New Sorption Isotherms Derived from a Gamma Distribution of Binding Constants.

New sorption isotherms for heterogeneous sorbents are derived by combining a Gamma distribution of binding constants with a local isotherm defined by a Langmuir or Hill equation. The new "Gamma isotherms" are expressed as Stieltjes transforms of the distribution and involve generalized exponential integrals. The related energy distributions are asymmetric and present a peak corresponding to the mean binding constant. The advantages of the new isotherms are (1) at low pressures or concentrations, with a Langmuir local isotherm, the global "Gamma-Langmuir" isotherm retrieves Henry's law; (2) contrary to the power Freundlich or hypergeometric Freundlich global isotherms, these Gamma isotherms do not need a redefinition of the standard state; (3) with a Hill local isotherm, the global "Gamma-Hill" isotherm allows a separate estimation of the cooperativity and heterogeneity parameters; and (4) the condensation approximation is a good approximation if the local isotherm is Hill and displays a high degree of cooperativity. The Gamma-Langmuir model is applied to three examples from the literature, with rather different Gamma distributions.

Proton binding to humic nano particles: electrostatic interaction and the condensation approximation.

Proton binding to "carboxylic" and "phenolic" sites of humic nano particles (HNPs) is determined by the total proton affinity that is due to a specific and an electrostatic affinity. Both affinities are accounted for in the bi-modal Langmuir-Freundlich (bi-LF)-equation extended with a Boltzmann factor that includes the electrostatic site potential(s), y. For y → 0 the equation reduces to the bi-LF Master Curve (MC). Commonly, an electrical double layer model is used to obtain y, e.g., the bi-LF-Donnan-Vapp (monocomponent NICA-Donnan) model and bi-LF-soft-particle-Poison-Boltzmann-Theory (SPBT). A new method is presented that combines the "condensation approximation" (CA) with the MC concept (CA-MC). With the CA, the proton binding curve and MC can be transformed in, respectively, the total and specific affinity distribution. The difference at a given charge density provides the electrostatic affinity and CA-potentials vs. charge density. The MC can be obtained theoretically or by using the convention that the electrostatic interaction is negligible at 1 M salt concentration. For five HNPs CA-potentials corresponding with the bi-LF-SPBT are compared with results of the bi-LF-Donnan-Vapp model using the MC(SPBT). The bi-LF-Donnan-Vapp model fails when the Debye length > hydrated particle radius. The CA-MC(1M) method does not require characteristics of the HNPs. Combination of the bi-LF-eq. with the CA-MC(1 M) method gives the bi-LF-CA-MC(1 M) model. The CA-MC(1 M) differs from the MC(SPBT); therefore, resulting parameters can only be compared when the same method is used.

Facet-dependent surface charge and Pb2+ adsorption characteristics of hematite nanoparticles: CD-MUSIC-eSGC modeling.

Accurate prediction of the environmental fate of Pb depends on the understanding of Pb coordination to mineral surfaces. Here, the proton and Pb adsorption and speciation on hematite nanocrystals with different exposed crystallographic facets were investigated. High-resolution transmission electron microscopy images revealed that hematite nanoplates (HNP) were of 75.3 ± 9.5% (001) facets and 24.6 ± 9.3% (012) facets, while hematite nanocubes (HNC) were of 76.0 ± 11.1% (012) facets and 24.0 ± 3.2% (110) facets. Our modeling results revealed that the proton affinity constant (log KH) of ≡FeOH-0.5 and ≡Fe3O-0.5 was 7.8 and 10.8 on hematite (012) facets, and changed to 7.7 and 11.7 on (110) facets, respectively. Owing to the different atomic arrangements, (012) facets not only have higher adsorption performance for Pb, but also present a greater dependence on pH than (110) facets. Additionally, our modeling further indicated that (012) facets bind Pb via both bidentate and tridentate complexes, while (110) facets bind Pb only through bidentate complexes at pH 3.0-6.5. These results facilitate a more detailed understanding of the complex species of Pb on hematite surface while also provide new insight into the reactivity mechanism of individual hematite facets.

