Effect of Sorption Heterogeneity on Moments of Solute Residence Time in Convergent Flows

In this paper, we analyze the impact of physical and chemical heterogeneity on solute travel time to a pumping well. We consider a solute undergoing reversible linear instantaneous equilibrium sorption. Both the distribution coefficient, K _d , and the transmissivity field, T, are considered spatially variable, and are modeled as partially correlated spatial random functions. Groundwater flow and solute transport are then solved within the context of a numerical Monte Carlo framework. The results are analyzed on the basis of dimensional analysis techniques. Simple and compact expressions characterizing the dependence of the target travel time moments on relevant dimensionless groups are proposed. The functional form of these expressions is inspired by, and is consistent with, the previous works of Sanchez-Vila and Rubin (Water Resour. Res. 39(4):1086, 2003) and Riva et al. (J. Contam. Hydrol. 82:23–43, 2006) A key result is that the effects of the chemical and physical heterogeneities on the mean travel time can be decoupled consistently with existing analytical results. The relative role of physical and geochemical heterogeneities in travel time variance is more complex, and such a decoupling is not observed. Potential uses of this work include the assessment of aquifer reclamation time by means of a single pumping well.     

Reach-Scale Cation Exchange Controls on Major Ion Chemistry of an Antarctic Glacial Meltwater Stream

McMurdo dry valleys of Antarctica represent the largest of the ice-free areas on the Antarctic continent, containing glaciers, meltwater streams, and closed basin lakes. Previous geochemical studies of dry valley streams and lakes have addressed chemical weathering reactions of hyporheic substrate and geochemical evolution of dry valley surface waters. We examine cation transport and exchange reactions during a stream tracer experiment in a dry valley glacial meltwater stream. The injection solution was composed of dissolved Li⁺, Na⁺, K⁺, and Cl^-. Chloride behaved conservatively in this stream, but Li⁺, Na⁺, and K⁺ were reactive to varying degrees. Mass balance analysis indicates that relative to Cl^-, Li⁺ and K⁺ were taken up in downstream transport and Na⁺ was released. Simulations of conservative and reactive (first-order uptake or generation) solute transport were made with the OTIS (one-dimensional solute transport with inflow and storage) model. Among the four experimental reaches of Green Creek, solute transport simulations reveal that Li⁺ was removed from stream water in all four reaches, K⁺ was released in two reaches, taken up in one reach, and Na⁺ was released in all four reaches. Hyporheic sediments appear to be variable with uptake of Li⁺ in two reaches, uptake of K⁺ in one reach, release of K⁺ in two reaches, and uptake of Na⁺ in one reach. Mass balances of the conservative and reactive simulations show that from 1.05 to 2.19 moles of Li⁺ was adsorbed per reach, but less than 0.3 moles of K⁺ and less than 0.9 moles of Na⁺ were released per reach. This suggests that either (1) exchange of another ion which was not analyzed in this experiment or (2) that both ion exchange and sorption control inorganic solute transport. The elevated cation concentrations introduced during the experiment are typical of initial flows in each flow season, which flush accumulated dry salts from the streambed. We propose that the bed sediments (which compose the hyporheic zone) modulate the flushing of these salts during initial flows each season, due to ion exchange and sorption reactions.     

Influential factors on the levels of cation exchange capacity in sediment at Langat river

An exploratory study was carried out at 22 sampling stations along the Langat River, Selangor in order to investigate on the vitality of cation exchange capacity (CEC) in sediment (0–5 cm). Parameters such as pH, Eh, salinity, and electrical conductivity (EC) were determined. The CEC in sediment has been calculated by the determination of Ca²⁺, Na⁺, Mg²⁺, and K⁺ using the flame atomic absorption spectrophotometer, while the organic matter content in sediment was ascertained using the loss on ignition method. The characteristic of the sediment shows that pH (3.09–7.46), salinity (0.02–10.71 ppt), EC (3.39–517 μS/cm) and Eh (?16.20–253.10 mV) were substantially high in variation. This study also revealed that exchangeable Ca²⁺ and Mg²⁺ were controlled by organic matter contents, while exchangeable Na⁺ and K⁺ were influenced by salinity. Salinity was observed to play a major part in controlling all the exchangeable cations, as it gives strong significant correlations with Na⁺, K⁺, Mg²⁺, CEC, and organic matter at p?<?0.01. The presence of seawater, clay mineralogy, and organic matter proves that it does play an important role in determining the CEC and soon relates to the pollution magnitude in the sediment.     

