A Model for Uptake of Pollutants by Vegetation

A mass transfer approach is used in developing a practical mathematical model of gaseous pollutant uptake by leaves in which a series of resistances is summed across a concentration difference. The body of information presented in this paper is directed to plant pathologists or physiologists in the field of vegetal-pollutant effects and to people interested in the natural removal of air pollutants by vegetation. Correlations are given to calculate the aerodynamic and the stomatal resistances to uptake, while both a qualitative investigation and quantitative estimates are made of the mesophyllic resistance. The factors which control the aerodynamic resistance, r_a, are leaf size and wind speed, while the leaf physiology is the determinant of the stomatal resistance, r_s . It is noted that the chemical reaction rate and pollutant diffusivity in the mesophyll control the mesophyllic resistance, r_m, though the overall gas phase mesophyllic resistance, Hr_m, is strongly a function of pollutant solubility in water. Finally, the overall model is compared to earlier experimental work on vegetal uptake of SO₂.     

Sorption of ozone by 'New Yorker' tomato leaves

Tomato (Lycopersicon esculentum Mill.) 'New Yorker' plants were exposed to O(3) to compare leaf diffusive conductance (LDC) before exposure to O(3) with O(3) sorption rates and visible injury ratings. Two plant development stages and four or five leaf growth stages were examined. The LDC varied among leaf growth stages and between plant development stages and leaf surfaces; there was no continuity in the LDC pattern. Sorption rates differed among some leaf growth stages, and between plant development stages in expanding leaves (growth stage 1). For both development stages high sorption rates occurred in fully mature leaves; otherwise little similarity between corresponding leaf growth stages was evident. Total O(3) flux to the leaf was not well predicted by the LDC for water vapour; nor was visible injury well related to total flux. Differential mesophyll processes and leaf surface sorption capabilities may have accounted for some of the inconsistencies observed.     

Cosolvent effects on sorption isotherm linearity

Sorption-desorption hysteresis, slow desorption kinetics, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic polymers associated with soils and sediments. In this study, aqueous and mixed solvent systems were used to investigate the effects of a cosolvent, methanol, on sorption isotherm linearity with natural organic matter (NOM), and to evaluate whether these results support, or weaken, the rubbery/glassy polymer conceptualization of NOM. All of the sorption isotherms displayed some nonlinear character. Our data indicates that all of the phenanthrene and atrazine isotherms were nonlinear up to the highest equilibrium solution concentration to solute solubility in water or cosolvent ratios (Ce/Sw,c) used, approximately 0.018 and 0.070, respectively. Isotherm linearity was also observed to increase with volumetric methanol content (fc). This observation is consistent with the NOM rubbery/glassy polymer conceptualization: the presence of methanol in NOM increased isotherm linearity as do solvents in synthetic polymers, and suggests that methanol is interacting with the NOM, enhancing its homogeneity as a sorptive phase so that sorption is less bimodal as fc increases. When the equilibrium solution concentration was normalized for solute solubility in water or methanol-water solutions, greater relative sorption magnitude was observed for the methanol-water treatments. This observation, in conjunction with the faster sorption kinetics observed in the methanol-water sediment column systems, indicates that the increase in relative sorption magnitude with fc may be attributed to the faster sorption kinetics in the methanol-water systems, and hence, greater relative sorptive uptake for the rubbery polymer fraction of NOM at similar time scales.     

Role of pH in partitioning and cation exchange of aromatic amines on water-saturated soils

Predicting the reversible interactions between aromatic amines and soil is essential for assessing the mobility, bioavailability and exposure from contaminated sites. Reversible sorption mechanisms of aniline and alpha-naphthylamine were investigated by using single and binary solute sorption to five soils at several pH values, and by applying a distributed parameter (DP) model. The DP model assumes linear partitioning of the neutral species into soil organic matter domains and organic cation binding on negative-charged sites with the exchange coefficients represented by a Gaussian probability distribution. Sorption nonlinearity was attributed to cation exchange with varying site affinities, which was adequately simulated using the DP model. Greater uptake by hydrophobic partitioning and selectivity for cation exchange sites was observed for alpha-naphthylamine compared to aniline. Sorption of alpha-naphthylamine was not impacted quantitatively by aniline under those conditions examined; however, aniline sorption was reduced by alpha-naphthylamine with the largest reduction occurring in the soil with the lowest pH. DP model simulations showed that although hydrophobic partitioning increases with soil-solution pH, cation exchange still contributes significantly to the total sorption even at soil-solution pH values greater than pKa + 2.     