Proton and Copper Binding to Humic Acids Analyzed by XAFS Spectroscopy and Isothermal Titration Calorimetry.

Proton and copper (Cu) binding to soil and lignite-based humic acid (HA) was investigated by combining X-ray absorption fine structure (XAFS) spectroscopy, isothermal titration calorimetry (ITC), and nonideal-competitive-adsorption (NICA) modeling. NICA model calculations and XAFS results showed that bidentate and monodentate complexation occurred for Cu binding to HA. The site-type-specific thermodynamic parameters obtained by combining ITC measurements and NICA calculations revealed that copper binding to deprotonated carboxylic-type sites was entropically driven and that to deprotonated phenolic-type sites was driven by entropy and enthalpy. Copper binding to HA largely depended on the site-type and coordination environment, but the thermodynamic binding mechanisms for Cu binding to the specific site-types were similar for the different HAs studied. By comparing the site-type-specific thermodynamic parameters of HA-Cu complexation with those of low molar mass organic acids, the Cu coordination could be further specified. Bidentate carboxylic-Cu complexes made the dominating contributions to Cu binding to HA. The present study not only yields molecular-scale mechanisms of ion binding to carboxylic- and phenolic-type sites of HA but also provides the new insight that the universal nature of site-type-specific thermodynamic data enables quantitative estimation of the binding structures of heavy metal ions to humic substances.

CD-MUSIC-EDL Modeling of Pb2+ Adsorption on Birnessites: Role of Vacant and Edge Sites.

The surface complexation modeling of metal adsorption to birnessites is in its infancy compared to the charge-distribution multisite ion complexation (CD-MUSIC) models for iron/aluminum (hydr)oxides. Therefore, using X-ray diffraction with Rietveld refinement to obtain the reactive sites and their densities, a CD-MUSIC model combined with a Stern-Gouy-Chapman electrical double layer (EDL) model for the external surface and a Donnan model for the interlayer surface is developed for birnessites with different Mn average oxidation state (MnAOS). Proton affinity constants and the charge distributions of Pb surface complexes were calculated a priori. By fitting Pb adsorption data to the model the obtained equilibrium constants (log KPb) of Pb complexes were 6.9-10.9 for the double-corner-sharing and double-edge-sharing Pb2+ complexes on the edge sites and 2.2-6.5 for the triple-corner-sharing Pb2+ complex on the vacancies. The larger log KPb value was obtained for higher MnAOS. Speciation calculations showed that with increasing MnAOS from 3.67 to 3.92 the interlayer surface contribution to the total Pb2+ adsorption increased from 43.2% to 48.6%, and the vacancy contribution increased from 43.9% to 54.7%. The vacancy contribution from interlayer surface was predominant. The present CD-MUSIC-EDL model contributes to understand better the difference in metal adsorption mechanism between birnessite and iron/aluminum (hydr)oxides.

Effect of Soil Fulvic and Humic Acids on Pb Binding to the Goethite/Solution Interface: Ligand Charge Distribution Modeling and Speciation Distribution of Pb.

The effect of adsorbed soil fulvic (JGFA) and humic acid (JGHA) on Pb binding to goethite was studied with the ligand charge distribution (LCD) model and X-ray absorption fine structure (XAFS) spectroscopy analysis. In the LCD model, the adsorbed small JGFA particles were evenly located in the Stern layer, but the large JGHA particles were distributed over the Stern layer and the diffuse layer, which mainly depended on the JGHA diameter and concentrations. Specific interactions of humic substances (HS) with goethite were modeled by inner-sphere complexes between the -FeOH20.5+ of goethite and the -COO- of HS and by Pb bridges between surface sites and COO- groups of HS. At low Pb levels, nearly 100% of Pb was bound as Pb bridges for both JGFA and JGHA. At high Pb levels and low HS loading, Pb-goethite almost dominated over the entire studied pH range, but at high HS loading, the primary species was goethite-HS-Pb at acidic pH and goethite-Pb at alkaline pH. Compared with JGFA, there was a constant contribution of Pb bridges of about 10% for JGHA. The linear combination fit of EXAFS, using Pb-HS and Pb-goethite as references, indicated that with increased HS loading more Pb was bound to adsorbed HS and less to goethite, which supported the LCD calculations.

