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Linkages between soil structure and physical–chemical soil properties are still poorly understood due to the wide size-range at which aggregation occurs and the variety of aggregation factors involved. To improve understanding of these processes, we collected data on aggregate fractions, soil porosity, texture and chemical soil properties of 127 soil samples from three European Critical Zone Observatories. First, we assessed mechanistic linkages between porosity and aggregates. There was no correlation between the fractions of dry-sieved aggregates (> 1 mm, DSA) and water-stable aggregates (> 0.25 μm, WSA). Soil microporosity and micro + mesoporosity increased with increasing abundance of aggregates, though this correlation was only significant for the WSA fraction. The fraction of DSA did not affect the overall porosity of the soil, but affected the ratio between micro- and mesopores (θ30 kPa/θ0.25 kPa), suggesting that micropores are dominantly located within DSA whereas mesopores are located in between DSA and loose particles. Second, we studied the relations between the physical and chemical soil properties and soil structure. Soil texture had only a minor effect on the fractions of WSA and DSA whereas Fe-(hydr)oxide content was correlated positively with both WSA fraction and porosity. This may be attributed to Fe-(hydr)oxides providing adsorption sites for organic substances on larger minerals, thereby enabling poorly reactive mineral particles to be taken up in the network of organic substances. The fraction of WSA increased with an increase in the soil organic carbon (SOC) and Fe-(hydr)oxides content and with a decrease in pH. This pH-effect can be explained by the enhanced coagulation of organically-coated particles at a lower pH. Overall, this study indicates that mechanistic linkages exist between soil chemical properties, aggregate formation and soil porosity.

Proper understanding of the basic processes and specific properties of engineered nanomaterials (NMs) that modify the fate and effects of NMs is crucial for NM-tailored risk assessment. This in turn requires developers of NMs and for regulators to consider the most important parameters governing the properties, behavior and toxicity of NMs. As fate and effect studies are commonly performed in laboratory settings, mimicking to a varying extent realistic exposure conditions, it is important to be able to extrapolate results of fate and effect studies in synthetic media to realistic environmental conditions. This requires detailed understanding of the processes controlling the fate and behavior of NMs in terrestrial and aquatic media, as dependent on the composition of the medium. It is the aim of this contribution to provide background reading to the NM and media specific properties and processes that affect the fate and behavior of NMs in aquatic environments, focusing on the specific properties of NMs that modulate the interactions in the aquatic environment. A general introduction on the dominant fate determining processes of NMs is supplemented by case studies on specific classes of NMs: metal NMs, stable oxides, iron oxides, and carbon nanotubes. Based on the synthesis of the current knowledge base toward essential data and information needs, the review provides a description of the particle specific properties and the water characteristics that need monitoring in order to allow for future quantification and extrapolation of fate and behavior properties of NMs in freshwater compartments of varying composition.

In this paper, the leaching behaviour of major components (Al, Ca, SO 4 , Mg, Si, Fe, Na and DOC) and trace elements (Ni, Zn, Cd, Cu, Pb, Mo and Sb) from MSWI bottom ash is studied as a function of time over a wide range of pH, under pH-controlled conditions. Equilibrium geochemical modelling using the modelling framework ORCHESTRA is used to enable a process-based interpretation of the results and to investigate whether ‘equilibrium’ is attained during the time scale of the experiments. Depending on the element and setpoint-pH value, net concentration increases or decreases of up to one order of magnitude were observed. Different concentration–time trends (increase or decrease) are observed in different pH ranges. The direction of the concentration–time trends depends on: (1) the shape of the ‘equilibrium’ solubility curve, and (2) the position of the setpoint-pH in the leaching test relative to the natural pH of the sample. Although the majority of the elements do not reach steady state, leached concentrations over a wide pH range have been shown to closely approach ‘equilibrium’ model curves within an equilibration time of 168 h. The different effects that leaching kinetics may have on the pH dependent leaching patterns have been identified for a wide range of elements, and can generally be explained in a mechanistic way. The results are in support of the currently prescribed equilibration time of 48 h in the European standard for the pH-static leaching test (TS14997). Finally, this study demonstrates that pH-static leaching experiments such as described in the European standards (TS14497 and TS14429), in combination with selective chemical extractions and a mechanistically based modelling approach, constitute a powerful set of tools for the characterization of leaching processes in waste materials over a wide range of conditions.

The adsorption of humic acids (HA) to goethite (at pH 3-11) and the proton co-adsorption (at pH 4.0, 5.5, and 7.0) were measured, and the results were compared to those of fulvic acids (FA). Compared to FA, the adsorption of HA is stronger and more ionic strength dependent. The adsorption of both HA and FA decreases with increasing pH. The relative change of the adsorption with pH is bigger for HA than for FA at relatively low pH. At relatively high pH, it is the opposite. Protons are released at pH 4.0 and co-adsorbed at pH 5.5 and 7.0 upon the adsorption of both HA and FA. The observed pH dependency of HA and FA adsorption is in agreement with the proton co-adsorption data. Model calculations show that the adsorbed FA particles are on average located in the Stern layer, whereas the adsorbed HA particles protrude beyond the Stern layer. The closer location to the surface of the adsorbed FA leads to stronger electrostatic interactions between the FA particles and the surface, which explains the larger amount of protons released at low pH and co-adsorbed at high pH with each mass unit of FA adsorbed than that with HA adsorbed. The model also reveals that for FA a mean-field (smeared-out) approximation is reasonable, but for HA a patchwise approach is more appropriate at relatively low loading.

We investigated the association between total trihalomethanes (TTHMs) and risk of stillbirth and low and very low birth weight in three water regions in England, 1992-1998; associations with individual trihalomethanes (THMs) were also examined. Modeled estimates of quarterly TTHM concentrations in water zones, categorized as low (30 microg/L), medium (30-59 microg/L), or high (or = 60 microg/L), were linked to approximately 1 million routine birth and stillbirth records using maternal residence at time of birth. In one region, where there was a positive socioeconomic deprivation gradient across exposure categories, there was also a positive, significant association of TTHM with risk of stillbirth and low and very low birth weight. Overall summary estimates across the three regions using a random-effects model to allow for between-region heterogeneity in exposure effects showed small excess risks in areas with high TTHM concentrations for stillbirths [odds ratio (OR) = 1.11; 95% confidence interval (CI), 1.00-1.23), low birth weight (OR = 1.09; 95% CI, 0.93-1.27), and very low birth weight (OR = 1.05; 95% CI, 0.82-1.34). Among the individual THMs, chloroform showed a similar pattern of risk as TTHM, but no association was found with concentrations of bromodichloromethane or total brominated THMs. Our findings overall suggest a significant association of stillbirths with maternal residence in areas with high TTHM exposure. Further work is needed looking at cause-specific stillbirths and effects of other disinfection by-products and to help differentiate between alternative (noncausal) explanations and those that may derive from the water supply.

