Effect of dissolved organic matter and bacteria on contaminant transport in riverbank filtration

A mathematical model for the transport of hydrophobic organic contaminants in an aquifer under simplistic riverbank filtration conditions is developed. The model considers a situation where contaminants are present together with dissolved organic matter (DOM) and bacteria. The aquifer is conceptualized as a four-phase system: two mobile colloidal phases, an aqueous phase, and a stationary solid phase. An equilibrium approach is used to describe the interactions of contaminants with DOM, bacteria, and solid matrix. The model is composed of bacterial transport equation and contaminant transport equation. Numerical simulations are performed to examine the contaminant transport behavior in the presence of DOM and bacteria. The simulation results illustrate that contaminant transport is enhanced markedly in the presence of DOM and bacteria, and the impact of DOM on contaminant mobility is greater than that of bacteria under examined conditions. Sensitivity analysis demonstrates that the model is sensitive to changes of three lumped parameters: K+1 (total affinity of stationary solid phase to contaminants), K+2 (total affinity of DOM to contaminants), and K+3 (total affinity of bacteria to contaminants). In a situation where contaminants exist simultaneously with DOM and bacteria, contaminant transport is mainly affected by a ratio of K+1/K+2/K+3, which can vary with changes of equilibrium distribution coefficient of contaminants and/or colloidal concentrations. In riverbank filtration, the influence of DOM and bacteria on the transport behavior of contaminants should be accounted to accurately predict the contaminant mobility.     

Transport of a non-volatile contaminant in unsaturated porous media in the presence of colloids

Stable colloidal particles can travel long distances in subsurface environments and carry particle-reactive contaminants with them to locations further than predicted by the conventional advective-dispersive transport equation. When such carriers exist in a saturated porous medium, the system can be idealized as consisting of three phases: an aqueous phase, a carrier phase, and a stationary solid matrix phase. However, when colloids are present in an unsaturated porous medium, the system representation should include one more phase, i.e. the air phase. In the work reported, a mathematical model was developed to describe the transport and fate of the colloidal particles and a non-volatile contaminant in unsaturated porous media. The model is based on mass balance equations in a four-phase porous medium. Colloid mass transfer mechanisms among aqueous, solid matrix, and air phases, and contaminant mass transfer between aqueous and colloid phases are represented by kinetic expressions. Governing equations are non-dimensionalized and solved to investigate colloid and contaminant transport in an unsaturated porous medium. A sensitivity analysis of the transport model was utilized to assess the effects of several parameters on model behavior. The colloid transport model matches successfully with experimental data of Wan and Wilson. The presence of air-water interface retards the colloid transport significantly counterbalancing the facilitating effect of colloids. However, the retardation of contaminant transport by colloids is highly dependent on the properties of the contaminant and the colloidal surface.     

Transport of reactive colloids and contaminants in groundwater: effect of nonlinear kinetic interactions

Transport of reactive colloids in groundwater may enhance the transport of contaminants in groundwater. Often, the interpretation of results of transport experiments is not a simple task as both reactions of colloids with the solid matrix and reactions of contaminants with the solid matrix and mobile and immobile colloids may be time dependent and nonlinear. Further colloid transport properties may differ from solute transport properties. In this paper, a one-dimensional model for coupled and contaminant in a porous medium (COLTRAP) is presented together with simulation results. Calculated breakthrough curves (BTC's) during contamination and decontamination show systematically the effect of nonlinear and kinetic interactions on contaminant transport in the presence of reactive colloids, and the effect of colloid transport properties that differ from solute transport properties. It is shown that in case of linear kinetic reactions, the rate of exchange of mobile and immobile colloids have a large impact on the shape of BTC's even if the solid matrix is saturated with respect to colloids. BTC's during the contamination and decontamination phase have identical shapes in this case. Moreover, the slow reactions of contaminants and colloids may lead to unretarded breakthrough of contaminants. Independent of reaction rates, nonlinear reactions lead to BTC's that are steeper during contamination than in the linear case. A characteristic aspect of nonlinear sorption is that shapes of BTC's differ during the contamination and decontamination phase. It has been observed that shapes of some of the simulated adsorption and desorption curves are similar as shapes found in experiments reported in literature. This stresses the importance of incorporating both kinetics and nonlinearity in models for coupled colloid and contaminant transport and the capability of COLTRAP to interpret experimental results. Finally, to figure out whether nonlinear processes play a role, it is very important to consider both contamination and decontamination in transport experiments.     