Influence of soil humic and fulvic acid on the activity and stability of lysozyme and urease.

Humic substances (HS), including humic acids (HA) and fulvic acids (FA), are important components of soil systems. HS form strong complexes with oppositely charged proteins, which will lead to changes in the enzyme activity. The effect of soil HS on the activity and stability of two enzymes was investigated as a function of pH, ionic strength, and mass ratio HS/enzyme. Humic acid (JGHA) and fulvic acid (JGFA) are negatively charged, lysozyme is net positive at pH values below 10.4, and urease is net positive below pH 5.2 or net negative above pH 5.2. The enzyme activities in the HS-enzyme complexes were suppressed when the enzymes were oppositely charged to the HS. The largest activity suppression was observed around the mass ratio HS/enzyme where the HS-protein complex was at its isoelectric point (IEP). At the IEP strong aggregation of the complexes led to encapsulation of the enzyme. The ionic strength was important; an increase decreased complex formation, but increased aggregation. Due to the larger hydrophobicity of JGHA than JGFA, the reduction in enzyme activity was stronger for JGHA. The enzyme stability also decreased maximally at mass ratio around the IEP of the complex when HS and protein were oppositely charged. When urease and HS were both negatively charged no complexes were formed, but the presence of JGHA or JGFA improved the activity and stability of the enzyme.

Lead binding to soil fulvic and humic acids: NICA-Donnan modeling and XAFS spectroscopy.

Binding of lead (Pb) to soil fulvic acid (JGFA), soil humic acids (JGHA, JLHA), and lignite-based humic acid (PAHA) was investigated through binding isotherms and XAFS. Pb binding to humic substances (HS) increased with increasing pH and decreasing ionic strength. The NICA-Donnan model described Pb binding to the HS satisfactorily. The comparison of the model parameters showed substantial differences in median Pb affinity constants among JGFA, PAHA, and the soil HAs. Milne's "generic" parameters did not provide an adequate prediction for the soil samples. The Pb binding prediction with generic parameters for the soil HAs was improved significantly by using the value n(Pb1) = 0.92 instead of the generic value n(Pb1) = 0.60. The n(Pb1)/n(H1) ratios obtained were relatively high, indicating monodentate Pb binding to the carboxylic-type groups. The nPb2/nH2 ratios depended somewhat on the method of optimization, but the values were distinctly lower than the n(Pb1)/nH1 ratios, especially when the optimization was based on Pb bound vs log [Pb(2+)]. These low values indicate bidentate binding to the phenolic-type groups at high Pb concentration. The NICA-Donnan model does not consider bidentate binding of Pb to a carboxylic- and a phenolic-type group. The EXAFS results at high Pb loading testified that Pb was bound in bidentate complexes of one carboxylic and one phenolic group (salicylate-type) or two phenolic groups (catechol-type) in ortho position.

Generic CD-MUSIC-eSGC model parameters to predict the surface reactivity of iron (hydr)oxides.

The surface reactivity of iron (hydr)oxides plays a crucial role in controlling their interfacial reactions, for which various surface complexation models have been developed. The diversity of mineralogical properties of iron (hydr)oxides has resulted in a redundancy of model parameters, which hampers the modeling of iron (hydr)oxides in soils and sediments, where goethite, hematite and ferrihydrite dominate the iron (hydr)oxide mass fraction. To capture their combined surface reactivity, optimized generic protonation parameters of the Charge Distribution-Multisite Complexation (CD-MUSIC) extended-Stern-Gouy-Chapman (eSGC) model were derived by reanalyzing literature datasets and tested with some newly synthesized iron (hydr)oxides. It was observed that the proton and monovalent ion affinity constants of the different iron (hydr)oxides were located in a narrow range. For the singly- and triply-coordinated hydroxyl sites the obtained generic log(affinity constants) were 8.3 and 11.7 for the protonation reaction and -0.5 for the reaction with the monovalent background ions. Their combination with fixed site densities of singly-/triply-coordinated hydroxyl sites of 3.45/2.70, 5.00/2.50, and 5.80/1.40 sites/nm2 for goethite, hematite, and ferrihydrite, respectively, provided good results. The Stern layer capacitances of the inner and outer Stern layers were set equal and could be acquired by an empirical correlation with the sample specific surface area (SSA). The CD-MUSIC-eSGC model with the generic model parameters enables good quality predictions of the proton reactivity of iron (hydr)oxides in 1:1 electrolyte solutions regardless of the sample heterogeneity. The advantages of the generic CD-MUSIC-eSGC model are twofold: (1) protonation of iron (hydr)oxides can be described without making use of spectroscopic measurements and proton titrations, and (2) the model calculations are greatly simplified.

