Comparative kinetic desorption of 60Co, 85Sr and 134Cs from a contaminated natural silica sand column: influence of varying physicochemical conditions and dissolved organic matter

In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces.     

Laboratory migration experiments with radionuclides and natural colloids in a granite fracture

Natural colloids in groundwater could facilitate radionuclide transport, provided the colloids are mobile, are present in sufficient concentrations and can adsorb radionuclides. This paper describes the results of a laboratory migration study carried out with combinations of radionuclides and natural colloids within a fracture in a large granite block to experimentally determine the impact of colloids on radionuclide transport. The 85Sr used in this study is an example of a moderately sorbing radionuclide, while the 241Am is typical of a strongly sorbed radionuclide with very low solubility. The natural colloids used in this study were isolated from granite groundwater from Atomic Energy of Canada (AECL) Underground Research Laboratory (URL), and consisted of mostly 1-10 nm organic colloids, along with lesser amounts of 10-450 nm colloids (organics and aluminosilicates). The measured coefficients for radionuclide sorption onto these colloids were between 3 x 10(2) and 1 x 10(3) ml/g for 85Sr, and between 7 x 10(4) and 7 x 10(5) mg/l for 241Am. The 85Sr sorption on the natural colloids appeared to be reversible. Migration experiments in the granite block were carried out by establishing a flow field between two boreholes (out of a total of nine) intersecting a main horizontal fracture. These experiments showed that dissolved 85Sr behaved as a moderately sorbing tracer, while dissolved 241Am was completely adsorbed by the fracture surfaces and showed no evidence of transport. However, when natural colloids were injected together with dissolved 241Am, a small amount of 241Am transport was observed, demonstrating the ability of natural colloids to facilitate the transport of radionuclides with low solubility. Natural colloids had only a minor effect on the transport of 85Sr. In a separate experiment to test the effect of higher colloid concentrations on 85Sr migration, synthetic colloids were produced from Avonlea bentonite. The introduction of a relatively high concentration of bentonite colloids actually reduced 85Sr transport because, compared to natural colloids, the bentonite colloids were less mobile and they sorbed 85Sr more strongly.     

Colloid‐facilitated transport of metolachlor through intact soil columns

Abstract

This study evaluated the role of water dispersible colloids with diverse physicochemical and mineralogical characteristics in facilitating the transport of metolachlor through macropores of intact soil columns. The soil columns represented upper solum horizons of an Alfisol in the Bluegrass region of Kentucky. Three different colloid suspensions tagged with metolachlor [2‐chloro‐N‐(2‐ethyl‐6‐methylphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide] were introduced at a constant flux into undisturbed soil columns. The eluents were collected and analyzed periodically for colloid and metolachlor concentrations. Colloid recovery in the eluents ranged from 54 to 90 %. The presence of colloids enhanced the transport of metolachlor by 22 to 70 % depending on the colloid type and mobility. Colloids with higher pH, organic carbon, cation exchange capacity (CEC), total exchangeable bases (TEB), surface area (SA), and electrophoretic mobility (EM), showed better mobility, greater affinity for interaction with the herbicide and, thus, greater potential to co‐transport metolachlor. In contrast, increased level of kaolinite, Fe, and Al inhibited metolachlor adsorption and transport. In spite of the increased transportability of metolachlor by the presence of soil colloids, the colloid bound herbicide portion accounted for a very small part of the observed increase. This suggests that surface site exclusion mechanisms and preferential sorption induced by the presence of colloids are more important than ion exchange phenomena in promoting herbicide mobility in subsurface environments.     