Effects of degree of water saturation on dispersivity and immobile water in sandy soil columns

Three natural nonaggregated soil samples, with similar grain-size distributions, have been used to determine the dispersive behavior of porous media under steady, saturated and unsaturated flow conditions. Tritium was used as a tracer and was found to have no sorption on the solid matrix. Generated breakthrough curves (BTCs) for the unsaturated experiments were symmetrical with no evidence of tailing. The unsaturated experiments for two of the soils were adequately described by considering all the water in the pore volume as mobile. However, about 10% of the pore water, independent of the degree of saturation, was found to be immobile in the case of the third soil during unsaturated flow. For this soil, there was no mass transfer between the two water regions, indicating that the immobile water is essentially isolated from the flowing water fraction. For all three soils, dispersivity under unsaturated conditions was found to be higher, independent of the degree of water saturation, than the value determined for the saturated experiments. This is inconsistent with what would be expected from the simple bundle-of-capillary-tubes model and does not agree well with a more sophisticated conceptualization of the porous medium. The data, however, clearly indicate a wider range in pore-water velocities when these soils are desaturated.     

Use of tracer tests to investigate changes in flow and transport properties due to bioclogging of porous media

Tracer tests were conducted in three laboratory columns to study changes in the hydraulic properties of a porous medium due to bioclogging. About 30 breakthrough curves (BTCs) for each column were obtained. The BTCs were analyzed using analytical equilibrium and dual-porosity models, and estimates of the hydrodynamic dispersion and mass transfer coefficients were obtained by curve fitting. The change in transport properties developed in three stages: an initial phase (I) with no significant changes in transport properties, phase II with growth of biomass near the inlet of the columns causing changes in dispersivity, and phase III with added growth of micro-colonies deeper in the columns causing mass transfer of solutes from the water phase to the biophase. Tracer transport changed from being uniform to more non-uniform with increase in mass transfer of the tracer between the mobile phase and the immobile biomass. An increase in the bulk dispersivity value of up to one order of magnitude was observed. Numerical simulations suggest that local dispersivity values may be as much as 40 times higher in the more severe clogged areas inside the column. The bulk hydraulic conductivities of the columns decreased by up to three orders of magnitude. The hydraulic conductivity and dispersivity parameters were almost recovered after disinfection of the columns. Different models relating the changes of the hydraulic conductivity to the changes in the mobile porosity due to bioclogging were reviewed, and the micro-colony relation of Thullner et al. [Thullner, M., Zeyer, J., Kinzelbach, W., 2002. Influence of microbial growth on hydraulic properties of pore networks, Transport in Porous Media, 49, 99-122.] was found to best describe the relation between the bulk hydraulic parameters.     

Biogeochemical influence on transport of chromium in manganese sediments: experimental and modeling approaches

Hexavalent chromium (Cr(VI)) was reduced to immobile and nontoxic Cr(III) by a dissimilatory metal reducing bacteria, Shewanella alga Simidu (BrY-MT) ATCC 55627. A series of kinetic batch and dynamic column experiments were conducted to provide an understanding of Cr(VI) reduction by the facultative anaerobe BrY-MT. Reduction of Cr(VI) was rapid (within 1 h) in columns packed with quartz sand and bacteria, whereas Cr(VI) reduction by BrY-MT was delayed (57 h) in the presence of beta-MnO2-coated sand. A mathematical model was developed and evaluated against data obtained from column experiments. The model takes into account (1) advective-dispersive transport of Cr(III), Cr(VI), lactate, and protein (mobile and immobile bacteria); (2) first-order kinetic adsorption of Cr(III) and lactate; (3) conversion of solid phase beta-MnO2 to solid phase MnOOH due to oxidation of Cr(III); (4) dual-Monod kinetics, where Cr(VI) is the electron acceptor and lactate is the electron donor. The breakthrough data for Cr(III), Cr(VI), lactate, and protein (mobile and immobile bacteria) were fitted simultaneously. The breakthrough data are well described by the mathematical model that considers the above processes. This result demonstrates the ability of the coupled hydrobiogeochemical model to simulate chromium transport in complex reactive systems.     

