Formation of iron-containing colloids by the weathering of phyllite

The formation of colloids during the weathering of phyllite was investigated by exposing ground phyllite to Milli-Q water. Secondary mineral colloids of 10¹–10² nm were detected in significant concentrations. At pH of about 8.5, the solution concentration of these colloids reached up to 10 mg/L (however, acidification to pH 4.0 prevented the formation of the colloids). The mineralogical composition of the secondary mineral colloids is assumed to be a mixture of ferrihydrite, manganese oxyhydroxides, aluminosilicates, amorphous Al(OH)₃ and gibbsite with possible additions of iron silicates and␣iron-alumino silicates. The colloids were stable over longer periods of time (at least several weeks), even in the presence of suspended ground rock. Direct formation of iron-containing secondary mineral colloids at the rock–water interface by the weathering of rock material is an alternative to the well-known mechanism of iron colloid formation in the bulk of water bodies by mixing of different waters or by aeration of anoxic waters. This direct mechanism is of relevance for colloid production during the weathering of freshly crushed rock in the unsaturated zone as for instance crushed rock in mine waste rock piles. Colloids produced by this mechanism, too, can influence the transport of contaminants such as actinides because these colloids have a large specific surface area and a high sorption affinity.     

地下水系统中镍污染和天然胶体共迁移特征

为了对地下水系统中天然胶体与Ni²⁺的共迁移特征进行研究,通过静态吸附实验和石英砂模拟含水层介质柱实验研究了土壤胶体对Ni²⁺在地下水中运移的影响,以及pH、离子强度（IS）、有机质等对土壤胶体吸附Ni²⁺的影响。结果表明：随着pH值升高,土壤胶体对Ni²⁺的吸附量增加;离子强度的增加会显著地降低土壤胶体吸附Ni²⁺的能力;腐殖酸（HA）的存在会增强胶体对Ni²⁺的吸附能力;在有胶体的情况下,Ni²⁺穿透砂柱的时间会缩短,吸附能力增强,吸附量增加,但当离子强度增加时,虽然Ni²⁺穿透砂柱的时间也被缩短,但是吸附量却降低。     

Diffusion,degradation or on-site stabilisation – Identifying causes of kinetic processes involved in metal–humate complexation

The applicability of equilibrium models for humic-bound transport of toxic or radioactive metals is affected by kinetic processes leading to an increasing inertness of metal–humic complexes. The chemical background is not yet understood. It is widely believed that bound metals undergo an in-diffusion process within the humic colloids, changing from weaker to stronger binding sites. This work is focussed on the competition effect of Al(III) on complexation of Tb(III) or Eu(III) as analogues of trivalent actinides. By using ion exchange and spectroscopic methods, their bound fractions were determined for solutions of Al and humic acid that had been pre-equilibrated for different periods of time. Whilst the amount of bound Al remained unchanged, its blocking effect was found to increase over a time frame of 2 days, which corresponds to the kinetics of the increase in complex inertness reported in most pertinent studies. Thus, the derived “diffusion theory” turned out to be inapplicable, since it cannot explain an increase in competition for the “initial” sites. A delayed degradation of polynuclear species (as found for Fe) does not occur. Consequently, the temporal changes must be based on structural rearrangements in the vicinity of bound Al, complicating the exchange or access. Time-dependent studies by laser fluorescence spectroscopy (steady-state and time-resolved) yielded evidence of substantial alterations, which were, however, immediately induced and did not show any significant trend on the time scale of interest, suggesting that the stabilisation process is based on comparatively moderate changes.     

Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.     

