Effects of lipids on the sorption of hydrophobic organic compounds on geosorbents: a case study using phenanthrene

The impact of the lipid fraction of natural geosorbents on the sorption of a polycyclic aromatic hydrocarbon was assessed using several experiments. In the first set of experiments phenanthrene was sorbed on a coastal sediment as well as on its humin and humic acid fractions before and after lipid extraction. Before lipid extraction, sorption shows dominantly partitioning characteristics. However, the extraction of lipids from sediment and humin drastically increases, by up to one order of magnitude, their sorption affinity for phenanthrene at low sorbate concentrations, resulting in increased isotherm nonlinearity. This effect is less pronounced for humic acids. One mechanism proposed for the increasing sorption is that lipids, despite their very low relative abundance in the sediments, can compete with phenanthrene for specific high affinity sorption sites (e.g., matrix pores and adsorption sites). This competition is not surprising considering the similar hydrophobic nature of lipids and phenanthrene. Lipids, or any non-polar molecules, could also act like plasticizers by swelling rigid domains and disrupting high affinity sites. In both cases, the removal of lipids (and extraction solvents) makes those sites available for phenanthrene. These provide alternative explanations to the previously proposed “solvent conditioning effect” believed to occur when geosorbents are treated with non-polar solvents modifying the matrix structure, an effect yet to be proven at molecular scale. To further investigate the impact of lipids on sorption, other independent experiments were performed. In a second experiment, re-addition of lipids to the extracted sediment restored the sorption isotherm linearity observed in the native material supporting the absence of irreversible extraction artifacts. However, high addition of lipids (i.e., after saturation of high affinity sites) seems to also enlarge the low affinity partitioning domain. These results are consistent with dual-mode, hole-filling, sorption models involving diffusion. In the final set of experiments, solid-state ¹⁹F-NMR using F-labeled lipids sorbed onto the sediments confirmed that lipids may be in different domains (mobile or rigid) that interact or not with phenanthrene. The possible effects of lipid removal on sorption have been overlooked and should be considered when geosorbents are pretreated.     

Competition between phenanthrene, chrysene, and 2,5-dichlorobiphenyl for high-energy adsorption sites in a sediment

We determined the maximum amounts of added phenanthrene, chrysene, and 2,5-dichlorobiphenyl sorbed onto high-energy adsorption sites in a sediment on bi-solute experiments. The bi-solute pairs were phenanthrene/chrysene and phenanthrene/2,5-dichlorobiphenyl. On the bi-solute sorption experiments, one solute was introduced and equilibrated with sediment prior to addition of the second solute. The values for the maximum amounts adsorbed onto high-energy sites revealed that, after equilibration of the first solute, still some high-energy sites could be occupied by the second solute. Phenanthrene, chrysene, and 2,5-dichlorobiphenyl seem to share about 30% of the accessible high-energy adsorption sites in the sediment employed.     

Assessment of adsorption behavior of dibutyltin (DBT) to clay-rich sediments in comparison to the highly toxic tributyltin (TBT)

The sorption behavior of dibutyltin (DBT) to four types of natural clay-rich sediments as a function of pH and salinity was studied. The strongest affinity of DBT was found to the montmorillonite-rich sediment, which is characterized by the highest specific surface area and cation exchange capacity of the four used sediments. Kd values range between 12 and 40 (l/kg) on simulated marine conditions (pH 8, salinity 32%). A maximum of DBT adsorption was found at a salinity of 0% and pH 6. Desorption occurred over the entire studied pH range (4-8) when contaminated sediments interact with butyltin-free water. The maximum of desorption coincided with the minimum of adsorption, and vice versa. The results of DBT adsorption are compared with tributyltin (TBT), and the mechanism of the adsorption process is discussed.     