Observation and characterization of colloids derived from leached cement hydrates

The possibility of colloid generation from cement hydrates in a cementitious repository environment has been investigated through leaching experiments. Pulverized samples of High Flyash and Silica fume-content Cement (HFSC) and 1:9 ordinary portland cement/blast furnace slag (1:9 OPC/BFS) hydrate were leached in low-salinity groundwater at three solid-to-liquid (S/L) mass ratios (1:5, 1:50 and 1:100), and two temperatures (20 and 60 degrees C) for durations of nearly 2 and 8 months. Detailed characterization of colloid populations has been undertaken by TEM coupled with X-ray analysis. In addition, the surface charge and stability behavior of colloids have been investigated. The colloid concentrations in HFSC hydrate leachates generated at 20 and 60 degrees C show similar trends with S/L ratio. The colloid concentrations of leachates with the lower S/L ratio (1:50 and 1:100) are in the range of 10(11)-10(12) particles per liter. The majority of these particles are composed predominantly of Si, Ca, and Al; the mean particle size is less than 100 nm. The lowest colloid concentrations are found in the leachates with the highest S/L ratios, and the colloid populations tend to be dominated by larger particles. HFSC-derived colloid stability is due to a high negative zeta potential at alkaline pH values, combined with a calcium concentration that is below the critical coagulation concentration (CCC) for the colloids. A preliminary interpretation of HFSC-derived colloid stability based on classical DLVO theory provides a semi-quantitative explanation of the dependence of colloid populations on the S/L ratio in the leaching experiments.     

Coagulation of colloidal material in surface waters: the role of natural organic matter

Organic matter has a great influence over the fate of inorganic colloids in surface waters. The chemical nature and structure of natural organic matter (NOM) will be an important factor in determining whether colloids will be stabilised or destabilised by NOM. Under environmentally relevant conditions, the ubiquitous fulvic acids are likely to be responsible for coating and imparting a negative charge to colloids. If the adsorbed polyelectrolyte coating produces an increase in absolute surface potential, it will act to stabilise colloids in the water column. On the other hand, colloidal organic carbon, especially chain-like structures, has been shown to be involved in the aggregation of inorganic colloids through the formation of bridges. It is highly probable that both adsorption and bridging flocculation are occurring simultaneously in the natural aquatic environment. The importance of each process depends directly on the nature and concentration of organic matter in the system and indirectly on the productivity of the lake, its hydrological pathways, temporal variations, temperature, etc. The present paper reports such results and emphasises the need to discriminate the different kinds of NOM.     

Characteristics of colloids and their affinity for heavy metals in road runoff with different traffic in Beijing,China

The characteristics of colloids in urban road runoff with different traffic in Beijing, China, such as concentration, particle size, chemical property, and affinity for heavy metals were determined. The concentration of colloids was high, and an evident first flush effect was found in the runoff of road with heavy traffic. A large portion of colloids were distributed in the range of 1–10 μm. Traffic activity, rainfall intensity, and time of sample collection would not change the size distribution of colloids in the road runoff. The chemical property of colloids in the road runoff would be influenced by the soil erosion nearby green space, causing the content of organic colloids was high. The correlation coefficient between the concentration of colloids in colloidal fractions and the concentration of heavy metals (Cu, Zn, Cd, Pb, Fe, and Mn) in the road runoff with different traffic decreased with the same sequence from 0.02–0.2 μm, 0.2–0.45 μm, 0.45–1 μm, to 1–10 μm, suggesting that the heavy metals had stronger affinity for the colloids with small size. The concentration of Cu, Pb, and Zn exhibited significant correlations with the concentration of organic colloids in the road runoff. More aggregated spherical particles were found in the TEM image of the road runoff with heavy traffic. Zeta potentials and RMV data showed that the colloids with smaller size and the colloids in the road runoff with lighter traffic were much more stable.

     

Mobility of radionuclides in soil/groundwater system: Comparing the influence of EDTA and four of its degradation products

The adsorption behavior of ²⁴¹Am, ⁶⁰Co, ¹³⁷Cs and ⁸⁵Sr in the presence and absence of chelating ligands (ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, iminodiaceiticacid and methyliminodiacetic acid) was investigated. Sorption affinity in the absence of chelating ligands followed: Am(III) > Co(II) > Cs(I) > Sr(II). The presence of chelating ligands generally had little effect on sorption of ⁸⁵Sr and ¹³⁷Cs with K_d values 110 and 690 mL g⁻¹, respectively. But at 0.02 M of ethylenediaminetetraacetic or hydroxyethyliminodiacetic, the K_d decreased to 5 or 63 mL g⁻¹, respectively, where thermochemical modeling indicated almost all ⁸⁵Sr is complexed with these ligands. The K_d values for ²⁴¹Am and ⁶⁰Co generally decreased with increasing chelating agent concentrations. In notable cases, the K_d values for Am increased at specific concentrations of 10⁻³ M for IDA, MIDA and 10⁻⁴ M for EDDA. This is proposed to be due to formation of a ternary surface complex.     