A spectrophotometric measurement of soil cation exchange capacity based on cobaltihexamine chloride absorbance

Among numerous methods for cation exchange capacity (CEC) determination for soils and sediments, the cobaltihexamine chloride method is frequently used due to its ability to measure CEC at soil pH. After exchange with Co(NH₃)₆³⁺ ions, CEC is estimated via the measurement of the Co remaining in solution. The modified method proposed allows a more rapid determination of CEC based on the measurement of the absorbance at 472 nm of the cobaltihexamine chloride solution before and after exchange. This method has been applied to various soil's horizons from four sites, selected to cover a wide range of CEC and pH values. The model obtained allows one to calculate CEC from absorbance at 472 nm with 95% confidence intervals. As CEC is of relevant meaning in agronomical and environmental purposes, and more recently in ecotoxicological studies, this modified method can be proposed as a rapid test for CEC evaluation.     

Computational study of tetrahedral Al–Si ordering in muscovite

 The nature of Al–Si ordering across the tetrahedral sites in muscovite, K₂Al₄(Si₆Al₂O₂₀)(OH)₄, was investigated using various computational techniques. Values of the atomic exchange interaction parameters J _l were obtained. From these parameters, a two-dimensional Al–Si ordering scheme was deduced. The transition temperature T _c for this two-dimensional ordering is 1900 K. There are several possible ordering schemes in three dimensions, based on different stacking sequences of ordered sheets of tetrahedral sites. Monte Carlo simulations of both two-dimensional and three-dimensional ordering were performed, but in the three-dimensional simulation only the two-dimensional ordering is seen, implying that three-dimensional ordering is too slow to be attained during the timescale of the simulation. The effect of the three-dimensional interactions is to raise the two-dimensional ordering temperature to 2140 K. From the three-dimensional Monte Carlo simulation, the frequency of occurrence of 4Si0Al, 3Si1Al, 2Si2Al and 1Si3Al clusters was determined, which match those inferred by ²⁹Si MAS–NMR measurements reasonably well. In fact, the match suggests that the cation ordering seen in experiments corresponds to a configuration with considerable short-range order but no long-range order, similar to a state that is at a temperature just above an ordering phase transition. Received: 28 August 2000 / Accepted: 12 March 2001     

Sorption behavior of the sandy residual unconsolidated materials from the sandstones of the Botucatu Formation,the main aquifer of Brazil

Pollutant transport through porous geological materials depends on the intrinsic characteristics of the materials that define the sorption behavior. This is the main environmental aspect that must be evaluated in terms of natural attenuation and retardation factor of the pollutants. Sorption is directly related to the electrostatic charge of the mineral, the organic matter, and the oxide and hydroxide contents. We assessed the sorption characteristics of the sandy residual unconsolidated material of the Botucatu Formation, which is part of the main aquifer of Brazil, using Batch Equilibrium Tests. The tests used multicomponent solutions of NaCl, KCl, ZnCl₂, and CuCl₂·H₂O with a total concentration that varied from 20 to 1,000 ppm. Different plotting systems were applied so that the isotherms better reflected the sorption behavior of the studied cations onto the unconsolidated materials. The cation Na⁺ was not sorbed. The Langmuir I and Freundlich equations adequately represent the behavior of Cu⁺⁺, the Langmuir II approximation better represented K⁺, and the Langmuir I and Freundlich equations were reasonably fitted Zn⁺⁺.     

