Specific Sorption Sites Research Articles

Simulating uranium sorption onto inorganic particles: The effect of redox potential

An analytical expression is proposed to simulate the effects of pH and redox potential (E) on the sorption of uranium onto model inorganic particles in aquatic environments instead of following an experimental approach providing a list of empirical sorption data. The expression provides a distribution coefficient (Kd) as function of pH, E and ligand concentration (complex formation) applying a surface complexation model on one type of surface sites (>SuOH). The formulation makes use of the complexation and hydrolysis constants for all species in solution and those sorbed at the surface, using correlations between hydrolysis constants and surface complexation constants, for the specific sorption sites. The model was applied for the sorption of uranium onto aluminol, iron hydroxide and silanol sites, mimicking respectively ‘clean’ clay or ‘dirty’ clay and ‘clean’ sand or ‘dirty’ sand (‘dirty’ referring to iron hydroxide contaminated), in absence or presence of carbonates in solution. The calculated distribution coefficients are very sensitive with the presence or absence of carbonates. The Kd values obtained by applying the model are compared with values reported in the literature for the sorption of uranium onto specific adsorbents. It is known that in surface water, U(VI) and its hydroxides are the primary stable species usually observed. However, reduction to U(IV) is possible and may be simulated during sorption or when the redox potential (E) decreases. Similar simulations are also applicable to study the sorption of other redox sensitive elements.

Calcium-deficient Hydroxyapatite as a Potential Sorbent for Strontium

A calcium (Ca)-deficient hydroxyapatite was investigated for its potential to remove Sr2+ from environmentally relevant water. We conducted sorption tests on solutions containing magnesium ion (Mg2+) and calcium ion (Ca2+) as competing cations at a strontium ion (Sr2+) concentration of 0.05 mmol/L. The Ca-deficient hydroxyapatite maintained a high Sr2+ sorption ratio of above 80% in the presence of Mg2+ and Ca2+ at the concentrations between 0.1 and 1.0 mmol/L, whereas the stoichiometric hydroxyapatite showed a lower ratio even in the presence of small amounts of Mg2+ and Ca2+ (72% for Mg2+ and 51% for Ca2+ at 0.1 mmol/L). For solutions with various Sr2+ concentrations between 0.01 and 10 mmol/L, Ca-deficient hydroxyapatite exhibited a higher Sr2+ sorption ratio than stoichiometric hydroxyapatite. The bonding states of Sr2+ on the Ca-deficient hydroxyapatite were evaluated by extended X-ray absorption fine structure measurements. The results indicated that there are specific sorption sites in Ca-deficient hydroxyapatite where Sr2+ is stably and preferentially immobilized.

Sorption of polychlorinated biphenyls onto biochars derived from corn straw and the effect of propranolol

The sorption of three polychlorinated biphenyls (PCBs) in single-solute and bi-solute systems in the presence of propranolol was studied on biochars at pyrolyzing temperatures of 200°C (BC200) and 700°C (BC700). Hydrophobicity and molecular planarity played a major role in PCB sorption onto BC200 and BC700, respectively. The steric hindrance caused by non-planarity made the strong specific sorption sites on BC700 less accessible to nonplanar PCBs. In bi-solute systems for BC200, propranolol monomers at an initial concentration (Cinit) of 0.8mg/L inhibited the sorption of PCB4 by competing for sorption sites. Propranolol at Cinit larger than 1.2mg/L could form hemimicelle structures on the biochar surface, providing a favorable phase for PCB4 partitioning, thereby increasing Koc up to 1.15 times. For BC700, propranolol prohibited PCB4 sorption mainly by pore-blocking, with the log Koc being reduced from 4.92 to 3.94. This study informs the application of biochar in mixture-contaminated environment.