Colloid transport in unsaturated porous media: the role of water content and ionic strength on particle straining

Packed column and mathematical modeling studies were conducted to explore the influence of water saturation, pore-water ionic strength, and grain size on the transport of latex microspheres (1.1 microm) in porous media. Experiments were carried out under chemically unfavorable conditions for colloid attachment to both solid-water interfaces (SWI) and air-water interfaces (AWI) using negatively charged and hydrophilic colloids and modifying the solution chemistry with a bicarbonate buffer to pH 10. Interaction energy calculations and complementary batch experiments were conducted and demonstrated that partitioning of colloids to the SWI and AWI was insignificant across the range of the ionic strengths considered. The breakthrough curve and final deposition profile were measured in each experiment indicating colloid retention was highly dependent on the suspension ionic strength, water content, and sand grain size. In contrast to conventional filtration theory, most colloids were found deposited close to the column inlet, and hyper-exponential deposition profiles were observed. A mathematical model, accounting for time- and depth-dependent straining, produced a reasonably good fit for both the breakthrough curves and final deposition profiles. Experimental and modeling results suggest that straining--the retention of colloids in low velocity regions of porous media such as grain junctions--was the primary mechanism of colloid retention under both saturated and unsaturated conditions. The extent of stagnant regions of flow within the pore structure is enhanced with decreasing water content, leading to a greater amount of retention. Ionic strength also contributes to straining, because the number of colloids that are held in the secondary energy minimum increases with ionic strength. These weakly associated colloids are prone to be translated to stagnation regions formed at grain-grain junctions, the solid-water-air triple point, and dead-end pores and then becoming trapped.     

Generation and stability of bentonite colloids at the bentonite/granite interface of a deep geological radioactive waste repository

The possible mechanisms of colloid generation at the near field/far field interface of a radioactive repository have been investigated by means of novel column experiments simulating the granite/bentonite boundary, both in dynamic and in quasi-static water flow conditions. It has been shown that solid particles and colloids can be detached from the bulk and mobilised by the water flow. The higher the flow rate, the higher the concentration of particles found in the water, according to an erosion process. However, the gel formation and the intrinsic tactoid structure of the clay play an important role in the submicron particle generation even in the compacted clay and in a confined system. In fact, once a bentonite gel is formed, in the regions where the clay is contacted with water, clay colloids can be formed even in quasi-static flow conditions. The potential relevance of these colloids in radionuclide transport has been studied by evaluating their stability in different chemical environments. The coagulation kinetics of natural bentonite colloids was experimentally studied as a function of the ionic strength and pH, by means of time-resolved light scattering techniques. It has been shown that these colloids are very stable in low saline (approximately 1 x 10(-3) M) and alkaline (pH > or = 8) waters.     

Numerical modeling of humic colloid borne americium (III) migration in column experiments using the transport/speciation code K1D and the KICAM model

The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parmeters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.     

Colloid and suspended particle migration experiments in a granite fracture

To determine the mobility of colloids (0.001–0.45 μm) and suspended particles (> 0.45 μm) in granite fractures, laboratory particle-migration and conservative tracer studies have been carried out in a natural fracture within a large granite block, with overall dimensions of 83×90×60 cm. Flow fields within this horizontal fracture were controlled through a set of 9 boreholes drilled orthogonally to the fracture. Laboratory experiments were performed using a range of average water velocities which contained values low enough to closely approximate the natural flow velocities of < 2 m yr⁻¹ in plutonic rocks of the Canadian Shield. The particles used had diameters between 0.02 and 22 μm, and included latex spheres, glass spheres and colloidal silica. Migration experiments were carried out with a filtered groundwater, ionic strength of 0.01 mol kg⁻¹, obtained from a granite fracture within the Whiteshell Research Area of Manitoba. Flushing experiments showed that suspended particles as large as 40 μm could be mobilized from the fracture surface. The mobility of suspended particles was significantly less than that of colloids. However, within the size range of colloids used in these studies (0.022–0.090 μm), colloid size did not affect colloid migration. Although, in general, colloids eluted ahead of the conservative tracer, colloid mobility was significantly reduced when the average groundwater velocity dropped below between 32 and 240 m yr⁻¹. Colloid transport was found to be very sensitive to flow path and flow direction.     