Modelling of diffusion-limited retardation of contaminants in hydraulically and lithologically nonuniform media

A new reactive transport modelling approach and examples of its application are presented, dealing with the impact of sorption/desorption kinetics on the spreading of solutes, e.g. organic contaminants, in groundwater. Slow sorption/desorption is known from the literature to be strongly responsible for the retardation of organic contaminants. The modelling concept applied in this paper quantifies sorption/desorption kinetics by an intra-particle diffusion approach. According to this idea, solute uptake by or release from the aquifer material is modelled at small scale by a "slow" diffusion process where the diffusion coefficient is reduced as compared to the aqueous diffusion coefficient due to (i) the size and shape of intra-particle pores and (ii) retarded transport of solutes within intra-particle pores governed by a nonlinear sorption isotherm. This process-based concept has the advantage of requiring only measurable model parameters, thus avoiding fitting parameters like first-order rate coefficients.In addition, the approach presented here allows for modelling of slow sorption/desorption in lithologically nonuniform media. Therefore, it accounts for well-known experimental findings indicating that sorptive properties depend on (i) the grain size distribution of the aquifer material and (ii) the lithological composition (e.g. percentage of quartz, sandstone, limestone, etc.) of each grain size fraction. The small-scale physico-chemical model describing sorption/desorption is coupled to a large-scale model of groundwater flow and solute transport. Consequently, hydraulic heterogeneities may also be considered by the overall model. This coupling is regarded as an essential prerequisite for simulating field-scale scenarios which will be addressed by a forthcoming publication.This paper focuses on mathematical model formulation, implementation of the numerical code and lab-scale model applications highlighting the sorption and desorption behavior of an organic contaminant (Phenanthrene) with regard to three lithocomponents exhibiting different sorptive properties. In particular, it is shown that breakthrough curves (BTCs) for lithologically nonuniform media cannot be obtained via simple arithmetic averaging of breakthrough curves for lithologically uniform media. In addition, as no analytical solutions are available for model validation purposes, simulation results are compared to measurements from lab-scale column experiments. The model results indicate that the new code can be regarded as a valuable tool for predicting long-term contaminant uptake or release, which may last for several hundreds of years for some lithocomponents. In particular, breakthrough curves simulated by pure forward modelling reproduce experimental data much better than a calibrated standard first-order kinetics reactive transport model, thus indicating that the new approach is of high quality and may be advantageously used for supporting the design of remediation strategies at contaminated sites where some lithocomponents and/or grain size classes may provide a long-term pollutant source.     

Experimental determination of sorption in fractured flow systems

Fracture "skins" are alteration zones on fracture surfaces created by a variety of biological, chemical, and physical processes. Skins increase surface area, where sorption occurs, compared to the unaltered rock matrix. This study examines the sorption of organic solutes on altered fracture surfaces in an experimental fracture-flow apparatus. Fracture skins containing abundant metal oxides, clays, and organic material from the Breathitt Formation (Kentucky, USA) were collected in a manner such that skin surface integrity was maintained. The samples were reassembled in the lab in a flow-through apparatus that simulated approximately 2.7 m of a linear fracture "conduit." A dual-tracer injection scheme was utilized with the sorbing or reactive tracer compared to a non-reactive tracer (chloride) injected simultaneously. Sorption was assessed from the ratio of the first temporal moments of the breakthrough curves and from the loss of reactive tracer mass and evaluated as a function of flow velocity and solute type. The breakthrough curves suggest dual-flow regimes in the fracture with both sorbing and non-sorbing flow fields. Significant sorption occurs for the reactive components, and sorption increased with decreasing flow rate and decreasing compound solubility. Based on moment analysis, however, there was little retardation of the center of solute mass. These data suggest that non-equilibrium sorption processes dominate and that slow desorption and boundary layer diffusion cause extensive tailing in the breakthrough curves.     