The influences of pH and ionic strength on the sorption of tylosin on goethite

As one of the widely used antibiotics in the world, the environmental risks of tylosin (TYL) received more and more attention. In order to assess its environmental fate and ecological effects accurately, it is necessary to understand the sorption properties of TYL on the soils/sediments. The sorption of TYL on goethite at different pH and ionic strength conditions were measured through a series of batch experiments and the sorption data of TYL were fitted by Freundlich and dual-mode sorption models. It was obvious that sorption was strongly dependent on pH and ionic strength. Sorption capacity of TYL increased as the pH increased and ionic strength decreased. The pH and ionic strength-dependent trends might be related with complexation between cationic/neutral TYL species and goethite. The sorption affinity of TYL on goethite decreased as ionic strength increased, which only occurred at higher TYL concentrations, suggested that inner complex might have dominated process at low concentrations and outer complex might occur at higher concentrations of TYL. Spectroscopic evidence indicated that tricarbonylamide and hydroxyl functional groups of TYL might be accounted for the sorption on mineral surfaces. The experimental data of TYL sorption could be fitted by surface complexation model (FITEQL), indicating that ≡FeOH with TYL interaction could be reasonably represented as a complex formation of a monoacid with discrete sites on goethite. The sorption mechanism of TYL might be related with surface complexation, electrostatic repulsion, and H-bounding on goethite. It should be noticed that the heterogeneous of sorption affinity of TYL on goethite at various environment to assess its environment risk.     

Equilibrium partitioning theory to predict the sediment toxicity of the anionic surfactant C(12)-2-LAS to Corophium volutator

The study of the effect of the sorption of linear alkylbenzene sulfonates (LAS) on the bioavailability to marine benthic organisms is essential to refine the environmental risk assessment of these compounds. According to the equilibrium partitioning theory (EqP), the effect concentration in water-only exposure will be similar to the effect concentration in the sediment pore water. In this work, sorption and desorption experiments with two marine sediments were carried out using the compound C₁₂-2-LAS. The effect of the sediment sorption on the toxicity of benthic organisms was studied in water-only and in sediment bioassays with the marine mud shrimp Corophium volutator. In addition, three common spiking methods were tested for its application in the toxicity tests, as well as the stability of the surfactant during the water-only and sediment-water test duration. LC50 values obtained from water-only exposure showed a good correspondence with the pore water concentrations calculated from the sorption and desorption isotherms in the spiked sediments.     

Competitive adsorption and desorption of arsenate,vanadate, and molybdate onto the low-cost adsorbent materials alum water treatment sludge and bauxite

When low-cost adsorbents are being used to remove contaminant ions (e.g. arsenate, vanadate, and molybdate) from wastewater, competitive adsorption/desorption are central processes determining their removal efficiency. Competitive adsorption of As, V, and Mo was investigated using equimolar oxyanion concentrations in single, binary, and tertiary combinations in adsorption isotherm and pH envelope studies while desorption of previously adsorbed oxyanions was examined in solutions containing single and binary oxyanion combinations. The low-cost adsorbent materials used were alum water treatment sludge (amorphous hydroxy-Al) and bauxite ore (crystalline Al oxides). Adsorption isotherm and pH envelope studies showed that Mo had only a small effect in decreasing adsorption of As and V but V and As had substantial and similar effects in reducing adsorption of the other. As had a greater effect than V in reducing adsorption of Mo and it was concluded that the affinity of oxyanions for the surfaces of water treatment sludge and bauxite followed the order As > V >> Mo. In 0.3 M NaCl electrolyte, desorption of previously adsorbed oxyanions amounted to 0.3–3.4% for V and As, and 11–20% for Mo. As had approximately four times greater effect than Mo in increasing desorption of V while V had about three times the effect of Mo in increasing desorption of As. Thus, the order of oxyanions in inducing desorption of the other oxyanions (i.e. As on V and As) was the same as that for adsorption selectivity: As > V >> Mo. Water treatment sludge was a more effective adsorbent than bauxite because it had a greater adsorption capacity for all three anions and, in addition, they were held more strongly so desorption in the background electrolyte was proportionately less. It was concluded that at similar molar concentrations, arsenate would tend to reduce adsorption of vanadate as well as displace vanadate already held on adsorbent surfaces while both anions will compete effectively with molybdate. The limiting factor for simultaneous removal of As, V, and Mo from multielement solutions by adsorption will therefore be the removal of Mo.     