Interactions of calcium and fulvic acid (Strichen) with the surface of goethite were studied with batch and titration experiments. The mutual influence of the interactions on the adsorption of fulvic acid, calcium ions and protons were examined. Adsorption of the fulvic acid to goethite decreased with increase in pH (pH range 3–11). Addition of Ca (1.0 mM) at intermediate and high pH significantly enhanced the adsorption of fulvic acid. Compared to the adsorption to pure goethite, the presence of fulvic acid enhanced the adsorption of Ca significantly. In comparison to the simple linear sum of Ca bound to fulvic acid and goethite, the interactions between goethite and fulvic acid led to a reduced adsorption of Ca at low pH and an enhanced adsorption at high pH. With the adsorption of fulvic acid, protons were released at low pH and coadsorbed at high pH. When Ca was added, fewer protons were released at low pH and fewer coadsorbed at high pH. The experimental results can be adequately described using a surface complexation model, the Ligand and Charge Distribution (LCD) model, in which the CD-MUSIC model for ion adsorption to mineral oxides and the NICA model for ion binding to humics are integrated. In the model calculations, adequate descriptions of the ternary system data (Ca-fulvic acid-goethite) were obtained with parameters derived from three binary systems (fulvic acid-goethite, Ca-goethite and Ca-fulvic acid) without further adjustment. The model calculations suggest that the interactions between Ca and fulvic acid at the surface of goethite are mainly due to the electrostatic effects.

The binding of organic contaminants to dissolved humic acids reduces the free concentration of the contaminants in the environment and also may cause changes to the solution properties of humic acids. Surfactants are a special class of contaminants that are introduced into the environment either through wastewater or by site-specific contamination. The amphiphilic nature of both surfactants and humic acids can easily lead to their mutual attraction and consequently affect the solution behavior of the humics. Binding of an anionic surfactant (sodium dodecyl sulfate, SDS) and two cationic surfactants (dodecyl- and cetylpyridinium chloride, DPC and CPC) to purified Aldrich humic acid (PAHA) is studied at pH values of 5, 7, and 10 in solutions with a 0.025 M ionic strength (I). Monomer concentrations of the surfactants are measured with a surfactant-selective electrode. At I = 0.025 M, no significant binding is observed between the anionic surfactant (SDS) and PAHA, whereas the two cationic surfactants (DPC, CPC) bind strongly to PAHA over the pH range investigated. The binding is due both to electrostatic and hydrophobic attraction. The initial affinity increases with increasing pH (i.e., negative charge of PAHA) and tail length of the surfactant. Binding reaches a pseudo-plateau value (2-5 mmol/g) when the charge associated with PAHA is neutralized by that of the bound surfactant molecules. The pseudo-plateau values for DPC and CPC are very similar and depend on the solution pH. The cationic surfactant-PAHA complexes precipitate when the charge neutralization point is reached. This occurs at approximately 10% of the critical micelle concentration or CMC. This type of phase separation commonly occurs during surfactant binding to oppositely charged polyelectrolytes. For CPC, the precipitation is complete, but in the case of DPC, a noticeable fraction of PAHA remains in solution. At very low CPC concentrations (less than 0.1% of the CMC), CPC binding to PAHA is cooperative. The investigated range of concentrations for DPC was too limited to reach a similar conclusion. The results of this study demonstrate that the fate of humic acids will be strongly affected by the presence of low cationic surfactant concentrations in aqueous environmental systems.

The adsorption of natural organic matter (NOM) on mineral (hydr)oxide plays an important role in the evaluation of the speciation of toxic metal ions in the environment. Because both NOM and mineral oxide have variable charges that adjust upon adsorption, a good understanding of proton binding is required before the binding of metal ions can be understood. In this study, the adsorption of purified Aldrich humic acid (PAHA) on goethite was examined as a function of the environmental conditions (pH, salt concentration, and free concentration of PAHA) together with the proton adsorption to PAHA, goethite, and their mixtures. The induced charges on both components were separated on the basis of the difference between the charge/pH curves of the mixture and those of the single components. The electrostatic potential profile across the adsorbed layer was obtained as a numerical solution of the Poisson-Boltzmann equation using the charge density of the adsorbed PAHA and the goethite surface. From the quantitative evaluation of the induced charge on both components, it is revealed that the degree of the charge adjustment is related to the electrostatic affinity between the PAHA segments and the goethite surface, the electrostatic repulsion between the PAHA segments, and the electrostatic shielding by salt ions. Considering the charge distribution of the adsorbed PAHA at the goethite surface, it is concluded that the change of the charge adjustment is sensitive to that of the conformation of the adsorbed PAHA. From the detailed inspection of the assumptions made and the comparison with the reported theoretical calculations, the obtained potential profiles are considered to broadly reflect the true potential profiles. Because a charge adjustment is not frequently considered in detail in relation to the NOM adsorption on metal (hydr)oxides, the obtained results can form the basis for the further development of modeling of the adsorption of NOM on (hydr)oxide surfaces.

C-13 CP-MAS NMR is used as a non-destructive technique to measure the distribution of carbon types in humic substances. Although it is well-known that quantification of CP-MAS is problematic because different parts of the spectrum have different optimal contact times, a single contact time is used in most studies and in such cases C-13 CP-MAS NMR is only qualitative. Using Variable Contact Time experiments and back-extrapolating the signals for the various chemical shift regions to t=0 significantly improves quantification. Because signals decrease markedly during the beginning of an experiment, samples need a steady-state condition before acquisition of the Free Induction Decay (FID). Well-defined processing of the raw data significantly improves data quality. The effect of these various treatments on overall accuracy is shown.

Environmental contextThe environmental behaviour of trace metals in soils and waters largely depends on the chemical form (speciation) of the metals. Speciation software programs combining models for the binding of metals to soil and sediment constituents are powerful tools in environmental risk assessment. This paper describes a new combination of speciation software with a fitting program to optimise geochemical model parameters that describes proton and metal binding to humic substances. AbstractHere we describe the coupling of the chemical speciation software ORCHESTRA with the parameter estimation software PEST. This combination enables the computation of optimised model parameters from experimental data for the ion binding models implemented in ORCHESTRA. For testing this flexible tool, the NICA-Donnan model parameters for proton-, Cd- and Zn-binding to Laurentian fulvic acid were optimised. The extensive description of the method implementation and the examples provided facilitate the use of this tool by students and researchers. Three procedures were compared which derive the proton binding parameters, differing in the way they constrain the model parameters and in the implementation of the electrostatic Donnan model. Although the different procedures resulted in significantly different sets of model parameters, the experimental data fit obtained was of similar quality. The choice of the relation between the Donnan volume and the ionic strength appears to have a strong influence on the derived set of optimal model parameters, especially on the values of the protonation constants, as well as on the Donnan potential and Donnan volume. Optimised results are discussed in terms of their physico-chemical plausibility. Coherent sets of NICA-Donnan parameters were derived for Cd and Zn binding to Laurentian fulvic acid.