Root versus canopy uptake of heavy metals by birch in an industrially polluted area: contrasting behaviour of nickel and copper

We investigated root versus canopy uptake of nickel and copper by mountain birch, Betula pubescens subsp. czerepanovi, close to a nickel-copper smelter on the Kola Peninsula, northwest Russia. To distinguish between aerial contamination of leaf surfaces by dust particles and root-derived contamination of leaves by soluble metals, we transplanted seedlings from a control site to clean and metal-contaminated soils and exposed these seedlings both in clean and polluted sites. Patterns of leaf surface contamination and root uptake were similar for nickel and copper; however, nickel but not copper was effectively translocated from roots to shoots and leaves. The majority (80-95%) of nickel and copper found in birch foliage in the heavily contaminated site was due to deposition of dust particles on leaf surfaces; 32-40% of foliar nickel and 9-19% of foliar copper were in water soluble forms. Washing of fresh leaves removed only a minor part of surface contaminants; boiling of unwashed leaves in distilled water for 15 min removed >90% of soluble nickel and copper.     

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.     

Current issues and uncertainties in the measurement and modelling of air-vegetation exchange and within-plant processing of POPs

Air-vegetation exchange of POPs is an important process controlling the entry of POPs into terrestrial food chains, and may also have a significant effect on the global movement of these compounds. Many factors affect the air-vegetation transfer including: the physicochemical properties of the compounds of interest; environmental factors such as temperature, wind speed, humidity and light conditions; and plant characteristics such as functional type, leaf surface area, cuticular structure, and leaf longevity. The purpose of this review is to quantify the effects these differences might have on air/plant exchange of POPs, and to point out the major gaps in the knowledge of this subject that require further research. Uptake mechanisms are complicated, with the role of each factor in controlling partitioning, fate and behaviour process still not fully understood. Consequently, current models of air-vegetation exchange do not incorporate variability in these factors, with the exception of temperature. These models instead rely on using average values for a number of environmental factors (e.g. plant lipid content, surface area), ignoring the large variations in these values. The available models suggest that boundary layer conductance is of key importance in the uptake of POPs, although large uncertainties in the cuticular pathway prevents confirmation of this with any degree of certainty, and experimental data seems to show plant-side resistance to be important. Models are usually based on the assumption that POP uptake occurs through the lipophilic cuticle which covers aerial surfaces of plants. However, some authors have recently attached greater importance to the stomatal route of entry into the leaf for gas phase compounds. There is a need for greater mechanistic understanding of air-plant exchange and the 'scaling' of factors affecting it. The review also suggests a number of key variables that researchers should measure in their experiments to allow comparisons to be made between studies in order to improve our understanding of what causes any differences in measured data between sites.     

The effects of coal dust on photosynthetic performance of the mangrove, Avicennia marina in Richards Bay, South Africa

Richards Bay, on the northern KwaZulu-Natal coast, is the largest coal exporting port in South Africa. The coal is stored at the Richards Bay Coal Terminal (RBCT) prior to export. Dust from coal operations is a major problem in the Richards Bay area. In this study, we tested the hypothesis that coal dust adversely affects photosynthetic performance of Avicennia marina (Forssk.) Vierh., the dominant mangrove species in the harbour. Photosynthetic performance was determined on 10 trees by measuring carbon dioxide uptake and chlorophyll fluorescence parameters at two elevation sites and on upper and lower leaf surfaces that were covered or uncovered with coal dust. Measurements were made on five clear, sunny days at saturating light (>1,000 micromol m(-2)s(-1)) and high temperature (28-30 degrees C). Coal dust significantly reduced carbon dioxide exchange of upper and lower leaf surfaces by 17-39%, the reduction being generally greater on the lower leaf surface that is covered by a dense mat of trichomes and salt glands. The reduction in carbon dioxide exchange by coal dust was higher at the high elevation site that supported isolated dwarfed trees. The chlorophyll fluorescence data indicated that leaves coated with dust exhibited significantly lower photosystem II (PS II) quantum yield, lower electron transport rate (ETR) through PSII and reduced quantum efficiency of PSII (FvFm). The chlorophyll fluorescence data supported the gas exchange measurements and are consistent with reduced photosynthetic performance of leaves coated with coal dust.     