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.     

The influence of colloid formation in a granite groundwater bentonite porewater mixing zone on radionuclide speciation

In the context of deep geological storage of high level nuclear waste the repository will be designed as multiple barrier system including bentonite as buffer/backfill material and the host rock formation as geological barrier. The engineered barrier (bentonite) will be in contact with the host rock formation and consequently it can be expected that bentonite porewater will mix with formation groundwater. We simulate in this study the mixing of Grimsel groundwater (glacial melt water) with synthetic Febex porewater (assuming already saturated state) in a batch-type study and investigate the formation of colloids by laser-induced breakdown detection (LIBD) and SEM-EDX as well as the changes in radionuclide (U, Th, Eu) speciation via ultrafiltration or via time-resolved laser fluorescence spectroscopy (TRLFS) analysis in the case of Cm(III). Based on PHREEQC saturation index (SI) calculations a precipitation of calcite might be expected at low Febex porewater (FPW) content (< 20%), fluorite precipitation at FPW contents < 60% and gibbsite precipitation at FPW contents above 10%. The colloids generated in the mixing zone aggregate when the synthetic FPW content exceeds 10%. LIBD analysis of the time-dependent colloid generation/aggregation revealed a low concentration of colloids to be stable with an estimated plateau value around 100–200 ppt and an average colloid diameter around 30 nm after 140 days reaction time at FPW admixture > 10%. SEM/EDX mostly identifies Al/Si containing colloidal phases and some sulfates could be found under certain admixture ratios. TRLFS studies show that the Cm speciation is strongly influenced by colloid formation in all solutions. In the Febex pore water/GGW mixing zone with high groundwater contents (> 80%) colloids are newly formed and Cm is almost quantitatively associated with most likely polysilicilic acid colloids.     

Field-scale colloid migration experiments in a granite fracture

An understanding of particle migration in fractured rock, required to assess the potential for colloid-facilitated transport of radionuclides, can best be evaluated when the results of laboratory experiments are demonstrated in the field. Field-scale migration experiments with silica colloids were carried out at AECL's Underground Research Laboratory (URL), located in southern Manitoba, to develop the methodology for large-scale migration experiments and to determine whether colloid transport is possible over distances up to 17 m. In addition, these experiments were designed to evaluate the effects of flow rate and flow path geometry, and to determine whether colloid tracers could be used to provide additional information on subsurface transport to that provided by conservative tracers alone. The colloid migration studies were carried out as part of AECL's Transport Properties in Highly Fractured Rock Experiment, the objective of which was to develop and demonstrate methods for evaluating the solute transport characteristics of zones of highly fractured rock. The experiments were carried out within fracture zone 2 as two-well recirculating, two-well non-recirculating, and convergent flow tests, using injection rates of 5 and 10 1 min⁻¹. Silica colloids with a 20 nm size were used because they are potentially mobile due to their stability, small size and negative surface charge. The shapes of elution profiles for colloids and conservative tracers were similar, demonstrating that colloids can migrate over distances of 17 m. The local region of drawdown towards the URL shaft affected colloid migration and, to a lesser extent, conservative tracer migration within the flow field established by the two-well tracer tests. These results indicate that stable colloids, with sizes as small as 20 nm, have different migration properties from dissolved conservative tracers. - 1997 Atomic Energy of Canada.     