Neutral and ionic per- and polyfluoroalkyl substances (PFASs) in atmospheric and dry deposition samples over a source region (Tianjin, China)

Per- and polyfluoroalkyl substances (PFASs) were detected in the atmosphere of a source region in Tianjin, China. Fluorotelomer alcohols (FTOHs) were the dominant neutral PFASs in the atmosphere with total concentrations of 93.6-131 pg/m3 and 8:2 FTOH contributing the most, whereas perfluorooctane sulfonamide derivatives (PFOSAs) were two magnitudes lower or undetected. In comparison, ionic PFASs (perfluoroalkyl carboxyl acids (PFCAs)) in the atmosphere were detected at similar or even higher levels. At wastewater treatment plants (WWTPs), the air over influent was found with higher levels of FTOHs than over aeration tank and effluent; whereas in the air over the aeration tank, the concentrations of PFOSAs and nonvolatile ionic PFASs substantially increased, suggesting a possible direct release of ionic PFASs to the atmosphere besides the atmospheric conversion from volatile precursors. In the air phase, a low proportion (1-5%) of PFCAs was subjected to dry deposition in the source region. Interestingly, the dry-deposition-to-bulk-air ratios of PFCA analogues were the lowest at medium chain lengths (C8 and C9) and increased with either shorter or longer chain length. The extraordinary affinity of shorter-chain PFCAs (C6-C7) to particles was presumed to be due to their smaller molecular size favoring the interactions between the carboxyl head groups and specific sorption sites on particulate matter.

Sorption of volatile organic compounds and their mixtures on montmorillonite at different humidity

The vapor-phase sorption of volatile organic compounds (VOCs), i.e. n-hexane, benzene and methanol, along with sorption of their binary mixtures, i.e. benzene/n-hexane and benzene-methanol, on montmorilllonite with different water content was studied. The absolutely dry mineral did not exhibit selectivity towards the studied VOCs sorbed separately. The hydration inhibited sorption of hydrocarbons and promoted that of methanol because of intercalation of its molecules to the interlayer space of the swelling mineral and dissolution in the water films on the external mineral surface. Unlike separate sorption of benzene and n-hexane, sorption of their binary mixture on the montmorillonite, even equal by volume, was selective. The components shared the same sorption sites with benzene being more active due to its ability to form the donor–acceptor complexes with the mineral surface in addition to Van-der-Waals interactions. Opposite, in the benzene/methanol mixture the undoubted predominance of hydrophilic methanol over benzene was revealed, which increased with increasing humidity and was significantly stronger compared to the differences in sorption of methanol and benzene sorbed separately. In the binary mixtures unequal by volume, preadsorption played an important role in VOCs competition with sorption of aliphatic n-hexane being suppressed stronger than that of aromatic benzene. In the benzene/methanol mixture, methanol was predominantly sorbed at all the studied volume ratios and hydration degrees, occupying its specific sorption sites. Hydration of the montmorillonite caused the reverse impact on the sorption of benzene and methanol. As a result, at the full hydration state methanol sorption in the mixture reached that of the pure methanol.

Modeling Sorption of Neutral Organic Compound Mixtures to Simulated Aquifer Sorbents with Pseudocompounds

The feasibility of the ideal adsorbed solution theory (IAST) in reducing the complexity associated with predicting the sorption behaviors of 12 neutral organic compounds (NOCs) contained in complex mixtures as a fewer number (four to six) of pseudocompounds (groups of compounds) to simulated aquifer sorbents was investigated. All sorption isotherms from individual- and multiple-pseudocompound systems were fit reasonably well ( ≥ 0.953) by the Freundlich sorption model over the range of aqueous concentrations evaluated (i.e., ≤200 μmol L). The presence and magnitude of mutual competition among pseudocompounds varied depending on the composition of the mixtures (i.e., concentrations and polarities of pseudocompounds) and the properties of sorbents (i.e., the fraction of organic carbon and the availability of hydrophilic specific sorption sites). Finally, comparisons between the IAST-based predictions with individual-pseudocompound sorption parameters and experimentally measured data revealed that the accuracy in predicting the sorption behaviors of several NOCs in terms of a fewer number of pseudocompounds decreased with increasing deviations from the assumption of equal and ideal competition in the IAST (i.e., differential availability of sorption sites and nonideal competitions among pseudocompounds).

