹) of the suspended sediment load in meltwaters (1400 Tg yr⁻¹) and the sediment delivered by icebergs (1500 Tg yr⁻¹) are within the range of earlier estimates. High-resolution microscopic observations show that suspended sediments from glacial meltwaters, supraglacial, and proglacial sediments, and sediments in basal ice, from Arctic, Alpine, and Antarctic locations all contain iron (oxyhydr)oxide nanoparticles, which are poorly crystalline, typically ∼5 nm in diameter, and which occur as single grains or aggregates that may be isolated or attached to sediment grains. Nanoparticles with these characteristics are potentially bioavailable. A global model comparing the sources and sinks of iron present as (oxyhydr)oxides indicates that sediment delivered by icebergs is a significant source of iron to the open oceans, beyond the continental shelf. Iceberg delivery of sediment containing iron as (oxyhydr)oxides during the Last Glacial Maximum may have been sufficient to fertilise the increase in oceanic productivity required to drawdown atmospheric CO₂ to the levels observed in ice cores.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

A comparison of two techniques for the isolation of adsorbed dissolved organic material from seawater

¹³C solid-phase NMR and pyrolysis-chemical ionization mass spectrometry were used to characterize adsorbed organic material isolated on an XAD-2 macroreticular resin. Pyrolysis-chemical ionization mass spectrometry was used directly to fingerprint the organics sorbed to a titanium foil exposed in the same marine environment. The XAD-2 isolate was shown to be fractionated relative to the native material and contaminated with the isolation resin.     

Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.     

Sorption and desorption of arsenate and arsenite on calcite

The adsorption and desorption of arsenate (As(V)) and arsenite (As(III)) on calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic concentrations were kept low (<33 μM) to avoid surface precipitation. The results show that little or no arsenite sorbs on calcite within 24 h at an initial As concentration of 0.67 μM. In contrast, arsenate sorbs readily and quickly on calcite. Likewise, desorption of arsenate from calcite is fast and complete within hours, indicating that arsenate is not readily incorporated into the calcite crystal lattice. The degree of arsenate sorption depends on the solution chemistry. Sorption increases with decreasing alkalinity, indicating a competition for sorption sites between arsenate and (bi)carbonate. pH also affects the sorption behavior, likely in response to changes in arsenate speciation or protonation/deprotonation of the adsorbing arsenate ion. Finally, sorption is influenced by the ionic strength, possibly due to electrostatic effects. The sorption of arsenate on calcite was modeled successfully using a surface complexation model comprising strong and weak sites. In the model, the adsorbing arsenate species were and . The model was able to correctly predict the adsorption of arsenate in the wide range of calcite-equilibrated solutions used in the batch experiments and to describe the non-linear shape of the sorption isotherms. Extrapolation of the experimental results to calcite bearing aquifers suggests a large variability in the mobility of arsenic. Under reduced conditions, arsenite, which does not sorb on calcite, will dominate and, hence, As will be highly mobile. In contrast, when conditions are oxidizing, arsenate is the predominant species and, because arsenate adsorbs strongly on calcite, As mobility will be significantly retarded. The estimated retardation factors for arsenate in carbonate aquifers range from 25 to 200.     

Sorption of cesium and iodide ions onto KENTEX-bentonite

The sorption of cesium and iodide ions onto KENTEX-bentonite was investigated using batch test and in-diffusion test methods. The cesium ions were highly sorbed on the bentonite, and the experimental data fit the Freundlich isotherm well. The distribution coefficient, K _d, of the cesium ions was variably affected by the chemical conditions of the solution (initial ion concentration, pH, salinity) and temperature. An increasing pH of solution increased the K _d. However, there were different K _d values that decrease with an increase in the initial ion concentration, salinity, and temperature. The iodide ions, on the contrary, were negligibly sorptive. The K _d values obtained from the in-diffusion tests were quite lower than those from the batch tests, which could be explained by changes in the pore water chemistry and surface area available for sorption.     

Molecular-level modes of As binding to Fe(III) (oxyhydr)oxides precipitated by the anaerobic nitrate-reducing Fe(II)-oxidizing Acidovorax sp. strain BoFeN1

Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as ferrihydrite, while As(III) did not show any preferential association regarding Fh or Gt.     

Effect of fulvic acids on sorption of U(VI), Zn,Yb, I and Se(IV) onto oxides of aluminum,iron and silicon

The sorption of Yb³⁺, UO²⁺₂, Zn²⁺, I⁻ and SeO²⁻₃ onto Al₂O₃, Fe₂O₃ and SiO₂ were determined by a batch technique in the presence and absence of fulvic acids. The effects of fulvic acid on sorption were compared. The existing general consensus, that humic substances tend to enhance metal cation sorption at low pH, reduce metal cation sorption at high pH and reduce inorganic anion sorption between pH values 3 to 10, was generally shown to be true. However, in this work many exceptions to the general consensus were found. The study indicated that the effect of humic substances on sorption of inorganic cations or anions depends not only on pH, but also on the nature of the oxide, the nature of humic substance, fractionation of the humic substance by sorption, the relative strength of complexes of both soluble and sorbed humic substances, the extent of surface coverage by humic substance, the initial concentration of humic substance and the inorganic electrolyte composition.