Effects of natural organic matter on the microporous sorption sites of black carbon in a Yangtze River sediment

Black carbon (BC), characterized by high microporosity and high specific surface area (SSA), has been demonstrated to have substantial contributions to the sorption of hydrophobic organic chemicals in soils and sediments. Other naturally occurring organic matters provide soft and penetrable sorption domains while may cling to BC and affect its original surface properties. In this work, we studied the sorption sites of a Yangtze River sediment sample with organic carbon (OC) content of 3.3 % and the preheated sediment (combusted at 375 °C) with reduced OC content (defined as BC) of 0.4 % by gas and pyrene sorption. The SSA and microporosity of the pristine and preheated sediments were characterized by N₂ and CO₂ adsorption. The results suggest that the adsorption of N₂ was hindered by amorphous organic carbon (AOC) in the pristine sediment but CO₂ was not. Instead, the uptake of CO₂ was higher in the presence of AOC, likely due to the partition of CO₂ molecules into the organic matter. The pyrene adsorptions to BC in pristine and preheated sediments show a similar adsorption capacity at high concentration, suggesting that AOC of ca. 2.9 % in the pristine sediment does not reduce the accessibility to the sorption sites on BC for pyrene.     

Cosorption of organic chemicals with different properties: their shared and different sorption sites

Complementary sorption of different chemicals was expected and investigating the relationship between the sorption inhibition of primary sorbate (ΔQ(pri)) and sorption of secondary sorbate (Q(sec)) could provide a new angle to understand coadsorption of different chemicals. This study used bisphenol A (BPA) as the primary adsorbate, sulfamethoxazole (SMX) as the competitor, and carbon nanotubes as model adsorbents to study their complementary and competitive adsorption. At low BPA concentrations, the sorption of SMX (Q(sec)) exceeded BPA sorption inhibition (ΔQ(pri)), indicating that these two chemicals complementarily adsorbed on their respectively preferred sorption sites. At high BPA concentrations, higher ΔQ(pri) was observed in comparison to Q(sec), which may be resulted from different packing efficiencies of the adsorbed SMX and BPA. This study emphasized that both competitive and complementary sorption should be discussed in binary sorption system.     

Studies on the sorption behaviors of nitrobenzene on marine sediments

The sorption behaviors of nitrobenzene on marine sediments were systematically investigated in this study. The nitrobenzene sorption on both HCl-treated and untreated sediments accorded well with the linear sorption isotherm. It occurred primarily through partition function of organic carbon of sediments. In comparison, the sorption behavior of nitrobenzene on H2O2-treated sediments was nonlinear and conformed to Langmuir isotherm. Sorption of nitrobenzene on H2O2-treated sediment was mainly through surface function of sediment minerals such as clays. With the increase of ionic strength (salinity), solubility of nitrobenzene in solution would decrease. At the same time, the release of dissolvable part of organic carbon into water solution would also decrease. As a result, partition coefficient and saturate adsorption amount of nitrobenzene on marine sediments increased with increasing salinity of seawater. Contrary to the influence of salinity, partition coefficient and saturate adsorption amount of nitrobenzene decreased with increasing temperature.     

The equilibria of bisolute sorption on soil

The goal of this study was to investigate the effects of both concentration levels and loading sequence or contamination history of each pollutant on the equilibrium sorption of mixed organic pollutants on soils. We measured binary sorption equilibria for a soil using ten concentration levels for both phenanthrene and naphthalene. Both solutes were either simultaneously loaded or sequentially loaded (i.e., the second sorbate was loaded after the sorption of the first sorbate had attained equilibrium) on soil. The results showed different competitive sorption equilibria between phenanthrene and naphthalene. In the presence of phenanthrene and regardless of loading sequence, naphthalene exhibited consistently lower sorption capacities and the ideal adsorbed solution theory (IAST) slightly underestimates the naphthalene sorption equilibria. Conversely, the sorption equilibria of phenanthrene in the presence of naphthalene depended upon the loading sequence of the two sorbates on the soil. Little competition from naphthalene on the sorption equilibria of phenanthrene was observed when phenanthrene was loaded either simultaneously with or sequentially after naphthalene, but appreciable competition from naphthalene was observed when the soil had been pre-contaminated with phenanthrene. IAST slightly underestimates the phenanthrene sorption equilibria observed in the latter system, but it cannot estimate the phenanthrene sorption equilibria in the former two systems. We proposed that adsorption on internal surfaces of ink-bottle shaped pores within relatively flexible sorbent matrix may have caused the competitive sorption phenomena observed in this study. The study suggests that contamination history may have strong influence on the equilibrium sorption of organic pollutant mixtures.     

