Complexation with dissolved organic matter and solubility control of heavy metals in a sandy soil

The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The results show that the DOM-complexed species is generally more significant for Cu and Pb than for Cd, Zn, and Ni. The ability of two advanced models for ion binding to humic substances, e.g., model VI and NICA-Donnan, in the simulation of metal binding to natural DOM was assessed by comparing the model predictions with the measurements. Using the default parameters of fulvic and humic acid, the predicted concentrations of free metal ions from the solution speciation calculation using the two models are mostly within 1 order of magnitude difference from the measured concentrations, except for Ni and Pb in a few samples. Furthermore, the solid-solution partitioning of the metals was simulated using a multisurface model, in which metal binding to soil organic matter, dissolved organic matter, clay, and iron hydroxides was accounted for using adsorption and cation exchange models (NICA-Donnan, Donnan, DDL, CD-MUSIC). The model estimation of the dissolved concentration of the metals is mostly within 1 order of magnitude difference from those measured except for Ni in some samples and Pb. The solubility of the metals depends mainly on the metal loading over soil sorbents, pH, and the concentration of inorganic ligands and DOM in the soil solution.     

Leaching of heavy metals from contaminated soils: an experimental and modeling study

In this paper, we characterize the leaching of heavy metals (Ni, Cu, Zn, Cd, and Pb) from eight contaminated soils over a wide range of pH (pH 0.4-12) using an original approach based on batch pH-static leaching experiments in combination with selective chemical extractions and geochemical modeling. The leached concentrations of the heavy metals are generally much lower than the total concentrations and show a strong pH dependency, resulting in "V-shaped" leaching curves with orders of magnitude changes in solution concentrations. The "multisurface" model used incorporates adsorption to dissolved and solid organic matter (NICA-Donnan), iron/aluminum (hydr)oxide (generalized two-layer model) and clay (Donnan model). These models were applied without modifications, and only the standard set of binding constants and parameters was used (i.e., without any fitting). The model predictions of heavy metal leaching are generally adequate and sometimes excellent. Results from speciation calculations are consistent with the well-recognized importance of organic matter as the dominant reactive solid phase in soils. The observed differences between soils with respect to element speciation in the solid phase correspond to the relative amounts of the reactive surfaces present in the soils. In the solution phase, complexes with dissolved organic matter (DOM) are predominant over most of the pH range. Free metal ions (Me2+) are generally the dominant species below pH 4. The combination of the experimental and modeling approach as used in this study is shown to be promising because it leads to a more fundamental understanding of the pH-dependent leaching processes in soils. The "multisurface" modeling approach, with the selected sorption models, is shown to be able to adequately predict the leaching of heavy metals from contaminated soils over a wide range of conditions, without any fitting of parameters.     

Immobilizing humic acid in a sol-gel matrix: a new tool to study humic-contaminants sorption interactions

Humic substances originated from aquatic, soil, or sediment environments are mixtures of humic compounds with various characteristics. Sorption interactions with isolated, well defined humic fractions can be studied either in an aqueous phase ("dissolved humic substances"), or in a solid-phase, by coating mineral particles with the humic materials, or simply by working with humic acid particles (powder) at low pH to minimize dissolution. Each attitude, by definition, can be studied by different experimental techniques and has a different meaning for understanding natural environmental processes. In this study, a new tool for studying sorption interactions is presented. Sol-gel was used as an inert matrix to immobilize (entrap) various humic acids (HAs), and then used to study the interactions of several polycyclic aromatic hydrocarbons (PAHs) with the entrapped HA. Linear and nonlinear sorption coefficients were highly correlated with contaminant hydrophobicity. Sorption of pyrene to immobilized HA was in the order of soil HA > Aldrich HA approximately = peat HA. It was concluded that the entrapped HAs retained their original properties in the gel matrix and were accessible to the external contaminant through the pore network. Additionally, binding coefficients of pyreneto dissolved humic substances and to dissolved organic matter (DOM) were determined from the reduction in pyrene sorption to immobilized HA in the presence of dissolved humic material or DOM in solution. Binding coefficients of pyrene were in the order of the following: dissolved Aldrich HA > dissolved peat fulvic acid (FA) > DOM derived from mature compost > DOM derived from fresh compost.     

Proton buffering and metal leaching in sandy soils

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.     