Sorption of tylosin on clay minerals

The equilibrium sorption of tylosin (TYL) on kaolinite and montmorillonite was measured at different solution pH using batch reactor systems. The results showed that all the sorption isotherms were nonlinear and that the nonlinearity decreased as the solution pH increased for a given clay. At a specific aqueous concentration, the single-point sorption distribution coefficient (K_D) of TYL decreased rapidly as the solution pH increased. A speciation-dependent sorption model that accounted for the contributions of the cationic and neutral forms of TYL fit the data well, suggesting that the sorption may be dominated by both ion exchange and hydrophobic interactions. The isotherm data also fit well to a dual mode model that quantifies the contributions of a site-limiting Langmuir component (ion exchange) and a non-specific linear partitioning component (hydrophobic interactions). X-ray diffraction analyses revealed that the interlayers of montmorillonite were expanded due to the uptake of TYL. TYL molecules likely form a monolayer surface coverage.     

Sorption of acidic organic solute onto kaolinitic soils from methanol-water mixtures

The fate of the acidic organic solute from the soil-water-solvent system is not well-understood. In this study, the effect of the acidic functional group of organic solute in the sorption from cosolvent system was evaluated. The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) by three kaolinitic soils and two model sorbents (kaolinite and humic acid) were measured as functions of the methanol volume fractions (f (c) ≤ 0.4) and ionic compositions (CaCl(2) and KCl). The solubility of 1-NAPA was also measured in various ionic compositions. The sorption data were interpreted using the cosolvency-induced sorption model. The K (m) values (= the linear sorption coefficient) of NAP with kaolinitic soil for both ionic compositions was log linearly decreased with f (c). However, the K (m) values of 1-NAPA with both ionic compositions remained relatively constant over the f (c) range. For the model sorbent, the K (m) values of 1-NAPA with kaolinite for the KCl system and with humic acid for both ionic compositions decreased with f (c), while the sorption of 1-NAPA with kaolinite for the CaCl(2) system was increased with f (c). From the solubility data of 1-NAPA with f (c), no significant difference was observed with the different ionic compositions, indicating an insignificant change in the aqueous activity of the liquid phase. In conclusion, the enhanced 1-NAPA sorption, greater than that predicted from the cosolvency-induced model, was due to an untraceable interaction between the carboxylate and hydrophilic soil domain in the methanol-water system. Therefore, in order to accurately predict the environmental fate of acidic pesticides and organic solutes, an effort to quantitatively incorporate the enhanced hydrophilic sorption into the current cosolvency-induced sorption model is required.     

Cu sorption on Phragmites australis leaf and stem litter: a kinetic study

Decaying organic matter plays an important role in the cycling of metals in wetland ecosystems. Sorption kinetics of Cu(II) on Phragmites australis leaf and stem litter were studied. Fresh leaf and stem litter was sampled from a surface flow wetland at the end of the growing season. The effect of decomposition stage was studied with litter that had been decomposing for a period of 5 months. The Lagergren pseudo-first-order model, the pseudo-second-order model, the Elovich equation and two diffusion models based on spherical intra-particle diffusion were fitted to the experimental data. The sorption capacity was significantly affected by the decomposition of the litter. The sorption process was best described by the pseudo-second-order kinetics (R(2) approximately 0.99) but the rate constant was strongly dependent on the initial Cu concentration. The intra-particle diffusion model fitted the data only slightly less (R(2)>0.95) than the pseudo-second-order model. A theoretical comparison revealed that the good fit with the pseudo-second-order kinetics could be indicative of intra-particle diffusion. Sorption kinetics observed for the leaf and stem litter at different metal concentrations showed a fast initial sorption followed by a slow sorption phase.     

Dry deposition of airborne sulfate and nitrate to soybeans

Dry deposition contributes a substantial part of the total deposition of acidic pollutants and acid precursors to agricultural systems. However, because of the relative intractability of measurement of dry deposition fluxes, little work has been done to directly quantify dry inputs of pollutants to crops. In this research, foliar surface sampling ('leaf-washing') methods were developed and shown to be a practical and fairly precise means of monitoring the accumulation of dry-deposited SO4(2-) and NO3- on plant surfaces. Leaching of these ions from plant tissues was shown to be negligible; however, uptake by plants (e.g. stomatal gas exchange of SO2 or HNO3 and/or assimilation of surface accumulations of materials) is not accounted for by the sampling method. The significance of dry deposition to modification of the chemical microenvironment of leaf surfaces appears to be a factor of 3 to 20 or more greater than that of wet deposition alone. This is due to the cyclic reactivation of accumulated materials by dew and light rains, which may dissolve and mobilize, but not remove, the pollutant surface deposit. Therefore, while dry deposition of SO2 and SO4(2-) containing particles may contribute only part of the total mass of sulfur inputs to crop systems, the exposure of plant surface tissue to pollutants can be dominated by the dry-deposited material. The alteration of leaf surface chemistry may contribute to possible stress-producing mechanisms such as reduction of cuticular integrity, cellular injury and death, enhanced leaching of primary and secondary metabolites, and changes in pathogen infection efficiency.     