In this study, chitosan was successfully grafted onto the top surface of a bromomethylated poly(phenylene oxide) (BPPO) ultrafiltration membrane without pretreating the membrane at harsh conditions and/or using other cross linkers. Due to the grafting of polar groups of chitosari onto the membrane top surface, the hydrophilicity of the membrane top surface and the polar component of the total surface energy are improved compared to the pristine BPPO membrane. Theoretical calculation shows that the polar component of surface energy is a major contributor to the reduction in interfacial free energy of the membrane surface and interaction strength between foulants and membrane surface Therefore, the foulants adsorbed onto the top surface of chitosan/BPPO composite membranes are much easier to desorb during the cleanning process and as a result, a higher flux recovery was obtained compared to the pristine BPPO membrane, Moreover, due to the antibacterial nature of chitosan, such composite membranes show a better antibacterial property and the antibacterial rate was improved by 70% in comparion with pristine BPPO membrane.

The partitioning of the natural polyelectrolyte humic acid (HA) from an aqueous dispersion into a model biomimetic gel (alginate) and a synthetic polyacrylamide gel (PAAm) is explored. In both gels, the spatial distribution of HA in the gel body, as measured by confocal laser scanning microscopy, is markedly nonhomogeneous. A striking feature is the enhanced accumulation of HA in a thin film of thickness ca. 15 μm at the surface of the gel body, resulting in average local concentrations that are, for PAAm and alginate respectively, a factor of 10 and 4 greater than that in the bulk solution. The time dependence of accumulation in the surface film is predominantly controlled by the diffusive supply of HA from the aqueous medium, with a time constant on the order of 10(3) s for both gels. The concentration of HA within the bulk gel body differs significantly from that in the bulk aqueous medium: substantially higher for PAAm but much lower for alginate. The results are significant for understanding the nature and rate of sink/source functioning at permeable phases in contact with aqueous media, e.g., biofilms and gel-like layers at biological interfaces or employed in chemical speciation sensors.

Colloids may facilitate the transport of trace elements and nutrients like phosphate in soil. In this study, we characterized soil colloids (

Solubilizing agents may enhance remediation of-soils contaminated with hydrophobic organic contaminants by diminishing sorption of the contaminants or increasing desorption rates. The effectiveness of rhamnolipid biosurfactants to enhance the removal of sorbed contaminants from soil was determined using column studies. Soil columns were contaminated with phenanthrene and subsequently eluted with electrolyte solution or with electrolyte solution containing 500 mg/L rhamnolipid. For the four soils studied, removal of 50% of the phenanthrene from the soil columns was accomplished in a 2-5-fold shorter time period, and the time required for 90% removal was reduced up to 3.5-fold when elution was performed with the rhamnolipid-containing solution as compared to the treatment without rhamnolipid. The effect of rhamnolipid on the removal of phenanthrene was satisfactorily simulated using independently obtained parameters with a two-component advective-dispersive model accounting for micellar solubilization and admicellar sorption. A more detailed analysis of the system showed that desorption rates of phenanthrene in the presence of 500 mg/L rhamnolipid were higher than predicted on the basis of desorption rate constants of phenanthrene determined in the absence of rhamnolipid. It is concluded that rhamnolipid enhanced the removal of phenanthrene mainly by micellar solubilization and also by influencing sorption kinetics.

With recent advances in nanotechnology, environmental and health consequences of nanomaterial disposal merit close attention. In the search for environmentally-friendly reagent, this study investigates the use of humic acid (HA) as an assist of dissolved air flotation (DAF) in the TiO2 nanoparticle (TNP) elimination. To determine mechanisms of TNPs interacting with HA, surface modification experiments were firstly carried out; thereafter, laboratory scaled DAF tests were applied to remove TNPs with HA assisting. Results of surface modification experiments showed that the zeta potential of TNP suspension system had a reversal trend due to counter ions of TNP and anions offered by the HA stock solution. The surface modified suspension was not easy to restabilize because of the close combination of TNPs and HA through sphere linkages or hydrogen-bonded surface complexes. Agglomeration took place more readily along with increasing HA concentration in the optimum dosage range (7.8-9.15 mg/L DOC). The flotation performance revealed that HA could improve the DAF efficiency in the optimum dosage range of HA. The interaction between TNPs and HA (Na+-humate), including surface charge neutralization (electrostatic interactions), sphere linkages or hydrogen-bonded surface complexes, hydrophobic interactions, and van der Waals interactions, played dominant roles. (C) 2013 Elsevier B.V. All rights reserved.

The novel properties of nanomaterials offer great promise of new technological breakthroughs. Consequently, their use in industry is expanding, and with it the risk of their being released in industrial effluents, and later in surface waters. This raises the problem of potential environmental hazards that are as yet unknown. The work presented in this paper evaluates the feasibility of membrane ultrafiltration for the removal of SiO2 nanoparticles (78 nm mean hydrodynamic diameter) in suspension at 0.14 wt% with the objective of treating them as pollutant compounds in industrial effluents. Regenerated cellulose membranes with two MWCOs of 10 and 100 kDa were implemented. The influence of the membrane MWCO, the TMP and the stirring rate during filtration were examined. Stirred filtrations were performed at increasing TMP so as to characterise flux behaviour and retention rates. The feasibility of membrane ultrafiltration for this application was proved since the results of the 10 kDa membrane showed the highest expectable retention rates (>99.6%) given the analytical methods used, and steady permeability results [30-40 L h(-1) m(-2) bar(-1)] independently of TMP and filtration course. Moreover, performance was shown to be sustainable as fouling was mostly reversible (>90%), being removable by simple membrane surface rinsing with ultrapure water. This was confirmed by the reconstruction of fouling mechanisms for both membranes. Unstirred and constant TMP 40, 80 and 200 kPa filtration experiments were run to study fouling phenomena and the filtration cake characteristics (compressibility and porosity). Two distinct fouling mechanisms were highlighted: the 100 kDa membrane underwent internal and sometimes irreversible fouling in the form of pore clogging before cake filtration, while the 10 kDa membrane was characterised by filtration cake only. This work proposes solutions for the predicament of nanoparticle release into the environment and opens up perspectives for efficient wastewater treatment in the context of their industrial development. (C) 2013 Elsevier B.V. All rights reserved.