Comparison of numerical simulation of solute transport with observed experimental data in a silt loam subsoil

 Solute transport experiments were conducted on loamy soils of north-eastern Iowa, USA, and the results were compared with a numerical solution of a classical advection-dispersion transport model developed in this study. Flow experiments in the laboratory on undisturbed soil columns showed a flow rate of water much higher than was estimated from the soil properties and grain-size analysis data, suggesting preferential flow regime in the soil. In contrast, the relative concentration peaks of Cl^– and Br^– in the effluent were only approximately 70% of those predicted by the classical advection-dispersion equation (ADE). In addition, the experimental breakthrough curves (BTCs) showed greater tailings of these ions than the model solution. These observations suggest a loss of solute mass during transport from the dynamic flowing regions to a stagnant, immobile water phase in the soil matrix. Experiments in small disturbed soil columns showed that movement of Cl^– and Br^– is in good agreement with predictions of the classical ADE when the tracers are applied as a continuous source. However, in the case of a pulse source, the BTCs of Cl^– and Br^– matched the model only in the ascending part of the curves. Such variation indicates greater retardation of these ions than that of simulation, probably caused by the decrease in soil permeability due to cation exchange reactions in the soil involving monovalent and divalent cation pairs such as K⁺–Ca²⁺ and K⁺–Mg²⁺. In addition, retardation occurred as a result of the continuous saturation of soil columns which seemed to have caused an expansion of clay minerals, thus resulting in decreased soil permeability. In both the continuous and the pulse-source experiments, K⁺ was not detected in the effluent samples, which seemed to have been lost in exchange reactions and adsorption. Received: 20 November 1998 · Accepted: 19 July 1999     

Geochemical controls on lead concentrations in stream water and sediments

The equilibrium distribution of lead in solution and adsorbed on cation exchange sites in sediment theoretically may be calculated from equations representing selectivities of substrate for lead over H⁺, Ca²⁺ and Na⁺, and the stabilities of lead solute species. Such calculations include consideration of total concentrations of major ions, cation exchange capacity (CEC) of substrate, and pH, at values expected in various natural systems. Measurements of CEC and selectivity coefficients were made for synthetic halloysite, a finely divided amorphous 1:1 clay prepared by precipitation from a mixture of solutions of aluminum and silica. Where suspended sediment having the same properties is present in concentrations of 10-1,000 mg/1 at pH 6–8, more than 90% of the lead present can be adsorbed on sediment surfaces. The cation exchange behavior of lead and other minor cationic species in natural systems could be predicted by this type of model if enough other supporting information were available. Information of the type needed describing natural stream sediments, however, is presently inadequate for accurate predictions.     

振荡交换-抽滤淋洗结合凯氏定氮法快速测定土壤中的阳离子交换量

测定土壤阳离子交换量(CEC)的行业标准方法(LY/T1243—1999)是采取离心分离结合手工蒸馏进行滴定,耗时长、操作繁琐。为了缩短反应时间,提高检测效率,本文利用乙酸铵对酸性和中性土壤进行处理,用氯化铵-乙酸铵对石灰性土壤进行处理,应用振荡和抽滤装置快速交换和清洗阳离子,通过全自动凯氏定氮仪对吸附的铵根离子进行测定,由此计算CEC值。结果表明:在最佳的振荡和蒸馏时间、滴定酸浓度、指示剂配比等实验条件下,一个批次样品(100件)的分析流程仅需要12h,比传统方法检测时间缩短近80%。经国家标准物质验证,测定结果与推荐值相符,5次测定的相对标准偏差均小于1. 5%。本方法免去了多次离心分离操作,解决了待测成分损失、CEC测定值偏低的问题,提高了检测效率和准确度,较林业标准方法的成本低,可操作性强,适用于土壤环境质量评价、地区土壤抽样调查等大批量土壤样品分析。     

Stochastic Modeling of Variably Saturated Transient Flow in Fractal Porous Media

This work presents the application of a Monte Carlo simulation method to perform an statistical analysis of transient variably saturated flow in an hypothetical random porous media. For each realization of the stochastic soil parameters entering as coefficients in Richards' flow equation, the pressure head and the flow field are computed using a mixed finite element procedure for the spatial discretization combined with a backward Euler and a modified Picard iteration in time. The hybridization of the mixed method provides a novel way for evaluating hydraulic conductivity on interelement boundaries. The proposed methodology can handle both large variability and fractal structure in the hydraulic parameters. The saturated conductivity K _s and the shape parameter _vg in the van Genuchten model are treated as stochastic fractal functions known as fractional Brownian motion (fBm) or fractional Gaussian noise (fGn). The statistical moments of the pressure head, water content, and flow components are obtained by averaging realizations of the fractal parameters in Monte Carlo fashion. A numerical example showing the application of the proposed methodology to characterize groundwater flow in highly heterogeneous soils is presented.     