Studies on the sorption and desorption characteristics of Zn(II) on the surface soils of nuclear power plant sites in India using a radiotracer technique

Zinc adsorption was studied in the soils of three nuclear power plant sites of India. 65Zn was used as a radiotracer to study the sorption characteristics of Zn(II). The sorption of zinc was determined at 25 and 45 degrees C at pH 7.8+/-0.2 in the solution of 0.01 M Ca(NO3)2 as supporting electrolyte. The sorption data was tested both in Freundlich and Langmuir isotherms and could be described satisfactorily. The effect of organic matter and other physico-chemical properties on the uptake of zinc was also studied in all the soil samples. The results showed that the cation exchange capacity, organic matter, pH and clay content were the main contributors to zinc sorption in these soils. The adsorption maximum was found to be higher in the soil on Kakarpara Atomic Power Plant sites soils having high organic matter and clay content. The zinc supply parameters of the soils are also discussed. In the desorption studies, the sequential extraction of the adsorbed zinc from soils showed that the diethylene triamine penta acetic acid extracted maximum amount of adsorbed zinc than CaCl2 and Mg(NO3)2. The zinc sorption on the soil and amount of zinc retention after extractants desorption shows a positively correlation with vermiculite and smectite mineral content present in the clay fraction of the soil. The amount desorbed by strong base (NaOH) and demineralised water was almost negligible from soils of all the sites, whereas the desorption by strong acid (HNO3) was 75-96% of the adsorbed zinc.     

A generalised sorption model for the concentration dependent uptake of caesium by argillaceous rocks

A three-site cation exchange model is proposed to describe the concentration dependent uptake of Cs on natural argillaceous rock systems. Major premises in the model are that the sorption of Cs is dominated by the illite mineral component in the rock and that there is a fixed relationship between the site capacities of the three site types denoted as frayed edge, type II and planar sites. The definition of a “reference illite” with a cation exchange capacity of 0.2 equiv. kg^-1 allows the three site capacities to be fixed in the model calculations over the weight fraction of illite in the argillaceous rocks. Up to Cs equilibrium concentrations of 10^-3 M sorption occurs predominantly on the frayed edge and type II sites (higher affinity sites), with the planar site type playing only a minor role. Competition with Cs for sorption on the former two site types arises predominantly from monovalent cations such as K, Rb and NH₄ which have low hydration energies. H and Na (except at high concentrations) are considerably less competitive and bivalent cations such as Mg, Ca and Sr are effectively non-competitive. A consistent set of selectivity coefficients for Cs with respect to K, Rb, NH₄ and Na was derived from analyses and modelling of a wide range of Cs sorption data available in the open literature on pure illites from many different sources. The model was tested against four Cs sorption isotherm data sets determined on argillaceous rocks: Boom clay, Oxford clay, Palfris marl and Opalinus clay. The water chemistries and illite contents given in these experiments allowed the Cs sorption isotherms to be predicted. It is concluded that the Cs sorption model presented here, in which there are no free parameters, can be used to predict the uptake of Cs at equilibrium concentrations below 10^-3 M to within a factor of 2 to 3 in natural argillaceous rock systems.     

Correlations of nonlinear sorption of organic solutes with soil/sediment physicochemical properties

The estimation of solute sorptive behaviors is essential when direct sorption data are unavailable and will provide a convenient way to assess the fate and the biological activity of organic solutes in soil/sediment environments. In this study, the sorption of 2,4-dichlorophenol (2,4-DCP) on 19 soil/sediment samples and the sorption of 13 organic solutes on one sediment were investigated. All sorption isotherms are nonlinear and can be described satisfactorily by a simple dual-mode model (DMM): q(e)=KpCe+Q0 . bCe/(1+bCe), where Kp (mlg(-1)) is the partition coefficient; Ce (microgml(-1)) is the equilibrium concentration; Q0 (microgg(-1)) is the maximum adsorption capacity; Q0 . b (mlg(-1)) is the Langmuir-type isotherm slope in the low concentration (Henry's law) range and b (mlmicrog(-1)) is a constant related to the affinity of the surface for the solute. Based on these nonlinear sorption isotherms and similar other nonlinear isotherms, it is observed that, for both polar 2,4-DCP and nonpolar phenanthrene, Kp, Q0 and Q0 . b are linearly correlated with soil/sediment organic carbon content (f(oc) in the range of 0.118-53.7%). The results indicate that the nonlinear sorption of organic solutes results primarily from interactions with soil/sediment organic matter. The K*oc K*oc=Kp/f(oc)), Qoc (Qoc=Q0/f(oc)), Loc (Loc=Q0 . b/f(oc)) and b for a given organic solute with different soils/sediments are largely invariant. Furthermore, logK*oc, logb and logLoc for various organic solutes are correlated significantly with the solute logKow or logSw (logKow in the range of 0.9 to 5.13 and logSw in the range of -6.176 to -0.070). A fundamental empirical equation was then established to calculate approximately the nonlinear sorption from soil/sediment f(oc) and solute Sw for a given solute equilibrium concentration.     