Prediction of mass-transfer coefficient for solute transport in porous media

Several previously reported laboratory studies related to transport of solutes through packed columns were utilized to develop predictive relationships for mass-transfer rate coefficient. The data were classified into two groups: those obtained under rate-limited mass transfer between mobile and immobile water regions (physical nonequilibrium conditions), and those derived from rate-limited mass transfer between instantaneous and slow sorption sites (sorption nonequilibrium conditions). The mass-transfer coefficient in all these studies was obtained by fitting breakthrough data to a transport model employing a first-order rate limitations with a "constant" mass-transfer coefficient, independent of flow conditions. This study demonstrated that the mass-transfer coefficient in these models is dependent on system parameters including pore-water velocity, length-scale, retardation coefficient, and particle or aggregate size. Predictive relationships were developed, through regression analysis, relating mass-transfer coefficient to residence time. The developed relationships adequately estimated previously reported field mass-transfer values. Successful simulations of field desorption data reported by Bahr [J. Contam. Hydrol. 4 (1989) 205] further demonstrate the potential applicability of the developed relationships.     

An independent prediction of the effect of dissolved organic matter on the transport of polycyclic aromatic hydrocarbons

The transport of polycyclic aromatic hydrocarbons (PAH) in porous media in the presence of dissolved organic matter (DOM) was predicted with a transport bicontinuum model using independently obtained relationships to derive transport parameters for describing the effect of PAH binding to the DOM. The sorption constants of PAHs to soil and their binding constants to DOM were derived from basic correlations with K(ow) (indicator of hydrophobicity). The kinetic (rate) constants were derived from previously published correlations with K(p) (sorption constant). The independently obtained sorption and rate constants were corrected for binding to DOM and were used to predict the breakthrough curves (BTC) of contaminants in the presence and the absence of DOM. Column results confirmed the independently predicted BTC of PAHs in the presence of DOM that did not sorb to the solid phase, as well as the effect of DOM on the rate of the sorption and desorption processes. These findings confirm the ability to quantitatively describe how DOM facilitates transport of contaminants in the subsurface using independently derived parameters.     

Single- and dual-porosity modelling of flow in reclaimed mine soil cores with embedded lignitic fragments

Lignitic mine soils represent a typical two-scale dual-porosity medium consisting of a technogenic mixture of overburden sediments that include lignitic components as dust and as porous fragments embedded within a mostly coarse-textured matrix. Flow and transport processes in such soils are not sufficiently understood to predict the course of soil reclamation or of mine drainage. The objective of this contribution is to identify the most appropriate conceptual model for describing small-scale heterogeneity effects on flow on the basis of the physical structure of the system. Multistep flow experiments on soil cores are analyzed using either mobile–immobile or mobile–mobile type 1D dual-porosity models, and a 3D numerical model that considers a local-scale distribution of fragments. Simulations are compared with time series' of upward infiltration and matric potential heads measured at two depths using miniature tensiometers. The 3D and the 1D dual-permeability models yielded comparable results as long as pressure heads are in local equilibrium; however, could describe either the upward infiltration or the matric potential curves but not both at the same time. The mobile–immobile type dual-porosity model failed to describe the data. A simultaneous match with pressure heads and upward infiltration data could only be obtained with the 1D dual-permeability model (i.e., mobile–mobile) by assuming an additional restriction of the inter-domain water transfer. These results indicate that for unsaturated flow conditions at higher matric potential heads (i.e., here >− 40 hPa), water in a restricted part of the fragment domain must be more mobile as compared to water in the sandy matrix domain. Closer inspections of the pore system and first neutron radiographic imaging support the hypothesis that a more continuous pore region exists at these pressure heads in the vicinity of the lignitic fragments possibly formed by fragment contacts and a lignitic dust interface-region between the two domains. The results suggest that the small-scale structure is too complex as to be represented by weighted contributions of individual components alone.     