International audience; Speciation of Eu(III) in the presence of purified Aldrich humic acid (PAHA) and/or aluminum oxide α-Al 2 O 3 has been studied by batch experiments and time-resolved luminescence spectroscopy at different pH, ionic strengths and PAHA concentrations. Macroscopic and spectroscopic data (sorption, spectra, and decay times analyses) are compared between the ternary system, i.e., Eu(III)/PAHA/α-Al 2 O 3 , and the corresponding binary systems. As expected, results show a weak influence of ionic strength on Eu(III) adsorption onto α-Al 2 O 3. However, in the binary Eu(III)/PAHA system, it is evidenced that variations of electrolyte concentration, which modify PAHA conformation, influence the symmetry of the humic-bound Eu(III) at high pH. In the ternary system, adsorption of both Eu(III) and PAHA onto the surface decreases with ionic strength. At 0.01 mol/L NaClO 4 , Eu(III) luminescence decay is much faster than at 0.1 mol/L NaClO 4. This is most likely due to the lower surface concentration of PAHA at lower ionic strength, leading to a lesser constrained environment for Eu(III) ions. At high pH, luminescence spectra are different at the two ionic strengths studied. Concerning the influence of PAHA concentration, spectroscopic results show that in the binary Eu(III)/PAHA system a complete complexation of 1 µmol/L Eu(III) is reached for 16 mg/L PAHA at pH 4, and for lower PAHA concentrations at higher pH. At same PAHA concentration, there is no difference in asymmetry ratios between the binary Eu(III)/PAHA system and the ternary system between pH 4 and 7.7. This means that the presence of mineral surface has almost no influence on Eu(III) environment symmetry below pH 8. Hence, the occurrence of europium-bridged humic surface complexes is not likely. In the ternary system, at different pH, luminescence decay times of Eu(III) increase with PAHA concentration. They are much higher in the ternary system than in the binary Eu(III)/PAHA system, which would mean that Eu(III) environment in PAHA-bound molecules is more constrained, as previously seen [1]. Macroscopic results show that the influence of PAHA on Eu(III) sorption onto α-Al 2 O 3 depends on pH: at low pH, Eu(III) retention is always higher in the ternary system, whereas at higher pH it depends on PAHA concentration. [1] N. Janot, M. F. Benedetti, P. E. Reiller, Environ. Sci. Technol. 2011, 45, 3224.

Some recent developments made during the European Union 6th Framework Integrated Project FUNMIG in the understanding and prediction of behaviour in ternary systems of radionuclides, humic substances and mineral surfaces are described. These developments are placed in the context of the existing literature. The aim is to describe the current understanding of humic substance mediated radionuclide transport as it may be applied to calculations in support of Radiological Performance Assessment. Some improvements in experimental techniques that provide the raw data to calibrate metal ion binding models are explained. The various metal ion binding models that are available are described and contrasted, before the recent development of ternary system models, in particular the Ligand Charge Distribution model that can predict metal ion and humic substance behaviour in ternary systems. The kinetic effects in ternary systems are described along with the models that are used to describe them. Finally, the remaining challenges in making predictions of radionuclide transport for the Radiological Performance Assessment of radioactive waste repositories are discussed. © 2011 Elsevier Ltd. All rights reserved

Made available in DSpace on 2019-09-12T16:53:47Z (GMT). No. of bitstreams: 0 Previous issue date: 2012 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Fenton's reagent was used as a coagulating agent in the treatment of water samples with high true color caused by humic substances (HS) extracted from peat. The effects of the apparent molecular size of HS on coagulation, flocculation, and flotation were studied. Four distinct water samples having the same true colors were prepared using HS with different molecular sizes obtained through ultrafiltration fractioning. Through optimization of the coagulant dosage and coagulation pH and the construction of coagulation diagrams for each water sample, it was verified that the sample with the smallest apparent molecular size of HS was the most difficult to treat, requiring higher coagulant (Fenton's reagent) dosages than samples prepared with larger HS molecular sizes. Furthermore, filtration experiments after dissolved air flotation were carried out to simulate conventional treatment. The most representative results in filtered water were: absorbance at 254 nm

International audience; We used of a set of mechanistic adsorption models (1-pK TPM, ion exchange and Nica-Donnan) within the framework of the component additive (CA) approach in an attempt to determine the effect of repeated massive application of inorganic P fertilizer on the processes and mechanisms controlling the concentration of dissolved inorganic phosphorus (DIP) in soils. We studied the surface layer of a Luvisol with markedly different total concentrations of inorganic P as the result of different P fertilizer history (i.e. massive or no application for 40 years). Soil pH was made to vary from acid to alkaline. Soil solutions were extracted with water and CaCl2 (0.01 M). The occurrence of montmorillonite led us to determine the binding properties of P and Ca ions for this clay mineral. Satisfactory results were obtained using generic values for model parameters and soil-specific ones, which were either determined directly by measurements or estimated from the literature. We showed that adsorption largely controlled the variations of DIP concentration and that, because of kinetic constrains, only little Ca-phosphates may be precipitated under alkaline conditions, particularly in the P fertilized treatment. The mineral-P pool initially present in both P treatments did not dissolve significantly during the course of the experiments. The adsorption of Ca ions onto soil minerals also promoted adsorption of P ions through electrostatic interactions. The intensity of the mechanism was high under neutral to alkaline conditions. Changes in DIP concentration as a function of these environmental variables can be related to changes in the contribution of the various soil minerals to P adsorption. The extra P adsorbed in the fertilized treatment compared with the control treatment was mainly adsorbed onto illite. This clay mineral was the major P-fixing constituent from neutral to alkaline pH conditions, because the repulsion interactions between deprotonated hydroxyl surface sites and P ions were sufficiently counterbalanced by Ca ions. The drastic increase of DIP observed at acid pH was due to the effect of the lower concentration of surface sites of Fe oxides and kaolinite. In addition to confirming the validity of our approach to model DIP concentrations in soils, the present investigation showed that adsorption was the predominant geochemical process even in the P fertilized soil, and that Ca ions can have an important promoting effect on P adsorption. However the influence of the dissolution of the mineral-P pool under field conditions remained questionable.

Micropollutants occur in natural waters from a range of sources. Estrogenic compounds are naturally excreted by humans and hence stein predominantly from wastewater effluents. Due to their small molecular weight and concentration their effective control is a challenge. In this study magnetic ion exchange(MIEX (R)), which was developed to remove natural organic matter (NOM) from surface water, was investigated for such a micropollutant, estrone. The interaction of estrone with the resin occurs as a side effect when NOM is removed. This interaction results in some degree of removal. However, the accumulation of those hazardous materials on the resin, which can be associated with accidental release, as well Lis the concentration in the regeneration brine of the process, is environmentally more significant. For this reason a thorough investigation of interaction phenomena was undertaken. Estrone and polymeric materials (such as ion exchange resins or membranes) interact through a number of mechanisms including specific and non-specific interactions. Sorption and desorption of estrone were studied as a function of pH, temperature, natural organic matter concentration, sulfate concentration and ionic strength to elucidate possible mechanisms. The results demonstrated that the resin removed around 70% estrone at high pH conditions (>10.4) when estrone was predominantly negatively charged. However, below pH 10.4, when estrone was neutral, approximately 40% of estrone still sorbed due to hydrogen bonding. The optimum temperature for estrone sorption was observed to be in the 15 to 35 degrees C range, while the presence of other anions, including natural organic matter reduced estrone removal due to competition for anion exchange sites. Desorption of estrone was most effective with 2 M NaCl regeneration brine concentration when estrone was negatively charged (98% desorption). However, when estrone was neutral there was no significant difference between 1 M and 2 M NaCl. The results presented in this Study indicate that polar non-ionic micropollutants were removed by magnetic ion exchange resin due to sorption to the resin polymer. This has implications for treatment, however, the accumulation of micropollutants on polymeric materials in water treatment as well as the abundance of such micropollutants in the regeneration brine are risks that warrant monitoring.