Effect of sediment properties on the sorption of C12-2-LAS in marine and estuarine sediments

Linear alkylbenzene sulfonates (LAS) are anionic high production volume surfactants used in the manufacture of cleaning products. Here, we have studied the effect of the characteristics of marine and estuarine sediments on the sorption of LAS. Sorption experiments were performed with single sediment materials (pure clays and sea sand), with sediments treated to reduce their organic carbon content, and with field marine and estuarine sediments. C₁₂-2-LAS was used as a model compound. Sorption to the clays montmorillonite and kaolinite resulted in non-linear isotherms very similar for both clays. When reducing the organic content, sorption coefficients decreased proportionally to the fraction removed in fine grain sediments but this was not the case for the sandy sediment. The correlation of the sediment characteristics with the sorption coefficients at different surfactant concentrations showed that at concentrations below 10 μg C₁₂-2-LAS/L, the clay content correlated better with sorption, while the organic fraction became more significant at higher concentrations.     

Fate of nickel in a lime-stabilized biosolid,a calcareous soil and soil–biosolid mixtures

Soil contamination with anthropogenic metals resulting from biosolid application is widespread around the world. To better predict the environmental fate and mobility of contaminants, it is critical to study the capacity of biosolid-amended soils to retain and release metals. In this paper, nickel adsorption onto a calcareous soil, a lime-stabilized biosolid, and soil–biosolid mixtures (30, 75, and 150 t biosolid/ha) was studied in batch experiments. Sorption experiments showed that (1) Ni adsorption was higher onto the biosolid than the calcareous soil, and (2) biosolid acted as an adsorbent in the biosolid–soil mixtures by increasing Ni retention capacity. The sorption tests were complemented with the estimation of Ni adsorption reversibility by successive applications of extraction solutions with water, calcium (100 mg/L), and oxalic acid (equivalent to 100 mg carbon/L). It has been shown that Ni desorption rates in soil and biosolid-amended soils were lower than 30 % whatever the chemical reagent, indicating that Ni was strongly adsorbed on the different systems. This adsorption/desorption hysteresis effect was particularly significant at the highest biosolid concentration (150 t/ha). Finally, an adsorption empirical model was used to estimate the maximum permissible biosolid application rate using French national guideline. It has been shown that desorption effects should be quantitatively considered to estimate relevant biosolid loadings.     

The effect of hydrocarbon mixtures on adsorption of substituted naphthalenes by clay and sediment from water

Adsorption of methyl and dimethyl naphthalenes, and of these compounds as components of JP8 and synthetic jet fuel mixtures, has been measured on two sediments and montmorillonite clay in water. Isotherms were linear, and hydrocarbons of similar structure gave similar adsorption coefficients on a particular clay or sediment. Individual component adsorption coefficients were dependent upon mixture composition, but coefficients usually varied by less than a factor of two. This implies that single component adsorption coefficients may be adequate for use in environmental fate models of hydrocarbon mixtures.     

Competing TCE and cis-DCE degradation kinetics by zero-valent iron-experimental results and numerical simulation

The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Sch?fer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of permeable reactive iron barriers. Even if TCE is present in only small concentrations (>3% of molar cis-DCE concentration) it is the contaminant limiting the residence time and the required thickness of the iron barrier.     

