Modelling of silica diffusion experiments with Si in Boom Clay

A mathematical model describing the dissolution of nuclear glass directly disposed in clay combines a first-order dissolution rate law with the diffusion of dissolved silica in clay. According to this model, the main parameters describing the long-term dissolution of the glass are ηR, the product of the diffusion accessible porosity η and the retardation factor R, and the apparent diffusion coefficient D_app of dissolved silica in clay.For determining the migration parameters needed for long-term predictions, four Through-Diffusion (T-D) experiments and one percolation test have been performed on undisturbed clay cores. In the Through-Diffusion experiments, the concentration decrease after injection of ³²Si (radioactive labelled silica) was measured in the inlet compartment. At the end of the T-D experiments, the clay cores were cut in thin slices and the activity of labelled silica in each slice was determined. The measured activity profiles for these four clay cores are well reproducible.Since no labelled silica could be detected in the outlet compartments, the Through-Diffusion experiments are fitted by two In-Diffusion models: one model assuming linear and reversible sorption equilibrium and a second model taking into account sorption kinetics. Although the kinetic model provides better fits, due to the sufficiently long duration of the experiments, both models give approximately similar values for the fit parameters. The single percolation test leads to an apparent diffusion coefficient value about two to three times lower than those of the Through-Diffusion tests.Therefore, dissolved silica appears to be strongly retarded in Boom Clay. A retardation factor R between 100 and 300 was determined. The corresponding in situ distribution coefficient K_d is in the range 25–75 cm³ g⁻¹. The apparent diffusion coefficient of dissolved silica in Boom Clay is estimated between 2×10⁻¹³ and 7×10⁻¹³ m² s⁻¹. The pore diffusion coefficient is in the range from 6×10⁻¹¹ to 1×10⁻¹⁰ m² s⁻¹.     

An analytical model for the interpretation of pulse injection experiments performed for testing the spatial variability of clay formations

This paper presents an analytical model to describe pulse injection experiments. This model solves the advection-diffusion equation while taking into account back diffusion from the clay core to the inlet and from the outlet to the clay core. In most analytical models, back diffusion is neglected. For sufficiently high Péclet numbers, this is a good approximation. However, in experiments where the Péclet number is low, back diffusion is important and must be taken into account. An additional advantage of the present model is that both concentration and flux are conserved at the inlet and at the outlet of the clay core. This model is used to fit pulse injection experiments with iodide and tritiated water (HTO) in clay cores. The (new) model is required for fitting the experimental results since in clay layers advection is very slow leading to a low Péclet number. The experiments are performed on clay cores taken from different depths from the Boom Clay and the Ypres Clay layer under the site of the nuclear power plant of Doel (Belgium). The quality of all fits is excellent and the obtained parameter values are coherent. For HTO, the fitted value for the diffusion accessible porosity is consistent with measurements of the water content in Ypres Clay cores. In both types of clays, the apparent diffusion coefficient at zero flow is between 10(-10) and 2 x 10(-10) m(2)/s for iodide and between 2 x 10(-10) and 3 x 10(-10) m(2)/s for HTO. The dispersion length is in the order of 10(-3) m. The average value for the diffusion accessible porosity is between 0.35 and 0.4 for HTO and between 0.2 and 0.25 for iodide.     

Experimental and modeling studies on sorption and diffusion of radium in bentonite

The sorption and desorption behavior of radium on bentonite and purified smectite was investigated as a function of pH, ionic strength and liquid to solid ratio by batch experiments. The distribution coefficients (Kd) were in the range of 10(2) to > 10(4) ml g-1 and depended on ionic strength and pH. Most of sorbed Ra was desorbed by 1 M KCl. The results for purified smectite indicated that Ra sorption is dominated by ion exchange at layer sites of smectite, and surface complexation at edge sites may increase Ra sorption at higher pH region. Reaction parameters between Ra and smectite were determined based on an interaction model between smectite and groundwater. The reaction parameters were then used to explain the results of bentonite by considering dissolution and precipitation of minerals and soluble impurities. The dependencies of experimental Kd values on pH, ionic strength and liquid to solid ratio were qualitatively explained by the model. The modeling result for bentonite indicated that sorption of Ra on bentonite is dominated by ion exchange with smectite. The observed pH dependency was caused by changes of Ca concentration arising from dissolution and precipitation of calcite. Diffusion behavior of Ra in bentonite was also investigated as a function of dry density and ionic strength. The apparent diffusion coefficients (Da) obtained in compacted bentonite were in the range of 1.1 x 10(-11) to 2.2 x 10(-12) m2 s-1 and decreased with increasing in dry density and ionic strength. The Kd values obtained by measured effective diffusion coefficient (De) and modeled De were consistent with those by the sorption model in a deviation within one order of magnitude.     