Origin and mobility of humic colloids in the Gorleben aquifer system

The origin and mobility of humic colloids in the Gorleben aquifer system have been examined. For this purpose, the distribution of humic colloids and relevant hydrological and geochemical parameters were examined. An investigation area was selected where sediments have been disturbed by salt dome uplift and glacial events. It is shown that, on a local scale, considerable groundwater movement and intermixing takes place from the surface down to the salt dome. Consequently no effective separation of groundwater layers occurs. Two different humic colloid sources are identified: influx from the humus horizon with recharge water and continuous in situ generation via mineralization of sedimentary organic carbon (SOC). The in situ generation leads to groundwaters with humic colloid concentrations approaching 0.4 g/L, compared to concentrations of less than 0.005 g/L in recharge waters. Young groundwaters (no ¹⁴C decay detected) between approximately 50 and 200 m depth exhibit these highly elevated humic colloid concentrations. At greater depth, salt brines are found with low humic colloid concentrations. This can be attributed to precipitation of humic acid and/or hampering of the in situ generation process due to the high salt content. There is no indication of retention or decomposition of humic colloids. The fate of in situ generated humic colloids cannot be precisely evaluated due to analytical limitations and insufficient understanding of groundwater movement.     

腐植酸改性强化磁铁矿吸附水体中铅镉的实验研究

磁铁矿是一种绿色廉价的矿物材料,对水体中重金属离子具有良好的吸附性,但吸附容量低,选择性差,易团聚,通过改性可以克服该缺点并提高其吸附性能。本文以腐植酸为改性剂,采用常温水相反应制备了腐植酸改性磁铁矿吸附材料。通过傅里叶红外光谱(FTIR)、扫描电镜(SEM)和X射线光电子能谱(XPS)表征研究其表面形貌和微观结构。采用静态平衡实验考察了pH、吸附时间等因素对铅、镉吸附性能的影响,探讨了吸附动力学规律,拟合了吸附等温线。结果表明:腐植酸上的羧基、羟基被成功地接枝到了磁铁矿表面。在室温下,溶液初始pH对Pb~(2+)的吸附率几乎无影响,对Cd~(2+)的影响较大,当pH=7时,Pb~(2+)和Cd~(2+)吸附率均达到了95%。对初始质量浓度为10mg/L的Pb~(2+)、Cd~(2+)最佳吸附平衡时间为360min,吸附过程符合准二级动力学方程。吸附等温线实验得到的竞争吸附顺序为Pb~(2+)Cd~(2+),由Langmuir等温吸附模型得到Pb~(2+)、Cd~(2+)饱和吸附容量分别为39.27mg/g、28.95mg/g,显著大于磁铁矿的饱和吸附容量,表明磁铁矿经腐植酸改性后增强了对水中铅镉的吸附能力。     

Effects of humic acid and Tween-80 on behavior of decabromodiphenyl ether in soil columns

The effects of organic matter, humic acid and Tween-80 on decabromodiphenyl ether (BDE-209) behavior in soil columns were investigated. The BDE-209 transport was simulated in 4-cm-length soil columns whether organic matter was added or not. A high concentration of BDE-209 was washed out of the soil column in the presence of 500 mg L^?1 of Tween-80 for forming and suspending contaminated soil colloids in more than 4-cm-length ones (especially in 10-cm-length ones). While the humic acid was to facilitate BDE-209 adsorption onto soil particles (like soil colloids), Tween-80 was to enhance BDE-209 movement in porous media. The significant concentration averaged from 0.2 to 0.1 μg L^?1 in soil columns of length from 10 to 24 cm with Tween-80 addition by comparing the estimated marginal means (p < 0.05, SPSS). Contrasted with humic acid-binding BDE-209 in soil particles, Tween-80 could carry contaminant soil colloids into deeper layers and even affect the final effluents of 25-cm-length columns. It was visibly presented that the BDE-209 concentration in the effluents was mainly induced by Tween-80. Thus, BDE-209 was carried by soil colloids to transport and pollute longer and wider soil distance with the help of the effective promoters and stabilizers of Tween-80 and humic acid in soil matrix.     