Time-dependent changes of phytoavailability of Cs added to allophanic Andosols in laboratory cultivations and extraction tests

Although it is well known that phytoavailability of radiocaesium is gradually lost after its deposition on the ground by fixation to soil minerals, the decreasing rates during early period after the deposition is not yet quantitatively evaluated. In this study, stable Cs was added to 5 types of soil, including Andosols, a sand-dune regosol and a smectic lowland soil, in a laboratory soil incubation experiment to assess the aging effect of radiocaesium. Aliquots of a soil sample were put into pots and incubated in an artificial climate chamber. Orchardgrass or red clover was cultivated for 28 d in soil pots containing one of the allophanic Andosol samples seven times during about 1200 d using new pots for each cultivation. The soil-to-plant transfer factors of Cs declined exponentially until about 100 d and were almost constant thereafter. The extractabilities of Cs by water and 1 M NH4OAc solution from this allophanic Andosol soil sample also decreased with time and their decreasing patterns were similar to that of the transfer factor. The temporal changes of extractabilities of Cs in other soil samples were also examined 6 times during about 600 d. Rate of decline for the extracted yield of the added Cs by 1 M NH4OAc varied widely among all the soil types. Two allophanic Andosol samples showed relatively higher extractabilities in comparison with the other soils throughout the incubation experiment, which may be attributable to the lower contribution of Cs specific sorption sites to total cation exchange capacity of the allophonic Andosol soil samples.

Salinity increases the mobility of Cd, Cu, Mn, and Pb in the sediments of Yangtze Estuary: Relative role of sediments’ properties and metal speciation

Batch leaching experiments, Freudlich isotherm, correlation analysis (CA) and principal component analysis (PCA) were undertaken to explore the mechanisms that govern the release of sediment–associated metals (i.e. Cd, Cu, Mn and Pb) under the salinity stress in the Yangtze River Estuary. Special attention has been paid to the role of sediments’ physico-chemical properties and metal chemical speciation. The increase of salinity promoted the metal mobility which followed the order: Cd>Mn>Cu>Pb. Sediments properties (e.g., particle component and organic carbon) governed the mobility of Cd; metal chemical speciation controlled the release of Mn, while the mobility of Cu and Pb were simultaneously affected by the two factors. Different metal release mechanisms caused by salinity changes might be explained by: the chloro-complexation for Cd, the encouragement of acidity changes for Mn, and the high affinity to Fe–Mn oxides, organic substances and specific sorption sites in the sediments for Cu and Pb. Under salinity effect, Cd and Mn exhibited higher ecological risk and mobility, while Cu and Pb seemed to be more conservative.

Competitive sorption and desorption of cadmium and lead in paddy soils of eastern China

To assess the competitive sorption and desorption of cadmium (Cd) and lead (Pb), batch equilibrium experiments were performed using single- and binary-metal solutions in surface samples of three paddy soils from eastern China. Sorption isotherms were well fitted with one-metal and competitive Langmuir equation for single- and binary-metal system, respectively. The distribution coefficient (Kd) values were Kd single (Pb) > Kd binary (Pb) > Kd single (Cd) > Kd binary (Cd), indicating that Pb was stronger sorbed by these soils than Cd in binary metal system. Soils with high pH and clay content had the greatest sorption capacity as estimated by the maximum sorption parameter (Q). The co-existence of both metals reduces their tendency of sorption, whereas Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (b) in binary sorption system was greater than that in single sorption system for all soils (b < b1), indicating that competition for sorption sites promote the retention of both metals into more specific sorption sites. Sorption of Cd and Pb decreased soil pH by 1.61 U for YRS, 1.39 U for PCS, and 0.91 U for SLS. The decreases of pH in binary metal system were greater than in single-metal system for three soils. Cadmium and Pb desorption increased with increasing Cd and Pb sorption saturation for all soils; however, Cd desorption ratio in binary metal system (dCd*) was much greater than Pb (dPb*), indicating that under the competitive sorption conditions, the sorbed Cd was more readily desorbed from the soils than the sorbed Pb.