A statistical approach to estimate O3 uptake of ponderosa pine in a mediterranean climate

In highly polluted sites, stomatal behavior is sluggish with respect to light, vapor pressure deficit, and internal CO2 concentration (Ci) and poorly described by existing models. Statistical models were developed to estimate stomatal conductance (gs) of 40-year-old ponderosa pine at three sites differing in pollutant exposure for the purpose of calculating O3 uptake. Gs was estimated using julian day, hour of day, pre-dawn xylem potential and photosynthetic photon flux density (PPFD). The median difference between estimated and observed field gs did not exceed 10 mmol H2O m(-2) s(-1), and estimated gs within 95% confidence intervals. 03 uptake was calculated from hourly estimated gs, hourly O3 concentration, and a constant to correct for the difference in diffusivity between water vapor and 03. The simulation model TREGRO was also used to calculate the cumulative 03 uptake at all three sites. 03 uptake estimated by the statistical model was higher than that simulated by TREGRO because gas exchange rates were proportionally higher. O3 exposure and uptake were significantly correlated (r2>0.92), because O3 exposure and gs were highly correlated in both statistical and simulation models.     

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.     

Absorption of Gaseous Air Pollutants By a Standardized Plant Canopy

Concentration profiles for hydrogen fluoride(HF), sulfur dioxide(SO₂), ozone (O₃), nitrogen dioxide(NO₂), and nitric oxide(NO) generated in a standardized alfalfa canopy are presented. Wind, light, temperature, and carbon dioxide(CO₂) profiles, canopy pollutant uptake rates, and canopy structural data are also given. Canopy pollutant concentration profile characteristics were studied to evaluate the relative potentials for major air pollutants to penetrate into canopies. The study was conducted in an environmental growth chamber equipped to control automatically environmental conditions and monitor continuously gas exchange rates. HF, SO₂, and NO₂ profiles suggested that these gases were removed efficiently by the upper portion of the canopy as well as by the immediate subsurface vegetation. The steady state HF profile showed the greatest displacement within the canopy. The NO profile was displaced the least. The uptake rate of NO by plants was apparently too slow in comparison with gas transport and mixing within the canopy to affect the internal profile substantially. O₃ appeared to be readily deposited on the surface tissues, but the deeper tissues in the canopy had less effect on the concentration profile. Data are also presented to show the relationship between NO₂ concentration within the canopy and changes in the air concentration above the vegetation. The results indicated that gas transport between the atmosphere and canopy interior was rapid. The data presented should be of current interest to agriculturists, researchers, administrators, and environmental planners concerned with effects of air pollutants on plants and on the fate of pollutants in the microenvironment.     

The uptake of particulates by an urban woodland: site description and particulate composition

Woodlands may improve local air quality by increasing the uptake rates of gaseous, particulate and aerosol pollutants from the atmosphere and can also act as relatively permanent sinks for some pollutants. Rough Wood, Walsall was selected for a study of the material which accumulates on tree foliage because of its location in a densely populated urban area, and its proximity to a motorway with high traffic flow (the M6) and to other pollutant sources. Methods were developed for leaf washing to allow determination of the quantity of dust and the identification of the dust particles present on oak leaves. Elemental analysis of particles was also undertaken using scanning electron microscopy coupled with electron probe microanalysis. A large proportion of particles were organic in origin. Of the inorganic particles, the majority contained silicon and aluminium in varying proportions suggesting that they were soil derived. Some particles were clearly identified as the products of combustion, and sea or road salt was present on leaf surfaces. Some particles contained copper, tin and titanium which may reflect the proximity of Rough Wood to local metal workings. The number of particles counted on leaf surfaces decreased as distance from the motorway increased.     

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.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.