Diffusion along interphase boundaries and its effect on retrograde zoning patterns of metamorphic minerals

In this study we use two dimensional chemical patterns and numerical modeling to estimate the relative rates of chemical transport along interphase boundaries (ib) and through grain (s) interiors during retrograde Fe–Mg exchange between garnet and biotite at a garnet–biotite–quartz triple junction. We demonstrate that systematic variations in garnet–rim compositions, which are frequently observed along garnet–quartz interfaces, and deviations from concentric retrograde zoning patterns start to develop when chemical transport along the interphase boundaries becomes slow during cooling. The capacities for chemical transport along an interphase boundary depend on the product D ^ib K ^ib/s a, where D ^ib is the diffusion coefficient of the exchangeable components within the interphase boundary medium, K ^ib/s is the equilibrium partitioning coefficient between the cation exchange partners and the interphase boundary medium and a is the interphase boundary width. The model is applied to analyze the retrograde zoning patterns in garnets from the Mozambique belt (SE-Kenya), which cooled from 820°C at a rate of ca. 2°C/my. It is found that non-equilibrated compositions in garnet along garnet/quartz interphase boundaries started to develop below 700°C due to insufficient rates of chemical transport along these boundaries. The transport capacities of garnet/quartz interphase boundaries was estimated to have been between about 1E-23 cm³/s (575°C) and 1E-20 cm³/s (700°C) from modeling the observed X _Fe pattern in garnet close to a garnet–quartz–biotite triple junction and relying on published data on the diffusivity of Fe²⁺ in garnet. Similar transport capacities are obtained; when the interphase boundary is assumed to be filled with a material that has the transport properties and chemical composition of a free melt in equilibrium with garnet, biotite and quartz at the respective conditions. In contrast, if the transport properties of the interphase boundary medium are related to the diffusivities and solubility of Fe²⁺ and FeOH⁺ within a free aqueous solution, chemical transport along the interphase boundaries would be much more efficient, and exchange equilibrium would have been maintained during the entire cooling history of the rocks. The observation of systematic deviations from local equilibrium along the garnet–quartz interphase boundaries leads us to exclude the presence of an aqueous fluid along the interphase boundary at any time during cooling.     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Vertical transport of polycyclic aromatic hydrocarbons in different particle-size fractions of sandy soils

Vertical transport of selected polycyclic aromatic hydrocarbons (PAHs) in different particle-size fractions of sandy soils was investigated by simulation experiments in soil columns. Tested soil samples were fractionized into three particle-sizes including sand, coarse silt and fine silt (2,000–50, 50–20 and <20 μm). Rainfall simulations were conducted in artificially PAHs contaminated soil columns with 30 cm length and 5 cm diameter in 40 days. PAHs were extracted from soil samples and determined by high performance liquid chromatography (HPLC). Results showed that the residue level of PAHs in fine silt fraction reached 35.85 mg/kg, which was significantly higher than those in sand and coarse silt fraction (16.28 and 11.80 mg/kg, respectively), probably because PAHs in macroporous fractions were prone to volatilize or degrade compared with that in microporous fractions. Linear relationship between the residue levels of individual PAH (R _PAHs) and the value of partition coefficient (log K _oc) was regressed as R _PAHs = 1.55 × log K _oc − 5.86, R ² = 0.91, n = 9. These results indicated that vertical transport of the mixed PAHs in soils were controlled both by the nature of PAHs (i.e. log K _oc, molecular weight), soil particle size and soil organic contents, which could influence the transport of PAHs.     