Coating effects on the glass adsorption of polychlorinated biphenyl (PCB) congeners

The effects of coating materials on polychlorinated biphenyl (PCB) adsorption in aqueous solution were assessed in an attempt to minimize PCB sorption loss during sampling processes. A coating material, which enhances PCB adsorption and allows adsorbed PCBs to be readily extracted by solvents, can act as a sampling concentrator to reduce PCB losses from both adsorption and evaporation. Several coating materials were evaluated, including paraffin oil, silicone oil, dimethyldichlorosilane (Sylon-CT), Prosil 28^® and polydimethylsiloxane (PDS) with viscosity 0.65, 50 (PDS 50), and 500 (PDS 500) cSt. PDS and silicone oil enhanced adsorption for all five congeners examined (IUPAC No. 28, 52, 101, 138, and 180). Sylon-CT, paraffin oil and Prosil 28^® had inconsistent effects on adsorption of different congeners. Desorption of adsorbed PCBs onto all coating types was assessed. The recovery efficiency of extracting PCBs with solvents was enhanced greatly with all coatings as opposed to non-coated surfaces, with the exception of paraffin oil. Coating with silicon oil, PDS 50, and 500 resulted in virtually 100% recovery of adsorbed PCBs. It was also found that Teflon containers were poor substitutes for glass containers and failed to minimize PCB losses. Among the materials studied, the best coating that could be used as a sampling concentrator was PDS 500.     

Sorption of cobalt and nickel on anaerobic granular sludges: isotherms and sequential extraction

The objective of this study was to investigate the sorption capacity and the fractionation of sorbed nickel and cobalt onto anaerobic granular sludges. Two different anaerobic granular sludges (non-fed, pH=7) were loaded with nickel and cobalt in adsorption experiments (monometal and competitive conditions). The combination of sequential extraction with the sorption isotherm analysis allowed the assessment of the sorption capacity of individual fractions present in the anaerobic granular sludges. The operational fractionation of the sorbed heavy metals was determined using a modified Tessier sequential extraction procedure. The sorption characteristics of each extracted fraction (exchangeable, carbonates, organic matter/sulfides and residual fractions) fitted well to the Langmuir model. The organic matter/sulfides fraction showed the highest affinity for cobalt and nickel in both sludges investigated compared to the other operationally defined fractions. The presence of iron negatively affected cobalt and nickel accumulation in this organic matter/sulfides fraction. The trace metals-iron sulfide interactions are likely to be the key process in controlling the distribution of cobalt and nickel during sorption onto non-fed methanogenic granules due to the high affinity of iron sulfides towards the metals studied.     

Geochemical interactions between process-affected water from oil sands tailings ponds and North Alberta surficial sediments

In Northern Alberta, the placement of out-of-pit oil sands tailings ponds atop natural buried sand channels is becoming increasingly common. Preliminary modeling of such a site suggests that process-affected (PA) pond water will infiltrate through the underlying clay till aquitard, reaching the sand channel. However, the impact of seepage upon native sediments and groundwater resources is not known. The goal of this study is to investigate the role of adsorption and ion exchange reactions in the clay till and their effect on the attenuation or release of inorganic species. This was evaluated using batch sorption experiments (traditional and a recent modification using less disturbed sediment samples) and geochemical modeling with PHREEQC. The results show that clay till sediments have the capacity to mitigate the high concentrations of ingressing sodium (600 mg L(-1)), with linear sorption partitioning coefficients (K(d)) of 0.45 L kg(-1). Ion exchange theory was required to account for all other cation behaviour, precluding the calculation of such coefficients for other species. Qualitative evidence suggests that chloride will behave conservatively, with high concentrations remaining in solution (375 mg L(-1)). As a whole, system behaviour was found to be controlled by a combination of competitive ion exchange, dissolution and precipitation reactions. Observations, supported by PHREEQC simulations, suggest that the influx of PA water will induce the dissolution of pre-existing sulphate salts. Sodium present in the process-affected water will exchange with sediment-bound calcium and magnesium, increasing the divalent ions' pore fluid concentrations, and leading to the precipitation of a calcium-magnesium carbonate mineral phase. Thus, in similar tailings pond settings, particularly if the glacial till coverage is thin or altogether absent, it is reasonable to expect that high concentrations of sodium and chloride will remain in solution, while sulphate concentrations will exceed those of the ingressing plume (150 mg L(-1)).