Factors affecting uranium removal from brackish groundwater using a direct solar powered ultrafiltration-nanofiltration/reverse osmosis membrane system were investigated during a field trial in the Australian outback. The key variables were uranium speciation (as a function of pH), groundwater type as well as energy variation over the course of a day. It was found that uranium was retained by the membranes over the pH range 3-11, but strongly adsorbed to membranes at pH 4-7. The speciation of uranium at pH 4-7 explained the adsorption to the membrane. The presence of other inorganic species, in particular calcium, was a likely cause of uranium co-precipitation at pH 10-11. During solar energy experiments, it was found that the specific energy consumption increased over the course of the day. This indicated fouling through precipitation on the membranes which caused reduced retention of uranium towards the end of the solar day. (C) 2009 Elsevier B.V. All rights reserved.

Magnetic ion exchange (MIEX (R)) is an ion exchange resin developed as an additive to existing water treatment plants where additional organic matter is to be removed. The smaller size, magnetic properties and simple regeneration using NaCl distinguishes MIEX (R) from conventional ion exchange resins and hence its use in international development applications is investigated in this review article. MIEX (R) has been demonstrated to remove varying levels of dissolved organic matter, inorganic anions such as nitrate and sulphate and micropollutants including non-ionic pesticides. The removal efficiency can also be influenced by temperature, pH and presence of other anions. As MIEX (R) is unable to disinfect water, the most likely application within international development is as pre-treatment before disinfection or membrane filtration.

Cellulose acetate 0.45-mu m syringe filters could be used to filter environmental samples containing steroidal hormones, such as estradiol, prior to analysis. Such pretreatment may result in significant loss of analyte due to either adsorption of analyte to the filter material or association with retained colloidal and particulate materials. To determine the quantity of such losses, several experiments were performed by filtering water spiked with estradiol at different concentrations ( 50, 100, and 500 ng/L) and pH (3-12) through cellulose acetate syringe filters. Further, the influence of added organic matter was studied. At all concentrations the experiments indicated that below pH 11, up to 50% of estradiol in the feed was adsorbed on the filter. This occurred regardless of the presence of bulk organic matter in solution, and was related to dissociation of estradiol with pH and subsequent changes in filter interaction. As a consequence, pretreatment of solutions containing estradiol should be adjusted to greater than pH 11 prior to filtration with 0.45-mu m cellulose acetate filters.

The present study examines the effect of humic acid on the uptake kinetics of Cd(II), Cu(II), and Pb(II) by the freshwater alga Chlorella kesslerii. The results demonstrated that the relative proportion of Pb in the cell wall layer is greater than that of the internalized Pb, while internalized Cd and Cu were comparable or greater than the adsorbed metal concentration. In the presence of 10 mg L-1 humic acid (HA), Cd and Cu uptake kinetics were consistent with that predicted by measured free metal concentrations. For Pb, the uptake flux and amount of lead bound to internalization and adsorption sites were an order of magnitude higher than those found at the same free lead ion concentrations in the presence of citric acid. Chemodynamic modeling suggested that the enhancement of the Pb uptake flux in the presence of HA originates from an increasing amount of Pb bound to the internalization sites through a ternary complex formation between lead-humic acid complex and internalization sites. Cell wall speciation calculations indicated that the lead-humic acid complex is the predominant species in the cell wall layer, while for Cu(II) and Cd(II) metal bound to the internalization (Cu) and adsorption (Cd) sites significantly dominated over the M-HA complex. The findings of the work show the relevance of the cell wall layer concentration and speciation and its key role in defining the local equilibrium conditions between metal and internalizations sites. The results of the present kinetic study have important consequences for improvement of the mechanistic understanding of the role of dissolved organic matter in metal uptake in phytoplankton and biogeochemical cycling of metals in the surface waters.

Average electrostatic potentials of purified Aldrich humic acid (PAHA) are measured, based on quenching of the PAHA fluorescence by neutral and cationic quencher molecules with similar structures. The obtained negative potentials increased with increasing pH at a given salt concentration and weakly decreased with increasing salt concentration at given pH. The trends and the magnitudes of the potentials correspond with the few experimental results available in the literature. Comparison with potentials calculated by the electrostatic models from the charge of PAHA revealed that the average potentials obtained from the ion permeable sphere model and Donnan-EDL model agreed with the measured average potentials. With these two models it is assumed that a part of the PAHA charge is neutralized by the electrical double layer (EDL) around the PAHA particle in line with the view that humic acid is a nano-size particle partly permeable to small ions and solvent molecules. The potentials calculated by these two models are averages of the potential “inside” the particle (which governs the proton binding) and that in the EDL. The Donnan models, with both the fixed charges and the counter charges distributed over a volume that is greater than the particle volume itself, result in more negative potentials than the measured average potentials of PAHA. These observations suggest that the quenchers are located close to the functional groups but diffusely bound.

Motivation: High-accuracy mass spectrometry is a popular technology for high-throughput measurements of cellular metabolites (metabolomics). One of the major challenges is the correct identification of the observed mass peaks, including the assignment of their empirical formula, based on the measured mass. Results: We propose a novel probabilistic method for the assignment of empirical formulas to mass peaks in high-throughput metabolomics mass spectrometry measurements. The method incorporates information about possible biochemical transformations between the empirical formulas to assign higher probability to formulas that could be created from other metabolites in the sample. In a series of experiments, we show that the method performs well and provides greater insight than assignments based on mass alone. In addition, we extend the model to incorporate isotope information to achieve even more reliable formula identification. Availability: A supplementary document, Matlab code, data and further information are available from http://www.dcs.gla.ac.uk/inference/metsamp. Contact: srogers@dcs.gla.ac.uk