Effect of humic acid on lysozyme interaction with montmorillonite and kaolinite.

Humic acid (HA) as a soil natural organic matter (NOM) can participate in the interaction between proteins and clay minerals, depending on clay type, HA and protein content, and solution conditions. The effect of HA on the interaction of lysozyme (LSZ) with kaolinite (Kao) and montmorillonite (Mont) was investigated at (initial) pHi 5 and 8. In the solutions containing both HA and LSZ, HA/LSZ complexes were formed with a net charge density depending on pH and HA/LSZ mass ratio f. LSZ adsorption on clays in the presence of HA is dominated by adsorption of HA/LSZ complexes. The HA/LSZ mass ratio (fIEP,pHi) at the isoelectric point (IEP) is pH dependent. At f fIEP,pHi the HA/LSZ complexes were negative, both conditions caused relatively high equilibrium concentrations of LSZ in solution that decreased with increasing initial LSZ concentration. The present results enhance our insight in protein soil interactions for the case that clay particles are brought in contact with aqueous solutions that contain modest amounts of both NOM and protein and stress the importance of the NOM/protein mass ratio and solution pH.

Spectroscopic investigation of conformational changes in urease caused by interaction with humic acid.

Urease in soil interacts with humic acid (HA), which results in a change of the enzymatic activity and stability. However, knowledge on the conformational change of urease in the presence of HA is still lacking. Therefore, the structure of urease (net zero charge at pH 5.2) interacting with HA and the microenvironments of the tyrosine (Tyr) and tryptophane (Trp) residues were investigated at pH 6.7 and 8.0 and 0.5 and 50 mmol L-1 KCl using spectroscopic techniques. Fluorescence intensity of urease was progressively inhibited by HA with increasing mass ratio f of HA/urease. Moreover, quenching of urease fluorescence by HA was strongest at pH 6.7 (and 50 mmol L-1 KCl) where the hydrophobic attraction was counteracted by only a weak electrostatic repulsion. HA exerted only a minor effect on the positions of the maximum excitation bands for Tyr and Trp residues, indicating insignificant changes in the microenvironment of these residues in the presence of HA. At pH 6.7, the amide I and amide II bands were inhibited by HA. Curve-fitting of the amide I band of urease in complexes indicated that the percentages of α-helix, ß-sheet and ß-turn were changed. At pH 8 HA had little effect on the circular dichroism and attenuated total reflectance Fourier transform infrared spectra of urease. At this pH the interaction between urease and HA was weak due to the relatively strong electrostatic repulsion and the conformational change was insignificant. The present results increase our understanding of negatively charged protein behavior in natural environments dominated by humic substances.

Conformational modifications of lysozyme caused by interaction with humic acid studied with spectroscopy.