Migration of colloids in discretely fractured porous media: effect of colloidal matrix diffusion

Numerical simulations of colloid transport in discretely fractured porous media were performed to investigate the importance of matrix diffusion of colloids as well as the filtration and remobilization of colloidal particles in both the fractures and porous matrix. To achieve this objective a finite element numerical code entitled COLDIFF was developed. The processes that COLDIFF takes into account include advective-dispersive transport of colloids, filtration and remobilization of colloidal particles in both fractures and porous matrix, and diffusive interactions of colloids between the fractures and porous matrix. Three sets of simulations were conducted to examine the importance of parameters and processes controlling colloid migration. First, a sensitivity analysis was performed using a porous block containing a single fracture to determine the relative importance of various phenomenological coefficients on colloid transport. The primary result of the analysis showed that the porosity of the matrix and the process of colloid filtration in fractures play important roles in controlling colloid migration. Second, simulations were performed to replicate and examine the results of a laboratory column study using a fractured shale saprolite. Results of this analysis showed that the filtration of colloidal particles in the porous matrix can greatly affect the tailing of colloid concentrations after the colloid source was removed. Finally, field-scale simulations were performed to examine the effect of matrix porosity, fracture filtration and fracture remobilization on long-term colloid concentration and migration distance. The field scale simulations indicated that matrix diffusion and fracture filtration can significantly reduce colloid migration distance. Results of all three analyses indicated that in environments where porosity is relatively high and colloidal particles are small enough to diffuse out of fractures, the characteristics of the porous matrix that affect colloid transport become more important than those of the fracture network. Because the properties of the fracture network tend to have greater uncertainty due to difficulties in their measurement relative to those of the porous matrix, prediction uncertainties associated with colloid transport in discretely fractured porous media may be reduced.     

Estimating first-order reaction rate coefficient for transport with nonequilibrium linear mass transfer in heterogeneous media

A travel-time based approach is developed for estimating first-order reaction rate coefficients for transport with nonequilibrium linear mass transfer in heterogeneous media. Tracer transport in the mobile domain is characterized by a travel-time distribution, and mass transfer rates are described by a convolution product of concentrations in the mobile domain and a memory function rather than predefining the mass transfer model. A constant first-order reaction is assumed to occur only in the mobile domain. Analytical solutions in Laplace domain can be derived for both conservative and reactive breakthrough curves (BTCs). Temporal-moment analyses are presented by using the first and second moments of conservative and reactive BTCs and the mass consumption of the reactant for an inverse Gaussian travel-time distribution. In terms of moment matching, there is no need for one to specify the mass transfer model. With the same capacity ratio and the mean retention time, all mass transfer models will lead to the same moment-derived reaction rate coefficients. In addition, the consideration of mass transfer generally yields larger estimations of the reaction rate coefficient than models ignoring mass transfer. Furthermore, the capacity ratio and the mean retention time have opposite influences on the estimation of the reaction rate coefficient: the first-order reaction rate coefficient is positively linearly proportional to the capacity ratio, but negatively linearly proportional to the mean retention time.     

Modelling the migration of contaminants through variably saturated dual-porosity, dual-permeability chalk