Effects of pH and low molecular weight organic acids on competitive adsorption and desorption of cadmium and lead in paddy soils

The bioavailability and ultimate fate of heavy metals in the environment are controlled by adsorption-desorption process. Batch equilibrium experiments were performed to assess the effects of pH and low molecular weight organic acids (LMWOAs) on competitive adsorption and desorption of cadmium and lead in paddy soils from China. The results indicated that both soils exhibited greater sorption capacity for lead (Pb) (1.37-1.61-fold) than cadmium (Cd) as estimated by the maximum sorption parameter (Q) from the Langmuir equation. The Langmuir bonding energy coefficient (b) and distribution coefficient (K (d)) were greater for Pb than for Cd, furthermore, b (binary) and K (d) (single) were greater than b (single) and K (d binary), indicating that competition for sorption sites promote the retention of both metals on more specific sorption sites. Both Cd and Pb desorption as a function of solution pH was characteristic of "S" pattern. The presence of LMWOAs inhibited Cd or Pb desorption at the low concentrations (≤0.1 mmol L(-1)) but promoted Cd and Pb desorption at higher concentrations (≥0.5 mmol L(-1) for citric acid and ≥1 mmol L(-1) for malic and oxalic acid). The two paddy soils had a greater d (Cd) than d (Pb) in the presence of LMWOAs, indicating that Cd desorption was more affected by the presence of LMWOAs in binary metal system.

Effect of glycerol and corn oil on physicochemical properties of polysaccharide films – A comparative study

The aim of this work was to evaluate the influence of glycerol and corn oil on physicochemical properties of polysaccharide-based films. The polysaccharides used were galactomannan from Gleditsia triacanthos and chitosan. Fourier-transform infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis were performed, together with determinations of moisture content, solubility, water vapor permeability and mechanical properties. Structure–properties relationships were established, relating the two polysaccharides’ structures with the way they interact with water, other film’s constituents (glycerol and oil) and the resulting properties. The presence of glycerol and corn oil originated a more hydrophilic structure and a decreased affinity of the film matrix to water, respectively, in both polysaccharides. However, the two polysaccharides presented different behaviors in terms of glass transition temperature, water vapor permeability and elongation-at-break that have been related with the particularities of their structure: while for the galactomannan the specific sorption sites for water are the O–H groups, for chitosan those are O–H and/or NH 2 groups. The present work provides insight regarding the physicochemical properties of polysaccharide-based films and established relationships with polymers’ structure, showing that the two polysaccharides studied here have adequate properties to be used as packaging materials for specific food applications.

Cs sorption to potential host rock of low-level radioactive waste repository in Taiwan: Experiments and numerical fitting study

A reliable performance assessment of radioactive waste repository depends on better knowledge of interactions between nuclides and geological substances. Numerical fitting of acquired experimental results by the surface complexation model enables us to interpret sorption behavior at molecular scale and thus to build a solid basis for simulation study. A lack of consensus on a standard set of assessment criteria (such as determination of sorption site concentration, reaction formula) during numerical fitting, on the other hand, makes lower case comparison between various studies difficult. In this study we explored the sorption of cesium to argillite by conducting experiments under different pH and solid/liquid ratio ( s/ l) with two specific initial Cs concentrations (100 mg/L, 7.5 × 10 −4 mol/L and 0.01 mg/L, 7.5 × 10 −8 mol/L). After this, numerical fitting was performed, focusing on assessment criteria and their consequences. It was found that both ion exchange and electrostatic interactions governed Cs sorption on argillite. At higher initial Cs concentration the Cs sorption showed an increasing dependence on pH as the solid/liquid ratio was lowered. In contrast at trace Cs levels, the Cs sorption was neither s/ l dependent nor pH sensitive. It is therefore proposed that ion exchange mechanism dominates Cs sorption when the concentration of surface sorption site exceeds that of Cs, whereas surface complexation is attributed to Cs uptake under alkaline environments. Numerical fitting was conducted using two different strategies to determine concentration of surface sorption sites: the clay model (based on the cation exchange capacity plus surface titration results) and the iron oxide model (where the concentration of sorption sites is proportional to the surface area of argillite). It was found that the clay model led to better fitting than the iron oxide model, which is attributed to more amenable sorption sites (two specific sorption sites along with larger site density) when using clay model. Moreover, increasing s/ l ratio would produce more sorption sites, which helps to suppress the impact of heterogeneous surface on Cs sorption behavior under high pH environments.