Diffusive flux and pore anisotropy in sedimentary rocks

Diffusion of dissolved contaminants into or from bedrock matrices can have a substantial impact on both the extent and longevity of dissolved contaminant plumes. For layered rocks, bedding orientation can have a significant impact on diffusion. A series of laboratory experiments was performed on minimally disturbed bedrock cores to measure the diffusive flux both parallel and normal to mineral bedding of four different anisotropic sedimentary rocks. Measured effective diffusion coefficients ranged from 4.9×10(-8) to 6.5×10(-7)cm(2)/s. Effective diffusion coefficients differed by as great as 10-folds when comparing diffusion normal versus parallel to bedding. Differences in the effective diffusion coefficients corresponded to differences in the "apparent" porosity in the orientation of diffusion (determined by determining the fraction of pore cross-sectional area measured using scanning electron microscopy), with the difference in apparent porosity between normal and parallel bedding orientations differing by greater than 2-folds for two of the rocks studied. Existing empirical models failed to provide accurate predictions of the effective diffusion coefficient in either bedding orientation for all four rock types studied, indicating that substantial uncertainty exists when attempting to predict diffusive flux through sedimentary rocks containing mineral bedding. A modified model based on the apparent porosity of the rocks provided a reasonable prediction of the experimental diffusion data.     

Selenite reduction in Boom clay: Effect of FeS(2), clay minerals and dissolved organic matter

Several experiments were set up to study Se speciation and solubility in the reducing Boom clay environment, starting from oxidized Se species which were added in oversaturation with respect to the thermodynamic solubility of reduced Se solid phases. Upon introduction of SeO3(2-) to FeS(2)-containing samples, adsorption of SeO3(2-) occurred at the FeS2 surface, and led to a reduction and precipitation of a Se0 solid phase with a solubility of 3x10(-9) M (after 60 days). In the presence of humic substances, an association of Se with these humic substances was observed and the 3x10(-9) M solubility limit was not reached in the same time delay. Upon introduction of SeO3(2-) to Boom clay suspensions (equilibration up to 9 months), the initial adsorption of SeO3(2-) on the solid phase was increased with respect to systems containing only FeS2, due to the presence of (illite) clay minerals. This competing adsorption process, and the presence of humic substances, again decreased the kinetics of reduction with respect to FeS2 samples. Also, an association of Se with Boom clay humic substances was observed, and amounted up to approximately 10(-7) M in some samples after 9 months equilibration.     

The assessment of electromigration as a new technique to study diffusion of radionuclides in clayey soils

For the performance assessment study of a geological disposal of High Level Waste (HLW) in clayey formations, migration studies are essential. For low permeability soils (clays), classical diffusion studies take a very long time. In order to reduce the experimental time, we propose an electrical field as driving force to accelerate the migration of ionic species. This paper reports the assessment of the electromigration technique as a powerful new and fast technique for migration studies. The apparent molecular diffusion coefficient can be derived by two independent methods using the migration parameters obtained from an electromigration experiment, namely the apparent dispersion coefficient and the apparent convection velocity. First, it can be calculated from the velocity of the migrating species by the Einstein relation. But, corrections are necessary for electroosmotic flow. The apparent electroosmotic mobility is experimentally determined as 2.2·10⁻⁹ m²/Vs. Second, it can be calculated from the relation between the apparent dispersion coefficient and the total apparent convection velocity. But it is necessary to know the dispersion length of the medium. The dispersion length for Boom Clay is experimentally determined as 8·10⁻⁵ m. Because of the serious reduction in time, it becomes possible to run series of experiments at different electrical fields to obtain averaged values for the apparent molecular diffusion coefficient according to the two methods. Experiments at different electrical fields have another advantage: the intercept of the linear relationship between the total apparent convection velocity and the apparent dispersion coefficient gives the apparent molecular diffusion coefficient. The apparent molecular diffusion coefficients obtained for ⁸⁵Sr, ¹³¹I and HTO are respectively 0.8·10⁻¹¹, 15·10⁻¹¹, and 24·10⁻¹¹ m²/s. These values are confirmed by pure diffusion experiments. The excellent agreement with the apparent molecular diffusion coefficients obtained by classical diffusion tests clearly demonstrates the feasibility of the electromigration technique for the determination of diffusion coefficients.     