The coagulation,solubility and adsorption properties of Fe,Mn, Cu,Ni, Cd,Co and humic acids in a river water

River water (Water of Luce, Scotland) is used in laboratory experiments designed to investigate physical and chemical properties of Fe. Mn, Cu, Ni, Co, Cd and humic acids in riverine and estuarine systems. Using NaCl, MgCl₂ and CaCl₂ as coagulating agents, coagulation of dissolved (0.4 μm filtered) Fe, Cu, Ni, Cd and humic acids increases in a similar matter with increasing salt molarily: Ca²⁺ is the most dominant coagulating agent. Removal by coagulation with Ca²⁺ at seawater concentrations ranges from large (Fe-80%. HA-60%, Cu-40%) to small (Ni, Cd-15%) to essentially nothing (Cd, Mn-3%). Destabilization of colloids is the indicated mechanism. Solubility-pH measurements show that between a pH of 3 and 9, Fe, Cu, Ni, Mn, Co and Cd are being held in the dissolved phase by naturally occurring organic substances. Between pH of 2.2 and 1.2 a large proportion of dissolved Fe, Cu. Ni and Cd (72, 35,44 and 36% respectively) is precipitated along with the humic acids; in contrast, Mn and Co show little precipitation (3%). Adsorption-pH experiments, using unfiltered river water spiked with Cu, indicate that adsorption of Cu onto suspended particles is inhibited to a large extent by the formation of dissolved Cu-organic complexes.The experimental results demonstrate that solubilities and adsorption properties of certain trace metals in freshwaters can be opposite to those observed with artificial solutions or predicted with chemical models. Interaction with organic substances is a critical factor.     

Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.     

FeS胶体对三价铁吸附态As(Ⅴ)的解吸作用

地下水中的含铁胶体颗粒会携带污染物如砷等运移,但人们对该过程中的机理缺乏认识.通过群组静态吸附解吸模拟实验, 探究FeS胶体对吸附在覆Fe₂O₃石英砂上As(Ⅴ)的解吸作用, 以及腐殖酸(HA)、H₂PO₄-和HCO₃-对解吸的影响.实验结果表明,室内合成的FeS胶体具有纳米级粒径和较大的比表面积,且能均匀稳定存在于水溶液中.低浓度的FeS胶体主要通过竞争覆Fe₂O₃石英砂表面的吸附点位将As(Ⅴ)解吸,而高浓度的FeS胶体主要通过与覆Fe₂O₃石英砂竞争对As(Ⅴ)的吸附而导致解吸.HA、H₂PO₄-和HCO₃-对As(Ⅴ)的竞争解吸作用降低了FeS胶体导致的解吸效率.      

Adsorption of antimony(V) on kaolinite as a function of pH,ionic strength and humic acid

The present work investigated the adsorption and mobility (desorption) of Sb(V) on kaolinite using batch experiments. The adsorption of Sb(V) on kaolinite was studied as a function of contact time, pH, ionic strength, humic acid (HA), initial Sb(V) concentration and temperature. Kinetic studies suggest that the equilibrium is achieved within 24 h. The adsorption of Sb(V) was strongly affected by changes in I at low ionic strength and unaffected at high ionic strength. The adsorption is weakly dependent on the presence of humic acid, but is strongly dependent on pH. Within the range tested, the optimal pH for Sb(V) adsorption is 3.6, and close to 75% removal can be achieved. Desorption is dependent on the original suspension pH. The addition sequence of Sb(V)/HA do not influence the adsorption of Sb(V) on kaolinite. The adsorption data fit both the Freundlich and Langmuir isotherm. The thermodynamic parameters (ΔH ⁰, ΔS ⁰ and ΔG ⁰) were calculated from the temperature dependence, and the results suggest the endothermic and spontaneous nature of the process.     

Effet de l'agrégation sur le transport de la kaolinite recouverte d'acide humique à travers un sable de quartz d'origine naturelleAggregation effect on the transport of humic-coated kaolinite colloids through a natural quartz sand

To evaluate the risk of contaminant transport by mobile colloids, it is necessary to understand how colloids and associated pollutants behave during their migration through uncontaminated soil or groundwater. In this study, we investigated the influence of aggregation induced by Ca²⁺ and trace metals (Pb²⁺, Cu²⁺) concentrations on the transport of humic-coated kaolinite colloids through a natural quartz sand at pH=4. Adsorbed divalent cations reduce the colloids surface charge and thereby induce aggregation and deposition in porous media. To cite this article: R. Ait Akbour et al., C. R. Geoscience 334 (2002) 981–985.     

Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation

Published experimental data for Al(III) and Fe(III) binding by fulvic and humic acids can be explained approximately by the Humic Ion-Binding Model VI. The model is based on conventional equilibrium reactions involving protons, metal aquo ions and their first hydrolysis products, and binding sites ranging from abundant ones of low affinity, to rare ones of high affinity, common to all metals. The model can also account for laboratory competition data involving Al(III), Fe(III) and trace elements, supporting the assumption of common binding sites. Field speciation data (116 examples) for Al in acid-to-neutral waters can be accounted for, assuming that 60-70 % (depending upon competition by iron, and the chosen fulvic acid : humic acid ratio) of the dissolved organic carbon (DOC) is due to humic substances, the rest being considered inert with respect to ion binding. After adjustment of the model parameter characterizing binding affinity within acceptable limits, and with the assumption of equilibrium with a relatively soluble form of Fe(OH)₃, the model can simulate the results of studies of two freshwater samples, in which concentrations of organically complexed Fe were estimated by kinetic analysis.The model was used to examine the pH dependence of Al and Fe binding by dissolved organic matter (DOM) in freshwaters, by simulating the titration with Ca(OH)₂ of an initially acid solution, in equilibrium with solid-phase Al(OH)₃ and Fe(OH)₃. For the conditions considered, Al, which is present at higher free concentrations than Fe(III), competes significantly for the binding of Fe(III), whereas Fe(III) has little effect on Al binding. The principal form of Al simulated to be bound at low pH is Al³⁺, AlOH²⁺ being dominant at pH >6; the principal bound form of Fe(III) is FeOH²⁺ at all pH values in the range 4-9. Simulations suggest that, in freshwaters, both Al and Fe(III) compete significantly with trace metals (Cu, Zn) for binding by natural organic matter over a wide pH range (4-9). The competition effects are especially strong for a high-affinity trace metal such as Cu, present at low total concentrations (∼1 nM). As a result of these competition effects, high-affinity sites in humic matter may be less important for trace metal binding in the field than they are in laboratory systems involving humic matter that has been treated to remove associated metals.     

Biomineralization of lepidocrocite and goethite by nitrate-reducing Fe(II)-oxidizing bacteria: Effect of pH, bicarbonate, phosphate, and humic acids

Fe(III) solid phases are the products of Fe(II) oxidation by Fe(II)-oxidizing bacteria, but the Fe(III) phases reported to form within growth experiments are, at times, poorly crystalline and therefore difficult to identify, possibly due to the presence of ligands (e.g., phosphate, carbonate) that complex iron and disrupt iron (hydr)oxide precipitation. The scope of this study was to investigate the influences of geochemical solution conditions (pH, carbonate, phosphate, humic acids) on the Fe(II) oxidation rate and Fe(III) mineralogy. Fe(III) mineral characterization was performed using ⁵⁷Fe-Mössbauer spectroscopy and μ-X-ray diffraction after oxidation of dissolved Fe(II) within Mops-buffered cell suspensions of Acidovorax sp. BoFeN1, a nitrate-reducing, Fe(II)-oxidizing bacterium. Lepidocrocite (γ-FeOOH) (90%), which also forms after chemical oxidation of Fe(II) by dissolved O₂, and goethite (α-FeOOH) (10%) were produced at pH 7.0 in the absence of any strongly complexing ligands. Higher solution pH, increasing concentrations of carbonate species, and increasing concentrations of humic acids promoted goethite formation and caused little or no changes in Fe(II) oxidation rates. Phosphate species resulted in Fe(III) solids unidentifiable to our methods and significantly slowed Fe(II) oxidation rates. Our results suggest that Fe(III) mineralogy formed by bacterial Fe(II) oxidation is strongly influenced by solution chemistry, and the geochemical conditions studied here suggest lepidocrocite and goethite may coexist in aquatic environments where nitrate-reducing, Fe(II)-oxidizing bacteria are active.     