Dihydrogen adsorption isotherms (77 K) on carbon nanomaterials

Dihydrogen adsorption at 77 K on a number of fine-particle carbon materials, activated carbons, and carbon nanotubes has been investigated. The micropore structure parameters of these materials have been determined using a volumetric comparative method and nonlocal density functional theory (NLDFT). These data processing methods lead to different values of textural parameters. This difference is attributed to the presence of specific sorption sites on the surface of real carbon materials. The pore size range in which the NLDFT method is applicable to the C-H2 system has been determined. A comparison between the hydrogen sorption properties of different carbon nanotubes is presented.

Sorption and Selectivity Sequences of Cd, Cu, Ni, Pb, and Zn in Single- and Multi-Component Systems in a Cultivated Chilean Mollisol

The heavy-metal sorption ability of soils is one of the most important factors that determine the fate of these contaminants in this medium of the biosphere. When heavy-metal containing soil amendments are land applied, a multi-component soil-solution equilibrium may occur in which various metals compete simultaneously for the sorption sites on the soil particles. In order to determine the effect of competition among Cd, Cu, Ni, Pb, and Zn on sorption characteristics and the selectivity sequence of those heavy metals in a cultivated Mollisol of central Chile, batch sorption experiments were carried out in single- and multi-component systems. Heavy metal sorption isotherms in both types of system were well described by the Langmuir's equation. For all the metals evaluated, competition among them (multi-component system) decreased both the maximum sorption capacity, obtained from the Langmuir's isotherm, and the partition coefficient (Kd) compared to the single-component system. In addition, the simultaneous presence of the five metals promoted the sorption of Cd, and to a lesser extent of Ni, on more specific sorption sites of soil particles. Either in single- or multi-component system, Pb and Cu showed a higher selectivity and retention compared to Cd, Ni and Zn, which indicates that the later heavy metals would present a higher mobility in the soil-plant-water system. Since Langmuir's parameters and Kd were highly affected by competition for all heavy metals evaluated, the use of single-component parameters in modeling assessment might lead to an incorrect description of the transport and fate of these contaminants in receiving Mollisols.

Adsorption-Desorption Kinetics of Zn in Soils

The reactivities of heavy metals such as zinc in the soil environment are affected by several rate-limiting processes, including kinetic sorption and release reactions. In this study, kinetic batch experiments were carried out to evaluate sorption and desorption of Zn for soils having different properties. Sorption isotherms exhibited strong nonlinearity as well as kinetic behavior. Distinct differences in the amounts of Zn sorbed among the different soils were observed where lowest sorption was associated with acidic soils (Windsor and Olivier) soil. In contrast, Webster (neutral) soil exhibited highest sorption capacity. Discrepancies between adsorption and successive desorption isotherms indicate considerable hysteresis for Zn release, the extent of which varied among the three soils. For the two acidic soils, Zn release as a percentage of that total sorbed was 47% to 51% and 42% to 49% for the Windsor and Olivier soils, respectively; whereas for the neutral soil, only 9% to 11% of sorbed Zn was released over time. A second objective was to test the hypothesis that phosphate addition to soils increases Zn adsorption. The influence of the presence of P on increased Zn sorption was clearly manifested by the isotherms where similar trends were observed for all three soils. Moreover, P additions reduced Zn desorption, which indicates that the presence of P increased the affinity or specific sorption sites for Zn. A multireaction model that accounts for nonlinear equilibrium and kinetic retention reactions was successfully used to simulate the time-dependent behavior of Zn sorption-desorption for all three soils and at different P levels. Moreover, the addition of different levels of P did not affect the kinetic sorption-desorption behavior of Zn in all soils.