In situ anion diffusion experiments using radiotracers

Diffusion experiments in compacted bentonite have been carried out in situ using the borehole laboratory CHEMLAB. The "ordinary" anion iodide and the redox-sensitive pertechnetate ion have been investigated. In spite of strongly reducing groundwater conditions, technetium was found to diffuse mostly unreduced as TcO4-, although in some spots in the compacted clay, the activity was significantly higher, which may be explained by reduction of some TcO4- by iron-containing minerals in the bentonite. The measured concentration profiles in the clay cannot be accommodated by assuming one single diffusion process. The experimental data are modeled assuming two diffusion paths, intralamellar diffusion and diffusion in external water. The apparent diffusivity for the intralamellar diffusion was found to be 8.6 x 10(-11) m2 s(-1) for iodide with a capacity factor of 0.1, while the apparent diffusivity for the diffusion in external water was found to be 5 x 10(-14) m2 s(-1) with alpha=2.26. The corresponding values for Tc were found to be Da= 6 x 10(-11) m2 s(-1), alpha=0.1 and Da= 1 x 10(-13) m2 s(-1), alpha=0.46, respectively. The diffusion constants and capacity factors obtained in this study are in accordance with data from laboratory experiments.     

Sorption–desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions

Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd_ads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kf_ads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ～800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n_ads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.     

Direct simulation of heterogeneous diffusion and inversion procedure applied to an out-diffusion experiment. Test case of Palmottu granite

An out-diffusion laboratory experiment using a non-reactive tracer was fitted using the Time Domain Diffusion (TDD) method. This rapid particle tracking method allows simulation of the heterogeneous diffusion based on pore-scale images and local values of diffusivities. The superimposed porosity and mineral 2D maps act as computation grids to condition diffusion pathways. We focused on a Palmottu granite sample, in which the connected pore space has a composite microstructure with cracks linking microporous minerals and is above the percolation threshold. Three main results were achieved: (i) When compared to the fitting obtained with one coefficient (best mean square residual R = 1.6 x 10(-2)), diffusion is shown to be suitably characterised with two coefficients related to cracks and microporous minerals (best R = 6.5 x 10(-4)), (ii) rather than imposing a local apparent diffusion coefficient D(a) independent of the local porosity Phi, a best fit is obtained by applying Archie's relationship D(a) = D(0) x G with G = Phi(m) to each pixel of the calculation grids (G is the geometry factor, D(0) is the diffusion coefficient in free fluid, and m is Archie's exponent), and (iii) the order of magnitude of the fitted diffusion coefficient or Archie's exponents (m=0 for microcracks and m=1.82 for microporous minerals) is physically realistic.     

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient (K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.     

Diffusion of HTO, 36Cl- and 125I- in Opalinus Clay samples from Mont Terri. Effect of confining pressure

Diffusion coefficients (T=23 +/- 2 degrees C) and accessible porosities for HTO, 36Cl(-) and 125I(-) were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na(+) and Cl(-) as the main components (I=0.42 M). The measured values of the effective diffusion coefficients (D(e)) and rock capacity factors (alpha) are: D(e)=1.2-1.5 x 10(-11) m(2) s(-1) and alpha=0.09-0.11 for HTO, D(e)=4.0-5.5 x 10(-12) m(2) s(-1) and alpha=0.05 for 36Cl(-) and D(e)=3.2-4.6 x 10(-12) m(2) s(-1) and alpha=0.07-0.10 for 125I(-). For non-sorbing tracers (HTO, 36Cl) the rock capacity factor alpha is equal to the diffusion-accessible porosity epsilon. The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of approximately 17% for HTO, approximately 28% for 36Cl(-) and approximately 30% for 125I(-). Moreover, the diffusion coefficients for 36Cl(-) and 125I(-) are smaller than for HTO, which is consistent with an effect arising from anion exclusion. The diffusion coefficients of HTO and 125I(-) measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Capability and limitations of first-order and diffusion approaches to describe long-term sorption of chlortoluron in soil