A sequential partly iterative approach for multicomponent reactive transport with CORE2D

CORE^2D V4 is a finite element code for modeling partly or fully saturated water flow, heat transport, and multicomponent reactive solute transport under both local chemical equilibrium and kinetic conditions. It can handle coupled microbial processes and geochemical reactions such as acid–base, aqueous complexation, redox, mineral dissolution/precipitation, gas dissolution/exsolution, ion exchange, sorption via linear and nonlinear isotherms, and sorption via surface complexation. Hydraulic parameters may change due to mineral precipitation/dissolution reactions. Coupled transport and chemical equations are solved by using sequential iterative approaches. A sequential partly iterative approach (SPIA) is presented which improves the accuracy of the traditional sequential non-iterative approach (SNIA) and is more efficient than the general sequential iterative approach (SIA). While SNIA leads to a substantial saving of computing time, it introduces numerical errors which are especially large for cation exchange reactions. SPIA improves the efficiency of SIA because the iteration between transport and chemical equations is only performed in nodes with a large mass transfer between solid and liquid phases. The efficiency and accuracy of SPIA are compared to those of SIA and SNIA using synthetic examples and a case study of reactive transport through the Llobregat Delta aquitard in Spain. SPIA is found to be as accurate as SIA while requiring significantly less CPU time. In addition, SPIA is much more accurate than SNIA with only a minor increase in computing time. A further enhancement of the efficiency of SPIA is achieved by improving the efficiency of the Newton–Raphson method used for solving chemical equations. Such an improvement is obtained by working with increments of log concentrations and ignoring the terms of the Jacobian matrix containing derivatives of activity coefficients. A proof is given for the symmetry and non-singularity of the Jacobian matrix. Numerical analyses performed with synthetic examples confirm that these modifications improve the efficiency and convergence of the iterative algorithm. Changbing Yang is now at The University of Texas at Austin, USA.     

Cation distribution in pentlandites (Fe,Ni)9S8: Dependence on pressure and temperature and kinetics of the cation exchange reaction

This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)₉S₈. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol^–1, 20.52 J K^–1 mol^–1, and 6.99 × 10^–6 m³ mol^–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 10² T ^–1+8.41 x 10^–7 T ^–1 P, where K = (Fe/Ni)_octahedral /(Fe/Ni)_tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol^–1.     

Cation exchange capacity of loess and overlying soil in the non-carbonate loess sections, North-Western Croatia

The adsorption properties in terms of cation exchange capacity and their relation to the soil and sediment constituents (clay minerals, Fe-, Mn-, and Al-oxyhydroxides, organic matter) were investigated in loess, soil-loess transition zone, and soil at four loess-soil sections in North-Western Croatia. Cation exchange capacity of the bulk samples, the samples after oxalate extraction of Fe, Mn and Al, and after removal of organic matter, as well as of the separated clay fraction, was determined using copper ethylenediamine. Cation exchange capacity (pH～7) of the bulk samples ranges from 5 to 12 cmol _c /kg in soil, from 7 to 15 cmol _c /kg in the soil-loess transition zone, and from 12 to 20 cmol _c /kg in loess. Generally, CEC values increase with depth. Oxalate extraction of Fe, Mn, and Al, and removal of organic matter cause a CEC decrease of 3–38% and 8–55%, respectively, proving a considerable influence of these constituents to the bulk CEC values. In the separated clay fraction (<2 μm) CEC values are up to several times higher relative to those in the bulk samples. The measured CEC values of the bulk samples generally correspond to the clay mineral content identified. Also, a slight increase in muscovite/illite content with depth and the vermiculite occurrence in the loess horizon are concomitant with the CEC increase in deeper horizons, irrespective of the sample pretreatment.     

Conditional Probability Density Functions of Concentrations for Mixing-Controlled Reactive Transport in Heterogeneous Aquifers

This paper presents an approach conducive to an evaluation of the probability density function (pdf) of spatio-temporal distributions of concentrations of reactive solutes (and associated reaction rates) evolving in a randomly heterogeneous aquifer. Most existing approaches to solute transport in heterogeneous media focus on providing expressions for space–time moments of concentrations. In general, only low order moments (unconditional or conditional mean and covariance) are computed. In some cases, this allows for obtaining a confidence interval associated with predictions of local concentrations. Common applications, such as risk assessment and vulnerability practices, require the assessment of extreme (low or high) concentration values. We start from the well-known approach of deconstructing the reactive transport problem into the analysis of a conservative transport process followed by speciation to (a) provide a partial differential equation (PDE) for the (conditional) pdf of conservative aqueous species, and (b) derive expressions for the pdf of reactive species and the associated reaction rate. When transport at the local scale is described by an Advection Dispersion Equation (ADE), the equation satisfied by the pdf of conservative species is non-local in space and time. It is similar to an ADE and includes an additional source term. The latter involves the contribution of dilution effects that counteract dispersive fluxes. In general, the PDE we provide must be solved numerically, in a Monte Carlo framework. In some cases, an approximation can be obtained through suitable localization of the governing equation. We illustrate the methodology to depict key features of transport in randomly stratified media in the absence of transverse dispersion effects. In this case, all the pdfs can be explicitly obtained, and their evolution with space and time is discussed.     