Modification of enzyme/protein conformation will affect the activities and functionality of enzymes. Previous studies have shown that the activity of lysozyme (LSZ) in the presence of humic acid (HA) is largely determined by the mass ratio of HA/LSZ (f = mHA/mLSZ), pH and ionic strength. Here the interaction and conformation of LSZ in HA/LSZ-complex/aggregate (HA/LSZ-c/a) were investigated by spectroscopic techniques at (initial) pH 5 and 8 and ionic strength 5 mmol/L. The results indicated a strong interaction between HA and LSZ. Circular dichroism (CD), and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy showed that the helix content reached a minimum at the mass ratio of its iso electric point (IEP) at given initial pH, fIEP,pHi. The changes in ß-sheet and random coil of HA/LSZ-c/a were opposite with increasing f. The minimum of helix content at fIEP,pHi corresponded with the minimum LSZ activity and maximum aggregate size of HA/LSZ-c/a. UV-vis spectra and fluorescence measurements indicated that the amino acid residues (especially for tyrosine) in LSZ were in a more hydrophobic microenvironment before fIEP,pHi due to the formation of HA/LSZ-c/a, while were gradually exposed to a more polar microenvironment beyond fIEP,pHi with the disaggregation of HA/LSZ-c/a. HA and LSZ interaction caused a more hydrophobic microenvironment for the amino acid residues at initial pH 8. This study improves our understanding of enzyme/protein behavior in the natural environment.

Equilibrium mono- and multicomponent adsorption models: From homogeneous ideal to heterogeneous non-ideal binding.

Aqueous sorption processes play an important role in, for example, pollutant binding to natural nanoparticles, colloid stability, separation and enrichment of components and remediation processes. In this article, which is a tribute to Hans Lyklema, models of localized (ad)sorption of molecules and ions from aqueous solution on homogeneous and heterogeneous nanoparticles are presented. The discussed models range from ideal monocomponent sorption on homogeneous (Langmuir) and heterogeneous sites, to multicomponent ideal sorption on homogeneous and heterogeneous sites, multicomponent multisite ion complexation with charge distribution (CD-MUSIC) and non-ideal competitive adsorption on heterogeneous sites (NICA). Attention is also paid to lateral interaction, site-induced aggregation, binding stoichiometry and multilayer formation. Electrical double layer models are discussed in relation to ion binding on impermeable and permeable nanoparticles. Insight in models that can describe sorption of molecules and ions on nanoparticles leads to awareness of the limitations of using simple models for complex systems and is needed for the selection and application of an appropriate model for a given system. This is relevant for all practical sorption processes and for a better understanding of the role of natural nanoparticles in the binding of nutrients and pollutants.

Adsorption of heterogeneously charged nanoparticles on a variably charged surface by the extended surface complexation approach: charge regulation, chemical heterogeneity, and surface complexation.

Adsorption of randomly branched polyelectrolytes, "hairy" particles and internally structured macromolecules, collectively denoted as heterogeneously charged nanoparticles, on charged surfaces is important in many technological and natural processes. In this paper, we will focus on (1) the charge regulation of both the nanoparticle and the surface and (2) the surface complexation between the particle functional groups and the surface sites and will theoretically study the adsorption using the extended surface complexation approach. The model explicitly considers the electrochemical potential of a nanoparticle with an average (smeared-out) structure and charge both in bulk solution and on the surface to obtain the equilibrium adsorption. The chemical heterogeneity of the particle is described by a distribution of the protonation constant. Detailed analysis of the chemical potential of the adsorbed nanoparticle reveals that the pH and salt dependence of the adsorption can be largely explained by the balance between an energy gain resulting from the particle and surface charge regulation and the surface complexation and an energy loss from the unfavorable interparticle electrostatic repulsion close to the surface. This conclusion is also supported by the strong impacts that the chemical heterogeneity of the particle functional groups, the magnitude of the surface complexation, the number of the functional groups, and the size of the particle have on the adsorption.

Roles of different types of oxalate surface complexes in dissolution process of ferrihydrite aggregates.