Competitive sorption of lead and cadmium onto sediments

Single- and bi-solute competitive sorptions of Pb and Cd onto sediments were investigated. In single-solute sorption, Khan model was fitting better than the other models such as Freundlich, Langmuir, Dubinin–Radushkevich, Sips, Redlich–Peterson and Kargi–Ozmıhcı models. In bi-solute sorption, competition between the solutes reduced the sorbed amount of each solute compared with that in the single-solute system. Langmuir model parameters for single-solute ( q mL and b L ) and bi-solute ( q m L * and b L * ) competitive sorptions were compared. Sediment with higher pH, CEC and BET surface area had higher maximum sorption capacity ( q m L ) . In all sediments, maximum sorption capacity ( q m L ) of Pb was higher than that of Cd, and the presence of both metals reduced the tendency to be sorbed although Cd sorption was more affected than Pb. The b L * values of Pb decreased while those of Cd increased indicating that competition for sorption sites promotes the retention of Cd on more specific sorption sites. The competitive Langmuir model (CLM) and ideal adsorbed solution theory (IAST) coupled to the single-solute sorption models predicted Pb sorption in bi-solute competitive sorption favorably but not Cd sorption.

Interaction of the Macrolide Antimicrobial Clarithromycin with Dissolved Humic Acid

The association of the cationic macrolide antimicrobial clarithromycin (CLA) with dissolved Elliot soil humic acid (ESHA) was investigated as a function of solution chemistry. CLA-ESHA association was strongly pH-dependent, reaching a maximum near pH 6.5, and was modeled successfully using FITEQL as a 1:1 complexation reaction between CLA+ and discreet deprotonated acidic functional groups with pKa values of 4 and 6. Approximate order of magnitude increases in ionic strength produced approximately 10-fold decreases in CLA+ -ESHA association. Coefficients for CLA+ -ESHA association were significantly smaller in the presence of K+ vs Na+. Sorption data were well-fit by the Freundlich model; the Freundlich exponent was <1, suggesting CLA+ interacted with sites having a range of binding energies. Sorption appeared largely reversible; little sorption-desorption hysteresis was observed. The affinities of erythromycin and CLA+ for ESHA association sites were indistinguishable, suggesting interaction with specific sorption sites. Comparison of experimentally determined CLA-ESHA association coefficients with those predicted from single-parameter linear free energy relationships based on log Kow suggested limited contribution of hydrophobic interactions to CLA-ESHA association at environmentally relevant pH values. CLA-ESHA association constants were similar in magnitude (10(3.9)-10(4.6) to those of many nonpolar organic contaminants, and macroscopic binding data were consistent with cation exchange dominating CLA+ -ESHA association.

Effects of Crystal Modification on the Binding of Trace Metals and Arsenate by Goethite (7 pp)