This paper compares the capability of a first-order and a spherical diffusion model to describe and predict long-term sorption and desorption processes of chlortoluron in two soils. Chlortoluron sorption was investigated at different time scales utilizing one rate experiment (120 days) and two sorption/desorption experiments. Experimental periods for sorption and desorption were set to 1 day (five desorption steps) and 30 days (three desorption steps), respectively. Upon fitting, the two models satisfactorily described the whole set of data. The spherical diffusion model performed better than the first-order model. We then tested the predictive capability of the models by predicting 30-day sorption/desorption data using kinetic parameters fitted on 1-day sorption/desorption data only. While the spherical diffusion model was able to predict the 30-day data set, the first-order model failed completely. Fitting both models to subsets of the data corresponding to different experimental time scales revealed that the rate parameter as well as the Freundlich coefficient of the first-order model are strongly time-dependent--a property that is not shared by parameters of the spherical diffusion model. The apparent stability of the spherical diffusion model with regard to time dependency of its parameters indicates that sorptive uptake may be diffusion-controlled. This also explains the models greater predictive power across different time scales compared to the first-order model. Finally, we investigate the suitability of solute class specific log-linear relationships between the first-order rate parameter and the Freundlich coefficient presented by earlier researchers in the light of the time dependency observed for the parameters of the first-order model.     

LAS对土壤中多环芳烃吸附行为的影响

研究了阴离子表面活性剂十二烷基苯磺酸钠(LAS)对PAHs在土壤中吸附行为的影响.结果表明,LAS改变了PAHs在土水体系中的吸附/解吸平衡,吸附态LAS可提高土壤对PAHs的吸附,而溶解态LAS则增加了PAHs的表观溶解度,这2种作用的综合结果改变了PAHs在土水体系中的吸附系数.因此,文中用表观吸附系数来描述PAHs在土壤-水-LAS体系中的综合吸附行为.     

Solute transport properties of compacted Ca-bentonite used in FEBEX project

The present Spanish concept of a deep geological high level waste repository includes an engineered clay barrier around the canister. The clay presents a very high sorption capability for radionuclides and a very small hydraulic conductivity, so that the migration process of solutes is limited by sorption and diffusion processes. Therefore, diffusion and distribution coefficients in compacted bentonite (i.e. in "realistic" liquid to solid ratio conditions) are the main parameters that have to be obtained in order to characterise solute transport that could be produced after the canister breakdown. Through-Diffusion (TD) and In-Diffusion (ID) experiments with HTO, Sr, Cs and Se were carried out using compacted FEBEX bentonite, which is the reference material for the Spanish concept of radioactive waste disposal. Experiments were interpreted by means of available analytical solutions that allow the estimation of diffusion coefficients and, in some cases, distribution coefficients. Analytical solutions are simple to use, but rely on hypotheses that do not hold in all the experiments. These experiments were interpreted also using an automatic parameter estimation code that overcomes the limitations of analytical solutions. Numerical interpretation allows the simultaneous estimation of porosity, diffusion and distribution coefficients, accounts for the role of porous sinters and time-varying boundary concentrations, and can use different types of raw concentration data.     

Humic acid enhanced remediation of an emplaced diesel source in groundwater. 2. Numerical model development and application

A pilot scale experiment for humic acid-enhanced remediation of diesel fuel, described in Part 1 of this series, is numerically simulated in three dimensions. Groundwater flow, enhanced solubilization of the diesel source, and reactive transport of the dissolved contaminants and humic acid carrier are solved with a finite element Galerkin approach. The model (BIONAPL) is calibrated by comparing observed and simulated concentrations of seven diesel fuel components (BTEX and methyl-, dimethyl- and trimethylnaphthalene) over a 1500-day monitoring period. Data from supporting bench scale tests were used to estimate contaminant-carrier binding coefficients and to simulate two-site sorption of the carrier to the aquifer sand. The model accurately reproduced the humic acid-induced 10-fold increase in apparent solubility of trimethylnaphthalene. Solubility increases on the order of 2-5 were simulated for methylnaphthalene and dimethylnaphthalene, respectively. Under the experimental and simulated conditions, the residual 500-ml diesel source was almost completely dissolved and degraded within 5 years. Without humic acid flushing, the simulations show complete source dissolution would take about six times longer.     