The dissolution of ferrihydrite induced by low molar mass (LMM) organics is an important process that provides bioavailable iron for organisms. Here, ATR-FTIR analysis was combined with characterization of ferrihydrite nanoparticles and kinetic modeling to investigate the roles of different oxalate surface complex species in the dissolution of ferrihydrite aggregates. ATR-FTIR results revealed that at least four different species were present at or near the ferrihydrite surface in the process of ferrihydrite aggregate dissolution. At a relatively low addition of oxalate (oxalate/Fe < 0.1), oxalate was dominantly present as binuclear bidentate surface complexes and aqueous species. The binuclear bidentate complexes mainly caused electrostatic repulsion between particles, resulting in the disaggregation of large ferrihydrite aggregates into colloidal particles with hydrodynamic diameters of 116-174 nm. Kinetic modeling showed that these colloidal particles were stable at the oxalate/Fe ratio of 0.1. With increasing addition of oxalate (oxalate/Fe ≥ 0.1), mononuclear bidentate oxalate complexes and hydrogen-bonded surface complex replaced the binuclear bidentate complexes and aqueous species. The aggregates or larger colloidal particles were further disaggregated into smaller colloidal particles with hydrodynamic diameters of 35-64 nm. Additionally, the mononuclear bidentate oxalate complexes promoted the dissolution of ferrihydrite colloids into dissolved Fe.

Influence of humic acid on transport, deposition and activity of lysozyme in quartz sand.

Interaction with natural organic matter (NOM) is hypothesized to impact the fate and bioavailability of enzymes and some hazardous proteins in terrestrial and aquatic environments. By using saturated column transport experiments the transport and deposition of the model enzyme lysozyme (LSZ), in the absence and presence of purified Aldrich humic acid (PAHA), was investigated at a series of mass ratios PAHA/LSZ at pH 5 and 8 and two ionic strength values (0.5 mM and 50 mM KCl solution). PAHA decreased LSZ transport under all conditions. The shapes of breakthrough curves (BTCs) and retention profiles (RPs) during cotransport of both colloids evolved from symmetrical to blocking with time and from flat to hyper-exponential with depth, respectively, in response to increases in mass ratio PAHA/LSZ. The results indicated that the "size-selective retention" and concurrent homo- and hetero-aggregation induced straining, which resulted in preferential retention of relatively large PAHA-LSZ aggregates in the column and elution of relatively small ones. Due to differences in aggregate size, in general, the enzyme activity of LSZ in the effluent was larger and that of the retained LSZ was smaller than that of the influent. Therefore, protein transport process could partially increase the enzyme activity and bring potential environmental hazards.

Mechanisms of soil humic acid adsorption onto montmorillonite and kaolinite.

To explore the adsorption mechanisms of a soil humic acid (HA) on purified kaolinite and montmorillonite, a combination of adsorption measurements, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and isothermal titration calorimetry (ITC) was employed at pH 4.0, 6.0 and 8.0. The adsorption affinities and plateaus of HA on the two clays increased with decreasing pH, indicating the importance of electrostatic interaction. The effects were more significant for kaolinite than for montmorillonite. The substantial adsorption at pH 8.0 indicated hydrophobic interaction and/or H-bonding also played a role. The ATR-FTIR results at pH 8.0 showed that the Si-O groups located at basal faces of the two clays were involved in the adsorption process. For kaolinite, at pH 4.0 and 6.0, HA adsorption occurred via OH groups on the edge faces and basal octahedral faces (both positively charged), plus some adsorption at Si-O group. The exothermic molar adsorption enthalpy decreased relatively dramatically with adsorption up to adsorption values of 0.7µmol/g on montmorillonite and 1.0µmol/g on kaolinite, but the decrease was attenuated at higher adsorption. The high exothermic molar enthalpy of HA binding to the clays was ascribed to ligand exchange and electrostatic binding, which are enthalpy-driven. At high adsorption values, JGHA adsorption by hydrophobic attraction and H-bonding also occurs.

Ligand and Charge Distribution (LCD) model for the description of fulvic acid adsorption to goethite.