Association of dissolved radionuclides released by the Chernobyl accident with colloidal materials in surface water

The association of dissolved ⁹⁰Sr, ^239,240Pu and ²⁴¹Am with natural colloids was investigated in surface waters in the Chernobyl nuclear accident area. A 4-step ultrafiltration (UF) study (<1 kilodaltons (Da), 1–10 kDa, 10–100 kDa, 100 kDa<) showed that 49–83% of ^239,240Pu and 76% of ²⁴¹Am are distributed in colloids of the two size fractions larger than 10 kDa (nominal molecular weight limit of the filter, NMWL), while ⁹⁰Sr was found exclusively (85–88%) in the lowest molecular size fraction below 1 kDa (NMWL) for the Sahan River water at the highly contaminated area close to the Chernobyl Nuclear Power Plant (ChNPP). Consistent results were obtained by 2-step fractionation (larger than and smaller than 10 kDa (NMWL)) for river and lake waters including other locations within about 30 km away from ChNPP. It is likely that Pu and Am isotopes were preferentially associated with dissolved organic matter of high molecular size, as suggested by the fact that (i) only a few inorganic elements (Mg, Ca, Sr, Si, Mn, Al) were found in the colloidal size ranges, and (ii) the positive correlation between dissolved organic C (DOC) concentrations and UV absorbance at 280 nm, a broad absorption peak characteristic of humic substances (HS) was found. A model calculation on the complexation of Pu and Am with HS as an organic ligand suggests that the complexed form could be dominant at a low DOC concentration of 1 mgC L⁻¹, that is commonly encountered as a lower limit in fresh surface water. The present results suggest the general importance of natural organic colloids in dictating the chemical form of actinides in the surface aquatic environment.     

Metal sorption to dolomite surfaces

Potential human intrusion into the Waste Isolation Pilot Plant (WIPP) might release actinides into the Culebra Dolomite where sorption reactions will affect of radiotoxicity from the repository. Using a limited residence time reactor the authors have measured Ca, Mg, Nd adsorption/exchange as a function of ionic strength, P_CO2, and pH at 25°C. By the same approach, but using as input radioactive tracers, adsorption/exchange of Am, Pu, U, and Np on dolomite were measured as a function of ionic strength, P_CO2, and pH at 25°C. Metal adsorption is typically favored at high pH. Calcium and Mg adsorb in near-stoichiometric proportions except at high pH. Adsorption of Ca and Mg is diminished at high ionic strengths (e.g., 0.5M NaCl) pointing to association of Na⁺ with the dolomite surface, and the possibility that Ca and Mg sorb as hydrated, outer-sphere complexes. Sulfate amplifies sorption of Ca and Mg, and possibly Nd as well. Exchange of Nd for surface Ca is favored at high pH, and when Ca levels are low. Exchange for Ca appears to control attachment of actinides to dolomite as well, and high levels of Ca²⁺ in solution will decrease K_ds. At the same time, to the extent that high P_CO2s increase Ca²⁺ levels, K_ds will decrease with CO₂ levels as well, but only if sorbing actinide-carbonate complexes are not observed to form (Am-carbonate complexes appear to sorb; Pu-complexes might sorb as well. U-carbonate complexation leads to desorption). This indirect CO₂ effect is observed primarily at, and above, neutral pH. High NaCl levels do not appear to affect to actinide K_ds.     