In the Hesbaye region in Belgium, tracer tests performed in variably saturated fissured chalk rocks presented very contrasting results in terms of transit times, according to artificially controlled water recharge conditions prevailing during the experiments. Under intense recharge conditions, tracers migrated across the partially or fully saturated fissure network, at high velocity in accordance with the high hydraulic conductivity and low effective porosity (fracture porosity). At the same time, a portion of the tracer was temporarily retarded in the almost immobile water located in the matrix. Under natural infiltration conditions, the fissure network remained inactive. Tracers migrated downward through the matrix, at low velocity in relation with the low hydraulic conductivity and the large porosity of the matrix. Based on these observations, Brouyère et al. (2004a) [Brouyère, S., Dassargues, A., Hallet, V., 2004a. Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation, J. Contam. Hydrol., 72 (1-4), 135-164, doi: 10.1016/j.conhyd.2003.10.009] proposed a conceptual model in order to explain the migration of solutes in variably saturated, dual-porosity, dual-permeability chalk. Here, mathematical and numerical modelling of tracer and contaminant migration in variably saturated fissured chalk is presented, considering the aforementioned conceptual model. A new mathematical formulation is proposed to represent the unsaturated properties of the fissured chalk in a more dynamic and appropriate way. At the same time, the rock water content is partitioned between mobile and immobile water phases, as a function of the water saturation of the chalk rock. The groundwater flow and contaminant transport in the variably saturated chalk is solved using the control volume finite element method. Modelling the field tracer experiments performed in the variably saturated chalk shows the adequacy and usefulness of the new conceptual, mathematical and numerical model.     

Determination of the Sodium Carbonate-Sulfur Dioxide Reaction Rate Coefficient at 450°F

Abstract

Gas-phase dispersion in granular biofilter materials with a wide range of particle sizes was investigated using atmospheric air and nitrogen as tracer gases. Two types of materials were used: (1) light extended clay aggregates (LECA), consisting of highly porous particles, and (2) gravel, consisting of solid particles. LECA is a commercial material that is used for insulation, as a soil conditioner, and as a carrier material in biofilters for air cleaning. These two materials were selected to have approximately the same particle shape. Column gas transport experiments were conducted for both materials using different mean particle diameters, different particle size ranges, and different gas flow velocities. Measured breakthrough curves were modeled using the advection-dispersion equation modified for mass transfer between mobile and immobile gas phases. The results showed that gas dispersivity increased with increasing mean particle diameter for LECA but was independent of mean particle diameter for gravel. Gas dispersivity also increased with increasing particle size range for both media. Dispersivities in LECA were generally higher than for gravel. The mobile gas content in both materials increased with increasing gas flow velocity but it did not show any strong dependency on mean particle diameter or particle size range. The relative fraction of mobile gas compared with total porosity was highest for gravel and lowest for LECA likely because of its high internal porosity.     

Modeling colloid-facilitated transport of multi-species contaminants in unsaturated porous media

Colloid-facilitated transport has been recognized as a potentially important and overlooked contaminant transport process. In particular, it has been observed that conventional two phase sorption models are often unable to explain transport of highly sorbing compounds in the subsurface appropriately in the presence of colloids. In this study a one-dimensional model for colloid-facilitated transport of chemicals in unsaturated porous media is developed. The model has parts for simulating coupled flow, and colloid transport and dissolved and colloidal contaminant transport. Richards' equation is solved to model unsaturated flow, and the effect of colloid entrapment and release on porosity and hydraulic conductivity of the porous media is incorporated into the model. Both random sequential adsorption and Langmuir approaches have been implemented in the model in order to incorporate the effect of surface jamming. The concept of entrapment of colloids into the air-water interface is used for taking into account the effect of retardation caused due to existence of the air phase. A non-equilibrium sorption approach with options of linear and Langmuir sorption assumptions are implemented that can represent the competition and site saturation effects on sorption of multiple compounds both to the solid matrix and to the colloidal particles. Several demonstration calculations are performed and the conditions in which the non-equilibrium model can be approximated by an equilibrium model are also studied.     