Interactions of purified Aldrich humic acid (PAHA) with lysozyme (LSZ) are investigated. In solution LSZ is moderately positively and PAHA negatively charged at the investigated pH values. The proton binding of PAHA and of LSZ is determined by potentiometric proton titrations at various KCl concentrations. It is also measured for two mixtures of PAHA-LSZ and compared with theoretically calculated proton binding assuming no mutual interaction. The charge adaptation due to PAHA-LSZ interaction is relatively small and only significant at low and high pH. Next to the proton binding, the mass ratio PAHA/LSZ at the iso-electric point (IEP) of the complex at given solution conditions is measured together with the pH using the Mutek particle charge detector. From the pH changes the charge adaptation due to the interaction can be found. Also these measurements show that the net charge adaptation is weak for PAHA-LSZ complexes at their IEP. PAHA/LSZ mass ratios in the complexes at the IEP are measured at pH 5 and 7. At pH 5 and 50 mmol/L KCl the charge of the complex is compensated for 30-40% by K(+); at pH 7, where LSZ has a rather low positive charge, this is 45-55%. At pH 5 and 5 mmol/L KCl the PAHA/LSZ mass ratio at the IEP of the complex depends on the order of addition. When LSZ is added to PAHA about 25% K(+) is included in the complex, but no K(+) is incorporated when PAHA is added to LSZ. The flocculation behavior of the complexes is also different. After LSZ addition to PAHA slow precipitation occurs (6-24 h) in the IEP, but after addition of PAHA to LSZ no precipitation can be seen after 12 h. Clearly, PAHA/LSZ complexation and the colloidal stability of PAHA-LSZ aggregates depend on the order of addition. Some implications of the observed behavior are discussed. (c) 2008 Elsevier Ltd. All rights reserved.

For a period of 2 a, pore water composition in a heavily contaminated river floodplain soil was monitored in situ. Pore water samples were collected 12 times over all seasons in a profile ranging from aerobic to sulphidic redox conditions, and As, Cd, Cr, Cu, Pb, Zn, Mn, Fe, Ca, Cl, SO4. DOC,IOC and pH were determined. The variability of pH, IOC, DOC and Ca was found to be rather small during the year and within the profile (rsd

Polysaccharides, such as those occurring in cell walls and biofilms, play an important role in metal speciation in natural aqueous systems. This work describes the speciation of Cd(II) in alginate gels chosen as a model system for biogels. The gels are formed by bridging calcium ions at junction zones present along adjacent homopolymeric guluronic acid chain sequences. The free Cd2+ concentration in the gel phase is measured by a novel in situ microelectrode voltammetric technique that monitors the electroactive probe cation Cd2+ by its reduction at a Au-amalgam microelectrode. In situ voltammetric measurement coupled with total Ca(II) and Cd(II) determinations, as well as potentiometric titration, permits the full reconstruction of the charging environment and the cation binding for the gel phase. Three independent combinations of measuring and modeling the charged gel layer thereby permit accurate prediction of the Donnan potential, psi(D), and the Donnan enrichment coefficient, Pi(D). At an ionic strength of 10 mM, Donnan potentials in the gel ranged from approximately -10 to -20 mV, corresponding to an enhancement in the level of free Cd2+ ions in the gel phase relative to the bulk solution by a factor of approximately 3. In contrast, the total level of Cd(II) was found to be enhanced by a factor of approximately 60, resulting predominantly from the specific binding of the Cd by the uronic acids of the alginate gel. These results emphasize that large differences in Cd(II) speciation can arise due to the combination of specific and electrostatic modes of binding. The results of this speciation analysis, for charged biological gels, have important consequences for mechanistic interpretation of metal biouptake processes involved in complex media.

To improve the long-term environmental risk assessment of waste applications, a predictive “multi-surface” modelling approach has been developed to simultaneously predict the leaching and reactive transport of a broad range of major and trace elements (i.e., pH, Na, Al, Fe, Ca, SO4, Mg, Si, PO4, CO3, Cl, Ni, Cu, Zn, Cd, Pb, Mo) and fulvic acids from MSWI bottom ash. The geochemical part of the model approach incorporates surface complexation/precipitation on Fe/Al (hydr)oxides, complexation with humic and fulvic acids (HA and FA, respectively) and mineral dissolution/precipitation. In addition, a novel approach is used to describe the dynamic leaching of FA, based on the surface complexation of FA on Fe/Al (hydr)oxides. To enable reactive transport calculations, the geochemical part of the model is combined with advective/dispersive transport of water and first-order mass transfer between mobile and stagnant zones. Using a single, independently determined set of input parameters, adequate model predictions are obtained for the leaching of a broad range of elements under widely different conditions, as verified with data from the European standardised pH-static and percolation leaching tests (TS 14997 and TS 14405, respectively). The percolation tests were operated at different flow velocities and with flow interruptions to enable verification of the local equilibrium assumption. Although the combination of experimental and modelling results indicates that the leaching of major solubility-controlled elements occurs largely under local equilibrium conditions, this study has led to the identification of physical non-equilibrium processes for non-reactive soluble salts, as well as possible sorption-related non-equilibrium processes for the leaching of Mo, FA and associated trace metals. Further improvement of the reactive transport model can be achieved by a more mechanistic description of the (dynamic) leaching behaviour of humic substances. As the modelling approach outlined in this study is based on the fundamental processes that underlie leaching, the approach is expected to be also applicable to other granular contaminated materials application scenarios and conditions. Therefore, the combination of standardized leaching test methods, selective chemical extractions and mechanistic modelling, constitutes a promising generic approach to assess the long-term environmental impact of the application of granular contaminated materials in the environment.

This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration as Pb(II). However, Cd(II) and Zn(II) did not seem to compete with Pb(II) for strong binding sites of SRFA. These two metals did compete with Pb(II) for the weaker binding sites of SRFA. Heterogeneity of SRFA was found to play a crucial role in metal-SRFA interactions. The environmental significance of this research for freshwater is that even at relatively low Pb(II) loadings, the metals associated with lead in minerals, e.g. Cu(II), may successfully compete with Pb(II) for the same binding sites of the naturally occurring organic complexants, with the result that some of the Pb(II) may exist as free Pb2+ ions, which has been reported to be one of the toxic forms of Pb in aquatic environment.

International audience; Model VI and the NICA-Donnan model are two successful models presently available for describing metal ion binding by humic materials. Both models deal with the complexity of the underlying processes (intrinsic heterogeneity, partial correlation between affinity distributions, variable stoichiometry, electrostatics) in a pragmatic way. The parameters of the NICA-Donnan model and their determination are discussed. The current interpretation of the ion-specific "non-ideality" parameters, n(i), found in the NICA-Donnan model, emphasizes their role in determining the stoichiometry for the competitive binding of ions. The ratio n(M)/n(H) is reflected in the corresponding exchange ratios and the pH dependence of the metal ion binding. Experimental complications occur in testing models. Although Model VI and the NICA-Donnan models have much in common, there are differences that may become more apparent as the models are more widely tested. Recently ion binding to complexes of humics and oxides has been described by combining the NICA-Donnan model (ion binding to humics) with the CD-MUSIC model (ion binding to oxides). The impact of humic to oxide binding on both cation and anion binding is briefly discussed.