Evaluating methods for quantifying cation exchange in mildly calcareous sediments in Northern Alberta

Cation exchange capacity (CEC) and exchangeable cation composition are important properties in defining water–sediment interactions in contaminant transport scenarios, such as the seepage of process-affected water from oil sands tailings impoundments. At present, detailed characterization of these properties has been overlooked in the surficial Pleistocene sediments of the Athabasca Oil Sands region in Canada. Although a great variety of methods for determining CEC exist and continue to be developed, there is a deficiency in detailed comparisons amongst these methods in the literature, and consequently uncertainty still remains as to which extractants/methods are most suitable for use with sediments containing partially soluble carbonate salts. The present study (1) conducts an up-to-date evaluation of several distinct methods for their suitability in characterizing cation exchange properties in mildly calcareous sediments; using them to (2) evaluate the sorptive capacity and easily displaceable cations of mildly calcareous, surficial sediments near Fort McMurray, Alberta. Four conceptually different CEC methods were chosen: (a) a summation method (Lithium Chloride extractant); (b) a method that displaces an index cation after intermediary washes (Sodium Acetate–Ammonium Acetate); (c) a method using a high affinity cation complex (Silver Thiourea); and (d) a titration method using an organic cationic dye (Methylene Blue). Exchangeable cations were characterized using the Lithium Chloride and Silver Thiourea methods. Analysis suggests that the Methylene Blue test is least impacted by the presence of carbonate mineral phases. Results from field sediments suggest that the exchangeable cations, in decreasing abundance, consist of Ca > Mg > K > NH₄ > Na; while the CEC was found to be 4.7 ± 2.7 meq 100 g⁻¹ in the clay-rich glacial till, 0.7 ± 0.0 meq 100 g⁻¹ in the underlying sand and 4.1 ± 2.3 meq 100 g⁻¹ in the till-sand transition zone.     

Adsorption characteristics of heavy metals in soil zones developed on spilite

Various soil zones such as Bw, C1, and C3 are developed on spilite. Montmorillonite, vermiculite and chlorite is moderately occurred in the C1 and C3 soil zones, in contrast montmorillonite and vermiculite are absent in Bw soils whereas illite and sesquioxide are relatively increased. The high cation exchange capacity (CEC) of montmorillonite and vermiculte and moderate CEC of chlorite and illite resulted in the high adsorption of heavy metals. The adsorption of the heavy metals on spilite soil zones was studied at different concentrations and pH levels. Heavy metals like lead, cadmium, and copper were selected for adsorption studies considering their contribution as toxic metals in the environment. The initial solute concentrations ranged from 7.0 × 10⁻³ to 1.0 × 10² mg/L. The sorption behavior of Cd²⁺, Pb²⁺, and Cu²⁺ on soil zones of spilite was investigated using the batch equilibrium technique at 25°C. The characteristics of the adsorption process were investigated using Scatchard plot analysis (q/C vs. q) by the batch equilibrium technique at 25°C. In the adsorption of heavy metals, deviation from linearity in the plot of q/C versus q was observed, indicating the presence of multi-model interaction and non-Langmuirean behavior. When the Scatchard plot showed a deviation from linearity, greater emphasis was placed on the analysis of the adsorption data in terms of the Freundlich model, in order to construct the adsorption isotherms of the metal(s) at particular concentration(s) in solutions. The adsorption behavior of these metal ions on spilite soil zones is expressed by the Freundlich isotherms. Adsorption constants and correlation coefficients for the Cd, Pb, and Cu on spilite soil zones were calculated from Freundlich plots.