Dedicated to Prof. Dr. Ulrich Forstner on his 65th birthday Goethite (α-FeOOH) as the most frequently occurring iron oxide in the environment plays a significant role in the binding of inorganic pollutants. Accordingly, synthetic goethite is used for the purification of contaminated water. Goethite crystals can be prepared in different shape as porous and non-porous forms. The mineral can also be modified by partial substitution of structural Fe+3 for different foreign elements. The biggest possible substituent known so far is Cd+2 which causes a strong expansion of the unit-cell parameters. An incorporation of Pb+4 generates a permanent positive charge. Goethites with these morphological and structural modifications were selected for sorption experiments with Co2+, Ni2+, Zn2+, Cd2+, Pb2+, and arsenate. It was intended to demonstrate the potential of mineral modification for improving sorption properties. Batch sorption studies were carried out combining each mineral with a single element at different pH and reaction times. Cations were investigated at a single initial concentration only while arsenate was tested over a range of concentrations in order to establish sorption isotherms. The sorption step was followed by an extraction step to characterize time dependent immobilization reactions. A time dependent increase of trace metal and arsenate sorption is attributed to a migration of ions into pores of star-shaped goethite and to a binding by specific sorption sites at the surface. The migration into pores is related to the size of adsorbing cations. The almost identical sorption behaviour of Ni2+ and Co2+ on pure goethite is contrasted by a strong preference of Co over Ni on Cd-goethite. Expansion of the unit-cell dimensions in Cd+2 substituted goethite generates highly specific binding sites at the surface. These are accessible to Co and Zn only. A permanent positive charge in Pb+4 substituted goethite reduces the binding of cations and doubles the sorption capacity for arsenate. Pb-goethite also contains a limited portion of highly specific sites which can only be accessed by Zn2+. Immobilization takes place even after a short contact time of 16 hours. This process results in a growing fraction of non-extractable metals and arsenate with reaction time. Pores and foreign elements in the goethite structure greatly affect the reactivity of the mineral and the ability to immobilize inorganic pollutants. A possible mechanisms for the preferred sorption of Co and Zn by Cd-goethite is seen in the ability of these metal ions to adopt a smaller size: Co by oxidation of Co2+ to Co3+ and Zn by tetrahedral coordination of Zn2+. This kind of binding can be viewed as structural incorporation. The binding properties of modified goethites can well be characterized by sorption tests including an array of elements with different ionic size and charge. There is considerable potential for designing goethite modifications with improved surface reactivity for specific purposes such as water purification and possibly catalysis of reactions.

Hydration mechanism of polysaccharides: A comparative study

AbstractWater sorption was studied at 20 °C on films composed of different natural polymers. Three polysaccharides were investigated: chitosan, cellulose, and alginate. The major differences between these polymers, from a structural point of view, lay in the substitution of an OH group by an NH2 function for chitosan and by an ionic COO−Na+ group for alginate. An analysis of the experimental water sorption isotherms, expressed as the number of water molecules sorbed per repeating unit in the amorphous phase, associated with an analysis of the enthalpy profile related to the water sorption allowed us to propose a water sorption mechanism in two steps for all the polymers: water sorption on polymer‐specific sites in the first step and water clustering around the first sorbed water molecules in the second step. It was determined that two water molecules interacted with the polymer chains for cellulose and chitosan, whereas four water molecules were bonded to alginate chains. The specific sorption sites were identified as OH groups for cellulose, OH and NH2 groups for chitosan, and ionic and OH groups for alginate. A systematic reduction of the half‐sorption time was observed in the activity range corresponding to this first sorption step, and it was explained by a water plasticization effect. On the other hand, an increase in the half‐sorption time was observed in the second sorption step, at a high activity (&gt;0.8), for chitosan and alginate. A modelization associating the Guggenheim–Anderson–de Boer model and the clustering theory, applied to our systems, allowed us to relate the occurrence of this last phenomenon to the formation of water clusters containing more than two water molecules. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 48–58, 2005

Heavy metal distribution between fractions of humic substances in heavily polluted soils

Soil organic matter is important in controlling heavy metal behaviour in soils. This study aims to determine the distribution of organically bound Cd, Pb, and Zn between humic and fulvic acids in 20 samples of heavily polluted Fluvisols. Traditional procedure of alkaline sodium hydroxide/pyrophosphate extraction of humic substances with consequent humic acids precipitation by acidification was used. All of the three metals were bound predominantly on fulvic acids (mean share was 98.4, 82.0, and 95.7% of total organically bound Cd, Pb, and Zn content, respectively). Mainly the level of pollution controlled the amount of metals bound on fulvic acids. On humic acids, a limited amount of specific sorption sites for the metals is expected. Lead content bound on humic acids was negatively correlated with soil pH. The results suggest relatively high potential mobility of organic fractions of heavy metals in soils under this study. The selectivity of alkaline extracting agent is briefly discussed.