Travel time and trajectory moments of conservative solutes in two-dimensional convergent flows

We address advective transport of a solute traveling toward a single pumping well in a two-dimensional randomly heterogeneous aquifer. The two random variables of interest are the trajectory followed by an individual particle from the injection point to the well location and the particle travel time under steady-state conditions. Our main objective is to derive the predictors of trajectory and travel time and the associated uncertainty, in terms of their first two statistical moments (mean and variance). We consider a solute that undergoes mass transfer between a mobile and an immobile zone. Based on Lawrence et al. [Lawrence, A.E., Sánchez-Vila, X., Rubin, Y., 2002. Conditional moments of the breakthrough curves of kinetically sorbing solute in heterogeneous porous media using multirate mass transfer models for sorption and desorption. Water Resour. Res. 38 (11), 1248, doi:10.1029/2001WR001006.], travel time moments can be written in terms of those of a conservative solute times a deterministic quantity. Moreover, the moments of solute particles trajectory do not depend on mass transfer processes. The resulting mean and variance of travel time and trajectory for a conservative species can be written as functions of the first, second moments and cross-moments of trajectory and velocity components. The equations are developed from a consistent second order expansion in sigmaY (standard deviation of the natural logarithm of hydraulic conductivity). Our solution can be completely integrated with the moment equations of groundwater flow of Guadagnini and Neuman [Guadagnini, A., Neuman, S.P., 1999a. Nonlocal and localized analyses of conditional mean steady state flow in bounded, randomly non uniform domains 1. Theory and computational approach. Water Resour. Res. 35(10), 2999-3018.,Guadagnini, A., Neuman, S.P., 1999b. Nonlocal and localized analyses of conditional mean steady state flow in bounded, randomly non uniform domains 2. Computational examples. Water Resour. Res. 35(10), 3019-3039.], it is free of distributional assumptions regarding the log conductivity field, and formally includes conditioning. We present analytical expressions for the unconditional case by making use of the results of Riva et al. [Riva, M., Guadagnini, A., Neuman, S.P., Franzetti, S., 2001. Radial flow in a bounded randomly heterogeneous aquifer. Transport in Porous Media 45, 139-193.]. The quality of the solution is supported by numerical Monte Carlo simulations. Potential uses of this work include the determination of aquifer reclamation time by means of a single pumping well, and the demarcation of the region potentially affected by the presence of a contaminant in the proximity of a well, whenever the aquifer is very thin and Dupuit-Forchheimer assumption holds.     

Effects of water content on reactive transport of 85Sr in Chernobyl sand columns

It is known that under unsaturated conditions, the transport of solutes can deviate from ideal advective-dispersive behaviour even for macroscopically homogeneous porous materials. Causes may include physical non-equilibrium, sorption kinetics, non-linear sorption, and the irregular distribution of sorption sites. We have performed laboratory experiments designed to identify the processes responsible for the non-ideality of radioactive Sr transport observed under unsaturated flow conditions in an Aeolian sandy deposit from the Chernobyl exclusion zone. Miscible displacement experiments were carried out at various water contents and corresponding flow rates in a laboratory model system. Results of our experiments have shown that breakthrough curves of a conservative tracer exhibit a higher degree of asymmetry when the water content decreases than at saturated water content and same Darcy velocity. It is possible that velocity variations caused by heterogeneities at the macroscopic scale are responsible for this situation. Another explanation is that molecular diffusion drives the solute mass transfer between mobile and immobile water regions, but the surface of contact between these water regions is small. At very low concentrations, representative of a radioactive Sr contamination of the pore water, sorption and physical disequilibrium dominate the radioactive Sr transport under unsaturated flow conditions. A sorption reaction is described by a cation exchange mechanism calibrated under fully saturated conditions. The sorption capacity, as well as the exchange coefficients are not affected by desaturation. The number of accessible exchange sites was calculated on the basis that the solid remained in contact with water and that the fraction of solid phase in contact with mobile water is numerically equal to the proportion of mobile water to total water content. That means that for this type of sandy soil, the nature of mineral phases is the same in advective and non-advective domains. So sorption reaction parameters can be estimated from more easily conducted saturated experiments, but hydrodynamic behaviour must be characterized by conservative tracer experiments under unsaturated flow conditions.     