Preliminary 3-D site-scale studies of radioactive colloid transport in the unsaturated zone at Yucca Mountain,Nevada

The U.S. Department of Energy (DOE) is actively investigating the technical feasibility of permanent disposal of high-level nuclear waste in a repository to be situated in the unsaturated zone (UZ) at Yucca Mountain (YM), Nevada. In this study we investigate, by means of numerical simulation, the transport of radioactive colloids under ambient conditions from the potential repository horizon to the water table. The site hydrology and the effects of the spatial distribution of hydraulic and transport properties in the Yucca Mountain subsurface are considered. The study of migration and retardation of colloids accounts for the complex processes in the unsaturated zone of Yucca Mountain, and includes advection, diffusion, hydrodynamic dispersion, kinetic colloid filtration, colloid straining, and radioactive decay. The results of the study indicate that the most important factors affecting colloid transport are the subsurface geology and site hydrology, i.e., the presence of faults (they dominate and control transport), fractures (the main migration pathways), and the relative distribution of zeolitic and vitric tuffs. The transport of colloids is strongly influenced by their size (as it affects diffusion into the matrix, straining at hydrogeologic unit interfaces, and transport velocity) and by the parameters of the kinetic-filtration model used for the simulations. Arrival times at the water table decrease with an increasing colloid size because of smaller diffusion, increased straining, and higher transport velocities. The importance of diffusion as a retardation mechanism increases with a decreasing colloid size, but appears to be minimal in large colloids.     

Influence of pH and ozone dose on the content and structure of haloacetic acid precursors in groundwater

This study investigated the effects of pH (6-10) and ozone dose [0.4-3.0?mg O(3)/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85?±?0.18?mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65?% fulvic and 14?% humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309?±?15?μg/L). Ozonation at pH?6-10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65-90?% achieved using 3.0?mg O(3)/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH?10 (up to 68?% HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1?±?6.0?μg/mg DOC in raw water to 152?±?8?μg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH?10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.     

Interaction of latex colloids with mineral surfaces and Grimsel granodiorite

Bentonite clay is considered as possible backfill material for nuclear waste repositories in crystalline rock. The same material may also be a source of clay colloids, which may act as carriers for actinide ions possibly released from the repository. Depending on the geochemical parameters, these colloids may be retained by interaction with mineral surfaces of the host rock. In the present study interaction of carboxylated fluorescent latex colloids, used as a model for bentonite colloids, with natural Grimsel granodiorite and some of its component minerals is studied by fluorescence microscopy and SEM/EDX. The experiments are carried out by varying the pH from 2–10. Strong adsorption is observed at pH values close to or below the points of zero charge (pH_pzc) of the mineral surfaces. The influence of Eu(III), used as a chemical homologue for trivalent actinide ions, on colloid adsorption is investigated. Depending on mineral phase and pH, a significant increase of colloid adsorption is observed in the presence of Eu(III).     

Plant uptake of radionuclides in lysimeter experiments

The results of seven years lysimeter experiments to determine the uptake of 60Co, 137Cs and 226Ra into agricultural crops (endive, maize, wheat, mustard, sugarbeet, potato, Faba bean, rye grass) are described. The lysimeter consists of twelve monolithic soil profiles (four soil types and three replicates) and is located in Seibersdorf/Austria, a region with a pannonian climate (pronounced differences between hot and semi-arid summers and humid winter conditions, annual mean of precipitation: 517 mm, mean annual temperature: 9.8 degrees C). Besides soil-to-plant transfer factors (TF), fluxes were calculated taking into account biomass production and growth time. Total median values of TF's (dry matter basis) for the three radionuclides decreased from 226Ra (0.068 kg kg(-1)) to 137Cs (0.043 kg kg(-1)) and 60Co (0.018 kg kg(-1)); flux values exhibited the same ranking. The varying physical and chemical properties of the four experimental soils resulted in statistically significant differences in transfer factors or fluxes between the investigated soils for 137Cs and 226Ra, but not for 60Co. Differences in transfer between plant species and plant parts are distinct, with graminaceous species showing, on average, TF values 5.8 and 15 times lower than dicotyledonous species for 137Cs and 60Co, respectively. This pattern was not found for 226Ra. It can be concluded that 137Cs transfer is heavily influenced by soil characteristics, whilst the plant-specific factors are the main source of TF variability for 60Co. The variability of 226Ra transfer originates both from soil properties and plant species behaviour.