Nonideal transport of reactive contaminants in heterogeneous porous media: 7. distributed-domain model incorporating immiscible-liquid dissolution and rate-limited sorption/desorption

The purpose of this work is to present a distributed-domain mathematical model incorporating the primary mass-transfer processes that mediate the transport of immiscible organic liquid constituents in water-saturated, locally heterogeneous porous media. Specifically, the impact of grain/pore-scale heterogeneity on immiscible-liquid dissolution and sorption/desorption is represented in the model by describing the system as comprising a continuous distribution of mass-transfer domains. With this conceptualization, the distributions of the initial dissolution rate coefficient and the sorption/desorption rate coefficient are represented as probability density functions. Several sets of numerical experiments are conducted to examine the effects of heterogeneous dissolution and sorption/desorption on contaminant transport and elution. Four scenarios with different combinations of uniform/heterogeneous rate-limited dissolution and uniform/heterogeneous rate-limited sorption/desorption are evaluated. The results show that both heterogeneous rate-limited sorption/desorption and heterogeneous rate-limited dissolution can significantly increase the time or pore volumes required to elute immiscible-liquid constituents from a contaminated porous medium. However, sorption/desorption has minimal influence on elution behavior until essentially all of the immiscible liquid has been removed. For typical immiscible-liquid constituents that have relatively low sorption, the asymptotic elution tailing produced by heterogeneous rate-limited sorption/desorption begins at effluent concentrations that are several orders of magnitude below the initial steady-state concentrations associated with dissolution of the immiscible liquid. Conversely, the enhanced elution tailing associated with heterogeneous rate-limited dissolution begins at concentrations that are approximately one-tenth of the initial steady-state concentrations. Hence, dissolution may generally control elution behavior of immiscible-liquid constituents in cases wherein grain/pore-scale heterogeneity significantly influences both dissolution and sorption/desorption.     

Intrinsic degradation of volatile fatty acids in laboratory-compacted clayey soil

Volatile fatty acids (VFAs) represent the major organic constituent of landfill leachate and provide the greatest potential for leachate induced organic contamination of groundwater (e.g. as represented by an increase in the concentration of dissolved organic carbon and chemical oxygen demand). Long-term diffusion tests were performed for laboratory-compacted clayey soil plugs exposed to continuous supply of synthetic leachate containing VFAs. Significant microbial activity developed upon exposure of the soil's indigenous microorganisms to these degradable contaminants. The growth of heterotrophic aerobic bacteria (HAB, which include facultative anaerobes), sulfate reducing bacteria (SRB) and methanogenic bacteria carrying out fermentation and mineralization of the VFAs became evident after 30-50 days of testing. The maximum microbial counts of (2-8) x 10(8) and (0.1-1) x 10(8) cfu/g for HAB and SRB were localized in the soil layer at the interface with the source of organic and inorganic nutrients. Regardless of this rapid growth in microbial population, the VFA consumption was small and measurable only after a lag of 140-180 days. It is considered that this lag of otherwise readily degradable organic compounds (such as VFAs) persisted due to a combination of the effects of a high initial concentration of these acids (2.4 g/l as dissolved organic carbon, DOC) applied to carbon starved soil microorganisms and the small pore size of the compacted clay. Once the significant amounts of gas were generated from fermentation, conditions developed for improved mass transport and exchange of the nutrients and bacteria and the outcome of the intrinsic degradation was more apparent. The breakdown of VFAs that followed after the lag was localized near the top of the soil and was characterized by a short half-life of 0.75-5 days for DOC (total VFAs as dissolved organic carbon).     