The adsorption of aquatic humic substances by iron oxides

The interactions of humic substances from Esthwaite Water with hydrous iron oxides (α-FeOOH, α-Fe₂O₃, amorphous Fe-gel) have been examined by measuring adsorption isotherms and by microelectrophoresis. In Na⁺-Cl^?-HCO₃^?at I = 0.002 M (medium I) the extent of adsorption decreases with increasing pH. The results are consistent with a mechanism involving ligand exchange of humic anionic groups with H₂O and OH^?of surface Fe-OH₂⁺and Fe-OH groups respectively, with an increasing degree of protonation of the adsorbed humics as the adsorption density increases at constant pH.At pH 7 in a medium containing Mg²⁺, Ca²⁺ and SO₄^2?, at their Esthwaite Water concentrations and at I= 0.002 M (medium II) the adsorption capacity of goethite (α-FeOOH) is approximately twice that in medium I. Electrophoresis experiments show that the extra capacity is associated with coadsorption of Mg²⁺ and/or Ca²⁺ ions.When the iron oxides are added to samples of Esthwaite Water itself they become negatively charged and plots of electrophoretic mobility against pH for the natural water are identical to those in medium II plus humics.     

天然黏土矿物和腐殖酸对纳米乳化油吸持的实验研究

为探讨天然黏土矿物及有机质对纳米乳化油在多孔介质中迁移滞留的影响，本文选取高岭石和蒙脱石这两种黏土矿物以及有机质的典型代表腐殖酸，开展了单一矿物、有机质及有机矿质复合物对纳米乳化油的吸持批实验研究，并运用比表面积全分析、扫描电镜(SEM)、傅里叶红外光谱(FTIR)、X射线衍射(XRD)等技术手段探讨了吸持机理。实验结果表明，介质对纳米乳化油的吸持均符合Freundlich模型；单一矿物及腐殖酸对纳米乳化油的吸持能力表现为：蒙脱石>腐殖酸>高岭石，有机矿质复合样品的吸持能力表现为：蒙脱石-腐殖酸>高岭石-腐殖酸，且均大于其对应的单一样品，出现了“1+1>2”的现象，表明介质组成越复杂，对纳米乳化油的吸持滞留程度越大。进一步分析证实，纳米乳化油主要通过氢键和疏水作用吸持在矿物和腐殖酸表面，表面结构性质是高岭石和蒙脱石吸持过程中的主导因素，因此蒙脱石具有更强的吸持能力，而腐殖酸的吸持主要通过颗粒间聚集作用来实现；对于复合样品，吸持主要通过氢键、配体交换和疏水作用结合来实现。腐殖酸与矿物的复合会增加吸持位点并且增强矿物表面疏水性，从而促进吸持。腐殖酸与纳米乳化油的共吸...     

Formation of uranium(IV)-silica colloids at near-neutral pH

Evidence is provided by photon correlation spectroscopy, ultrafiltration and ultracentrifugation that uranium(IV) can form silicate-containing colloids of a size of ?20 nm. A concentration of up to 10⁻³ M of colloid-borne U(IV) was observed. The particles are generated in near-neutral to slightly alkaline solutions containing background chemicals of geogenic nature (carbonate, silicate, sodium ions). They remain stable in aqueous suspension over years. Electrostatic repulsion due to a negative zeta potential in the near-neutral to alkaline pH range caused by the silicate stabilizes the U(IV) colloids. The isoelectric point of the nanoparticles is shifted toward lower pH values by the silicate. The mechanism of the colloidal stabilization can be regarded as “sequestration” by silicate, a phenomenon well known from heavy metal ions of high ion potential such as iron(III) or manganese(III,IV), but never reported for uranium(IV) so far. Extended X-ray absorption fine structure (EXAFS) spectroscopy showed that U-O-Si bonds, which increasingly replace the U-O-U bonds of the amorphous uranium(IV) oxyhydroxide with increasing silicate concentrations, make up the internal structure of the colloids. The next-neighbor coordination of U(IV) in the U(IV)-silica colloids is comparable with that of coffinite, USiO₄. The assessment of uranium behavior in the aquatic environment should take the possible existence of U(IV)-silica colloids into consideration. Their occurrence might influence uranium migration in anoxic waters.