A control system for the in-line coagulation applied in an ultrafiltration process was developed. The dosing strategy aims to apply a minimal coagulant dose while maintaining desirable process performance by regulating the initial filtration resistance. This is achieved by a feedback controller. It was found that the control system performs well; adaptation to changing conditions is achieved adequately and sufficiently fast. The initial resistance of the last filtration before the chemical cleaning phase can be controlled within an accuracy of approximately 3% (of the total resistance) or 9% (of the fouling resistance). Compared to the current dosing strategy, a significant reduction of coagulant consumption can be achieved. (c) 2007 Elsevier B.V. All rights reserved.

In this paper, the LCD (ligand charge distribution) model is applied to describe the adsorption of (Tongbersven) humic acid (HA) to goethite. The model considers both electrostatic interactions and chemical binding between HA and goethite. The large size of HA particles limits their close access to the surface. Part of the adsorbed HA particles is located in the compact part at the goethite surface (Stern layers) and the rest in the less structured diffuse double layer (DDL). The model can describe the effects of pH, ionic strength, and loading on the adsorption. Compared to fulvic acid (FA), adsorption of HA is stronger and more pH- and ionic-strength-dependent. The larger number of reactive groups on each HA particle than on a FA particle results in the stronger HA adsorption observed. The stronger pH dependency in HA adsorption is related to the larger number of protons that are coadsorbed with HA due to the higher charge carried by a HA particle than by a FA particle. The positive ionic-strength dependency of HA adsorption can be explained by the conformational change of HA particles with ionic strength. At a higher ionic strength, the decrease of the particle size favors closer contact between the particles and the surface, leading to stronger competition with electrolyte ions for surface charge neutralization and therefore leading to more HA adsorption.

Among speciation techniques that are able to measure free metal ion concentrations, the Donnan membrane technique (DMT) has the advantage that it can measure many different free metal ion concentrations simultaneously in a multicomponent sample. Even though the DMT has been applied to several systems, like surface waters, soil solutions, and manure slurry, basic features and calibrations with model calculations of the laboratory and field DMT have not been done sufficiently yet. Therefore, we tested the application of the DMT on metal complexation with several synthetic and natural ligands and the applicability of the dynamic mode of the DMT. The results show that there is a high agreement between the calculated and measured free metal ion concentrations in solutions containing synthetic (nitriloacetic acid, diglycolic acid) and natural organic ligands (fulvic acid, humic acid) at various pH values. Both the laboratory DMT and the field DMT give very similar results. In a solution containing labile ligands, equilibrium time is smaller than in a donor solution containing inert ligands or no ligands. Moreover, when labile ligands are present in the donor solution, a dynamic procedure can be used to decrease equilibrium time. This procedure cannot be applied when no ligands or only inert ligands are present.

Commercial surfactants are introduced into the environment either through waste products or site-specific contamination. The amphiphilic nature of both surfactants and humic substances (HS) leads to their mutual attraction especially when surfactant and HS are oppositely charged. Binding of the cationic surfactants dodecyl-pyridinium chloride (DPC) and cetyl- or hexadecyl-pyridinium chloride (CPC) to purified Aldrich humic acid (PAHA), Dando humic acid (DHA), Inogashira humic acid (IHA), Laurentian fulvic acid (LFA) and Strichen Bs fulvic acid (SFA) is studied at pH 4.5–5 at 0.005 M NaCl. For PAHA CPC binding is also studied at pH 5 and 0.1 M NaCl. Measurements with the Mutek Particle Charge Detector (PCD) and poly-DADMAC, a strong cationic polyelectrolyte, are used to determine the charge of the HS samples. PCD measurements with the surfactants reveal that the surfactant–HS complexes reach their iso-electric-point (IEP) before the critical micelle concentration (CMC) is reached. At the IEP the adsorption values (mol/g) of CP + and DP + to PAHA are the same, i.e. at the IEP the charge associated with the HS is neutralized by bound surfactant ions. For the other humic acids (HAs) CPC binding at the CMC corresponds with the charge obtained with poly-DADMAC, but for the fulvic acid (FA) samples CP(C) adsorption at the IEP is larger than the FA charge. The surfactant–HS complexes flocculate around the IEP. Binding isotherms are obtained using surfactant electrodes. The results for CPC and DPC to the HA samples show a pseudo-plateau near the IEP, which is missing in the isotherms to the FA samples. The CP + –PAHA isotherms at 0.005 M and 0.1 M intersect at the IEP. The affinity of CP + binding to PAHA is larger than that of DP + due to the longer aliphatic tail of CPC. The bound amount of DP(C) decreases in the order PAHA ≫ IHA ≈ DHA ≫ LFA ≈ SFA. The results demonstrate that cationic surfactant binding to HS is due both to electrostatic and hydrophobic attraction and that the fate of HS in aqueous environmental systems can be strongly affected by cationic surfactants.

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 ( log K ˜ 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.

The effect of accelerated aging of Municipal Solid Waste Incinerator (MSWI) bottom ash on the leaching of Cu and Mo was studied using a "multisurface" modeling approach, based on surface complexation to iron/aluminum (hydr) oxides, mineral dissolution/precipitation, and metal complexation by humic substances. A novel experimental method allowed us to identify that the solid/liquid partitioning of fulvic acids (FA) quantitatively explains the observed beneficial effect of accelerated aging on the leaching of Cu. Our results suggest that iron/aluminum (hydr)oxides are the major reactive surfaces that retain fulvic acid in the bottom ash matrix, of which the aluminum (hydr)oxides were found to increase after aging. A new modeling approach, based on the surface complexation of FA on iron/aluminum (hydr) oxides is developed to describe the pH-dependent leaching of FA from MSWI bottom ash. Accelerated aging results in enhanced adsorption of FA to (neoformed) iron/aluminum (hydr) oxides, leading to a significant decrease in the leaching of FA and associated Cu. Accelerated aging was also found to reduce the leaching of Mo, which is also attributed to enhanced adsorption to (neoformed) iron/aluminum (hydr) oxides. These findings provide important new insights that may help to improve accelerated aging technology.

Variable-charge nanoparticles such as proteins and humics can adsorb strongly to charged macroscopic surfaces such as silica and iron oxide minerals. To model the adsorption of variable-charge particles to charged surfaces, one has to be able to calculate the adsorption free energy involved. It has been shown that the change in the free energy of variable-charge particles is related to the change in their average chemical state upon adsorption, which is commonly described using surface complexation models. In this work, expressions for the free-energy change in variable-charge particles due to changes in chemical binding are derived for three ion-binding models (i.e., the Langmuir, Langmuir-Freundlich, and NICA models) and for changes due to nonspecific binding for the Donnan model. The expressions for the adsorption free energy of the variable-charge particles to a charged surface are derived on the basis of the equality of the (electro)chemical potential of the particles in the bulk solution and adsorption phase. The expressions derived are general in the sense that they account for the competition between charge-determining ions that bind chemically to the particles, and they also apply in case of the formation of chemical bonds between particle ligands and surface sites. The derived expressions can be applied in the future to model the adsorption of variable-charge nanoparticles to charged surfaces. The results obtained for the NICA-Donnan model make it possible to apply this advanced surface complexation model to describe the adsorption of humics to minerals.