Transport of Escherichia coli bacteria through laboratory columns of glacial-outwash sediments: estimating model parameter values based on sediment characteristics

Bacterial transport through cores of intact, glacial-outwash aquifer sediment was investigated with the overall goal of better understanding bacterial transport and developing a predictive capability based on the sediment characteristics. Variability was great among the cores. Normalized maximum bacterial-effluent concentrations ranged from 5.4x10(-7) to 0.36 and effluent recovery ranged from 2.9x10(-4) to 59%. Bacterial breakthrough was generally rapid with a sharp peak occurring nearly twice as early as the bromide peak. Bacterial breakthrough exhibited a long tail of relatively constant concentration averaging three orders of magnitude less than the peak concentration for up to 32 pore volumes. The tails were consistent with non-equilibrium detachment, corroborated by the results of flow interruption experiments. Bacterial breakthrough was accurately simulated with a transport model incorporating advection, dispersion and first-order non-equilibrium attachment/detachment. Relationships among bacterial transport and sediment characteristics were explored with multiple regression analyses. These analyses indicated that for these cores and experimental conditions, easily-measurable sediment characteristics--median grain size, degree of sorting, organic-matter content and hydraulic conductivity--accounted for 66%, 61% and 89% of the core-to-core variability in the bacterial effective porosity, dispersivity and attachment-rate coefficient, respectively. In addition, the bacterial effective porosity, median grain size and organic-matter content accounted for 76% of the inter-core variability in the detachment-rate coefficient. The resulting regression equations allow prediction of bacterial transport based on sediment characteristics and are a possible alternative to using colloid-filtration theory. Colloid-filtration theory, used without the benefit of running bacterial transport experiments, did not as accurately replicate the observed variability in the attachment-rate coefficient.     

Competitive sorption of cis-DCE and TCE in silica gel as a model porous mineral solid

The competitive sorption of 1,2-cis-dichloroethene (cis-DCE) and trichloroethene (TCE) was investigated by means of column experiments using a model porous mineral solid represented by silica gel. The experimental isotherms were obtained by employing a chromatographic method. The competitive sorption isotherms were modelled with the extended Freundlich and extended Langmuir isotherms, using the parameters from single-solute experiments. The breakthrough curves were modelled with the advection-dispersion transport equation coupled with the lumped pore diffusion model. The best results were obtained when the extended Freundlich isotherm was employed. The competitive sorption was revealed with the presence of an overshoot in the breakthrough curve of cis-DCE and a decrease in the degree of sorption of cis-DCE (20%) and TCE (12%). A linear dependency of the overshoot with an increase in the concentration of cis-DCE at a fixed concentration of TCE was observed, between 16% and 20%, and at least at concentrations <6 mg L(-1) in the liquid phase. The displaced molecules of cis-DCE by TCE were accumulated through the column causing its overshoot; thus short columns may hinder its observation. Thermodynamic analysis shows an exothermic adsorption process of -34 to -41 kJ mol(-1), which is enhanced by sorption in micropores. The Gibbs free energy is positive for cis-DCE in the multi-component case, due to its displacement by TCE.     

Mercury sorption to sediments: dependence on grain size, dissolved organic carbon, and suspended bacteria

A combination of laboratory scale derived correlations and measurements of grain size distribution, DOC (dissolved organic carbon) concentration, and density of suspended bacteria promises to be useful in estimating Hg(II) sorption in heterogeneous streambeds and groundwater environments. This was found by shaking intact sediment and fractions thereof (<63-2000mum) with solutions of HgCl(2) (1.0-10.0ngml(-1)). The intact sediment was also shaken with the Hg(II) solutions separately in presence of DOC (6.5-90.2mugml(-1)) or brought in contact with suspensions of a strain of groundwater bacteria (2x10(4)-2x10(6)cellsml(-1)). Hg(II) sorption was rather weak and positively correlated with the grain size, and the sorption coefficient (K(d)) varied between about 300 and 600mlg(-1). By using the relative surface areas of the fractions, K(d) for the intact sediment was back calculated with 2% deviation. K(d) was negatively correlated with the concentration of DOC and positively correlated with the number of bacteria. A multiple regression showed that K(d) was significantly more influenced by the number of bacteria than by the grain size. The findings imply that common DOC concentrations in groundwater and streambeds, 5-20mugml(-1), will halve the K(d) obtained from standard sorption assays of Hg(II), and that K(d) will almost double when the cell numbers are doubled at densities that are common in aquifers. The findings suggest that simultaneous measurements of surface areas of sediment particles, DOC concentrations, and bacterial numbers are useful to predict spatial variation of Hg(II) sorption in aquifers and sandy sediments.