The LCD model (Ligand and Charge Distribution) has recently been proposed to describe the adsorption of humic substances to oxides, in which the CD-MUSIC model and the NICA model for ion binding to respectively oxides and humic substances are integrated. In this paper, the LCD model is improved by applying the ADAPT model (ADsorption and AdaPTation) to calculate the equilibrium distribution of the humic substances based on the change of the average chemical state of the particles. The improved LCD model is applied to calculate the adsorption of fulvic acid (Strichen) to goethite, in which it is assumed that the carboxylic type of groups of fulvic acid can form innersphere complexes with the surface sites. The charge of the carboxylic groups in the innersphere complexes is distributed between the 0- and d-plane, whereas the charge of the other carboxylic and phenolic groups is located in the d-plane. The average distribution of the carboxylic and phenolic groups among their various chemical states (carboxylic groups: innersphere complex, protonated and deprotonated; phenolic groups: protonated and deprotonated) depends on pH, ionic strength and loading, and are the outcome of the model. The calculation shows that the LCD model can describe sufficiently the effects of pH, ionic strength and loading on the adsorption of fulvic acid, using one adjustable parameter (logK (S,1)). The model calculations indicate that the chemical complexation between fulvic acid and goethite is the main driving force of the adsorption, while the electrostatic repulsion between the particles and the surface is the major limiting factor for further adsorption.

Surfactant adsorption to soil components and soils.

Soils are complex and widely varying mixtures of organic matter and inorganic materials; adsorption of surfactants to soils is therefore related to the soil composition. We first discuss the properties of surfactants, including the critical micelle concentration (CMC) and surfactant adsorption on water/air interfaces, the latter gives an impression of surfactant adsorption to a hydrophobic surface and illustrates the importance of the CMC for the adsorption process. Then attention is paid to the most important types of soil particles: humic and fulvic acids, silica, metal oxides and layered aluminosilicates. Information is provided on their structure, surface properties and primary (proton) charge characteristics, which are all important for surfactant binding. Subsequently, the adsorption of different types of surfactants on these individual soil components is discussed in detail, based on mainly experimental results and considering the specific (chemical) and electrostatic interactions, with hydrophobic attraction as an important component of the specific interactions. Adsorption models that can describe the features semi-quantitatively are briefly discussed. In the last part of the paper some trends of surfactant adsorption on soils are briefly discussed together with some complications that may occur and finally the consequences of surfactant adsorption for soil colloidal stability and permeability are considered. When we seek to understand the fate of surfactants in soil and aqueous environments, the hydrophobicity and charge density of the soil or soil particles, must be considered together with the structure, hydrophobicity and charge of the surfactants, because these factors affect the adsorption. The pH and ionic strength are important parameters with respect to the charge density of the particles. As surfactant adsorption influences soil structure and permeability, insight in surfactant adsorption to soil particles is useful for good soil management.

Copper binding to soil fulvic and humic acids: NICA-Donnan modeling and conditional affinity spectra.

Binding of Cu(II) to soil fulvic acid (JGFA), soil humic acids (JGHA, JLHA), and lignite-based humic acid (PAHA) was investigated through NICA-Donnan modeling and conditional affinity spectrum (CAS). It is to extend the knowledge of copper binding by soil humic substances (HS) both in respect of enlarging the database of metal ion binding to HS and obtaining a good insight into Cu binding to the functional groups of FA and HA by using the NICA-Donnan model to unravel the intrinsic and conditional affinity spectra. Results showed that Cu binding to HS increased with increasing pH and decreasing ionic strength. The amount of Cu bound to the HAs was larger than the amount bound to JGFA. Milne's generic parameters did not provide satisfactory predictions for the present soil HS samples, while material-specific NICA-Donnan model parameters described and predicted Cu binding to the HS well. Both the 'low' and 'high' concentration fitting procedures indicated a substantial bidentate structure of the Cu complexes with HS. By means of CAS underlying NICA isotherm, which was scarcely used, the nature of the binding at different solution conditions for a given sample and the differences in binding mode were illustrated. It was indicated that carboxylic group played an indispensable role in Cu binding to HS in that the carboxylic CAS had stronger conditional affinity than the phenolic distribution due to its large degree of proton dissociation. The fact was especially true for JGFA and JLHA which contain much larger amount of carboxylic groups, and the occupation of phenolic sites by Cu was negligible. Comparable amounts of carboxylic and phenolic groups on PAHA and JGHA, increased the occupation of phenolic type sites by Cu. The binding strength of PAHA-Cu and JGHA-Cu was stronger than that of JGFA-Cu and JLHA-Cu. The presence of phenolic groups increased the chance of forming more stable complexes, such as the salicylate-Cu or catechol-Cu type structures.