Humic acids have stable radicals that are indigenous to their structure. Hydroxybenzoic acid derivatives such as gallic acid (GA) and protocatechuic acid are appropriate models for the radical properties of humic acids. Here we show that the adsorption or intercalation of gallic acid in Laponite clay results in a significant thermodynamic stabilization of gallic acid radicals. Moreover, the formed organoclay shows enhanced stability against acid dissolution. The structural details of the association of gallic acid with Laponite depend on the GA/Laponite loading. At low GA/Laponite ratios (similar to 10(-6) M of gallic acid per gram of clay), gallic acid is adsorbed at the variable charge sites of Laponite. This adsorption can be adequately described by surface complexation modeling. At higher GA/Laponite ratios (similar to 10(-3) M of gallic acid per gram of clay), X-ray diffraction data show that gallic acid is intercalated at the interlamellar sites of Laponite. In the presence of Pb2+ ions, the formed GA/Pb complex is associated with Laponite in an analogous structural manner, that is, adsorption at variable charge sites or intercalation at the interlamellar sites of Laponite, depending on the loading. Laponite stabilizes the GA/Pb radicals. At prolonged exposure to ambient O-2, Laponite promotes the formation of stable oligomeric GA/Pb radical species, which are intercalated into interlamellar sites. Langmuir

Binding of heavy metal and actinide ions to natural colloids, such as humic substances (HSs) and metal (hydr)-oxides, plays an important role in the ecotoxicological behavior of these ions. Several thermodynamic models have been constructed to predict the speciation of these ions in metal/HS or metal/oxide binary systems. However, in natural environments the adsorption of HSs on oxides can influence the binding of target metals, leading to deviation from the additivity of calibrated binary models. In this study binding of copper (Cu2+) to the purified Aldrich humic acid (PAHA)/goethite complex in the neutral to acidic pH region was investigated by measuring Cu2+ binding isotherms. The measured isotherms were compared with the results obtained for the binary systems under similar conditions. The comparison revealed that Cu2+ binding in the ternary system is enhanced with respect to the sum of Cu2+ binding in the corresponding binary systems. From the analysis of the charging behavior of the adsorbed PAHA as well as the smeared-out potential profile near the PAHA/goethite interface, the increase of Cu2+ binding to the complex was mainly attributed to the decrease of proton competition to the functional groups of the adsorbed PAHA and the change of the electrostatic potential in the vicinity of the goethite surface.

Recent developments in acidification research focused on the leaching of metals from contaminated soil. In this paper the buffering of sandy soils upon acidification is studied in relation to the release of major (Al, Ca, Mg) and trace metals (Cu, Cd, Ni, Zn) from the soil reactive surface. The buffering process and the (de)sorption of metals are described with a mechanistic multisurface model, expressing the sorption onto different soil surfaces (organic matter, clay, Fe (hydr)oxides). The pH of sandy soil samples is predicted upon proton addition in combination with the behavior of major and trace metals. Acidification of contaminated sandy soil samples, with different pH levels and metal contents, is performed in a flow-through reactor by flushing the samples with acid solution. Acidification has taken place in successive steps of proton addition and followed by sampling. Prediction of pH upon acidification with a multisurface model gives satisfying results for all samples studied. The pH is modeled reasonably well between pH 6 and 4. Below pH 4 the predicted pH values are slightly too low, probably due to the buffering by Al-containing minerals (e.g., Al hydroxide), which are not included in the model. Desorption of major and trace metals upon pH decrease is, in general, predicted well, within a factor of 1-5 on a linear scale. Overall prediction of proton buffering in combination with desorption of metals in sandy soil samples, over a wide pH range and metal content, is done quite well for the studied metals with the multisurface model.

The aim of this study is to predict the solid-solution partitioning of heavy metals in river flood plain soils. We compared mechanistic geochemical modeling with a statistical approach. To characterize the heavy metal contamination of embanked river flood plain soils in The Netherlands, we collected 194 soil samples at 133 sites distributed in the Dutch part of the Rhine and Meuse river systems. We measured the total amounts of As, Cd, Cr, Cu, Ni, Pb, and Zn in the soil samples and the metal fraction extractable by 2.5 mM CaCl2. We found a strong correlation between heavy metal contamination and organic matter content, which was almost identical for both river systems. Speciation calculations by a fully parametrized model showed the strengths and weaknesses of the mechanistic approach. Cu and Cd concentrations were predicted within one log scale, whereas modeling of Zn and Pb needs adjustment of some model parameters. The statistical fitting approach produced better results but is limited with regard to the understanding it provides. The log RMSE for this approach varied between 0.2 and 0.32 for the different metals. The careful modeling of speciation and adsorption processes is a useful tool for the investigation and understanding of metal availability in river flood plain soils.

The impact of humic acids and the humic model compound, anthraquinone-2,6-disulfonate (AQDS), on the biodegradation of carbon tetrachloride (CT) by anaerobic granular sludge was studied. Addition of both humic acids and AQDS at sub-stoichiometric levels increased the first-order rate of conversion of CT up to 6-fold, leading to an increased production of inorganic chloride, which accounted for 40-50% of the CT initially added. Considerably less dechlorination occurred in sludge incubations lacking humic substances. By comparison, very limited dechlorination occurred in sterile controls with autoclaved sludge. Accumulation of chloroform (1-10%) and dichloromethane (traces) also accounted for the CT converted. The accumulation of a chlorinated ethene, perchloroethylene (up to 9% of added CT), is also reported for the first time as an end-product of CT degradation. A humus-respiring enrichment culture (composed primarily of a Geobacter sp.) derived from the granular sludge also dechlorinated CT, yielding products similar to the AQDS-supplemented granular sludge consortium. The dechlorination of CT by the Geobacter enrichment was dependent on the presence of AQDS or humic acids, which were reduced during the assays. The reduced form of AQDS, anthrahydroquinone-2,6-disulfonate, was shown to cause the chemical reduction of CT when incubated in sterile medium. The results taken as a whole indicate that the formation of reduced humic substances by quinone-respiring microorganisms can contribute to the reductive dechlorination of CT.

C-13 CP-MAS NMR is used as a non-destructive technique to measure the distribution of carbon types in humic substances. Although it is well-known that quantification of CP-MAS is problematic because different parts of the spectrum have different optimal contact times, a single contact time is used in most studies and in such cases C-13 CP-MAS NMR is only qualitative. Using Variable Contact Time experiments and back-extrapolating the signals for the various chemical shift regions to t=0 significantly improves quantification. Because signals decrease markedly during the beginning of an experiment, samples need a steady-state condition before acquisition of the Free Induction Decay (FID). Well-defined processing of the raw data significantly improves data quality. The effect of these various treatments on overall accuracy is shown.