Implications of non-equilibrium transport in heterogeneous reactive barrier systems: evidence from laboratory denitrification experiments

Organic substrates in reactive barrier systems are often heterogeneous material mixtures with relatively large contrasts in hydraulic conductivity and porosity over short distances. These short-range variations in material properties imply that preferential flow paths and diffusion between regions of higher and lower hydraulic conductivity may be important for treatment efficiency. This paper presents the results of a laboratory column experiment where denitrification is investigated using a heterogeneous reactive substrate (sawdust mixed with sewage sludge). Displacement experiments with a non-reactive solute at three different flow rates are used to estimate transport parameters using a dual porosity non-equilibrium model. Parameter estimation from breakthrough curves produced relatively consistent values for the fraction of the porosity consisting of mobile water (β) and the mass transfer coefficient (α), with average values of 0.27 and 0.42 d(-1), respectively. The column system removes >95% of the influent nitrate at low and medium flow, but only 50-75% of the influent nitrate at high flow, suggesting that denitrification kinetics and diffusive mass transfer rates are limiting the degree of treatment at lower hydraulic residence times. Reactive barrier systems containing dual porosity media must therefore consider mass transfer times in their design; this is often most easily accommodated by adjusting flowpath length.     

Transport of anthracene and benz(a)anthracene through iron-quartz and three aquifer materials in laboratory columns

In groundwater systems, dissolved natural organic matter (NOM) can influence the mobility of organic contaminants by altering the contaminant behavior in water and solid phases. The transport of anthracene and benz(a)anthracene (B(a)A) was studied in the presence and absence of NOM and/or soil organic matter (SOM) in column experiments. The results show that sorption are related to the properties of polycyclic aromatic hydrocarbons (PAHs), NOM and SOM. In the Fe-quartz media, the amount of NOM (20 mg/l) in solution had a little effect on increasing the apparent solubility of anthracene and countering increased anthracene sorption. In the natural (Bemidji) soil, Suwannee river fulvic acid (SRFA, 20 mg/l) and Suwannee river humic acid (SRHA) in water did not compete with SOM for anthracene, indicating that SOM has higher partition efficiency for anthracene. It was also observed that slow diffusion through an organic phase apparently caused most of the observed tailing in column breakthrough curves (BTCs). Even though the fOC of washed Bemidji sediment was very low, the transport of B(a)A was retarded significantly, however, and the transport of B(a)A was shown to be facilitated by dissolved NOM.     

Longevity of granular iron in groundwater treatment processes: changes in solute transport properties over time

Although progress has been made toward understanding the surface chemistry of granular iron and the mechanisms through which it attenuates groundwater contaminants, potential long-term changes in the solute transport properties of granular iron media have until now received relatively little attention. As part of column investigations of alterations in the reactivity of granular iron, studies using tritiated water (3H(2)O) as a conservative and non-partitioning tracer were periodically conducted to independently isolate transport-related effects on performance from those more directly related to surface reactivity. Hydraulic residence time distributions (HRTDs) within each of six 39-cm columns exposed to bicarbonate solutions were obtained over the course of 1100 days of operation. First moment analyses of the data revealed generally modest increases in mean pore water velocity (v) over time, indicative of decreasing water-filled porosity. Gravimetric measurements provided independent estimates of water-filled porosity that were initially consistent with those obtained from 3H(2)O tracer tests, although at later times, porosities derived from gravimetric measurements deviated from the tracer test results owing to mineral precipitation. The combination of gravimetric measurements and 3H(2)O tracer studies furnished estimates of precipitated mineral mass; depending on the assumed identity of the predominant mineral phase(s), the porosity decrease associated with solute precipitation amounted to 6-24% of the initial porosity. The accumulation of mineral and gas phases led to the formation of regions of immobile water and increased spreading of the tracer pulse. Application of a dual-region transport model to the 3H(2)O breakthrough curves revealed that the immobile water-filled region increased from initially negligible values to amounts ranging between 3% and 14% of the total porosity in later periods of operation. For the aged columns, mobile-immobile mass transfer coefficients (k(mt)) were generally in the range of 0.1-1.0 day(-1) and reflected a slow exchange of 3H(2)O between the two regions. Additional model calculations incorporating sorption and reaction suggest that although changes in HRTD can have an appreciable effect on trichloroethylene (TCE) transformation, the effect is likely to be minor relative to that stemming from passivation of the granular iron surface.