Solid-solution partitioning of Cd, Cu, Ni, Pb, and Zn in the organic horizons of a forest soil

We report the solid-liquid partitioning of Cd, Cu, Ni, Pb, and Zn in 60 organic horizon samples of forest soils from the Hermine Watershed (St-Hippolyte, PQ, Canada). The mean Kd values are respectively 1132, 966, 802, 3337 and 561. Comparison of those Kd coefficients to published compilation values show that the Kd values are lower in acidic organic soil horizons relative to the overall mean Kd values compiled for mineral soils. But, once normalized to a mean pH of 4.4, the Kd values in organic soil horizons demonstrate the high sorption affinity of organic matter, which is either as good as or up to 30 times higher than mineral soil materials for sorbing trace metals. Regression analysis shows that, within our data set, pH and total metal contents are not consistent predictors of metal partitioning. Indeed, metal sorption by the solid phase must be studied in relation to complexation by dissolved organic ligands, and both processes may sometime counteract one another.     

Effects of microbially mediated redox conditions on PAH-soil interactions

The impacts of microbially mediated redox conditions on the bioavailability of persistent polycyclic aromatic hydrocarbons (PAHs) in soils and sediments have received little study, despite the fact that most water-saturated soils and sediments spend a significant portion of the time under reduced conditions. To address this need an uncontaminated surface soil was incubated under various redox conditions (aerobic, nitrate-reducing, sulfate-reducing, and methanogenic). Depending on redox conditions, different quantities of fulvic and humic acids were liberated as dissolved organic matter (DOM) from the soil during incubation. The DOM released under highly reduced conditions was more nonpolar, aromatic, and polydisperse, of higher molecular weight, and had a higher sorption capacity for pyrene compared to that obtained from relatively oxic incubations. The soil-phase organic matter incubated under reduced conditions also became relatively more aromatic, containing nonpolar organic molecules of lower oxygen contents and exhibiting higher capacity and more nonlinear and hysteric sorption/desorption behavior for pyrene. These observations support the hypothesis that reduced environments established by indigenous soil microbes alter soil organic matter in a matter similar to diagenetic processes. Such humification-like alteration occurred principally in relatively more labile fractions of soil organic matter. These findings are important for assessing the ultimate fate and exposure risk of hydrophobic organic contaminants in soils and sediments where living microorganisms play a significant role in formation and evolution of soil/sediment organic matter.     

The sorption of iodide by soils as influenced by equilibrium conditions and soil properties

The sorption of iodide was reduced when soil was dried before equilibration with an iodide solution. With undried soils, sorption continued for > 48 h, maximum sorption occurred at pH values < 5 but a secondary sorption peak occurred at pH 8.5 to 9.0, particularly with a soil containing a high level of organic matter. Temperature had only a small effect on sorption over the range 10 to 35 °C. Maximum values for the sorption of iodide by two surface soils (0 to 10cm) at pH 6.6 to 6.8, assessed with a soil: solution ratio of 1:10, an equilibrium time of 40 h and at room temperature, were 25 and 6 fig I/g soil, respectively. The amounts of iodide sorbed by these soils, and by soils taken from successive 10 cm layers to a depth of 40 cm at the same two sites, were closely related to the contents of organic matter in the soils but not to contents of iron or aluminium oxides or of clay. Treatment of the surface soils with hydrogen peroxide to destroy organic matter greatly reduced the sorption of iodide at the pH of about 5.5 that resulted from the treatment. The removal of iron and aluminium oxides with Tamm reagent also resulted in a marked reduction in sorption at pH < 5. The results indicate that sorption was due in part to soil organic matter and in part to iron and/or aluminium oxides. At pH > 6, organic matter appeared to be the major sorbing constituent but under more acid conditions the oxides appeared to be increasingly important.     

The copper-mobilizing-potential of dissolved organic matter in soils varies 10-fold depending on soil incubation and extraction procedures

Copper is mobilized in soil by dissolved organic matter (DOM) but the role of DOM quality in this process is unclear. A one-step resin-exchange method was developed to measure the Cu-Mobilizing-Potential (CuMP) of DOM at pCu 11.3 and pH 7.0, representing background values. The CuMP of DOM was measured in soil solutions of 13 uncontaminated soils with different DOM extraction methods. The CuMP, expressed per unit dissolved organic carbon (DOC), varied 10-fold and followed the order water extracts > 0.01 M CaCl2 extracts > pore water. Soil solutions, obtained from soils that were stored air-dry for a long time or were subjected to drying-wetting cycles, had elevated DOC concentration, but the DOM had a low CuMP. Prolonged soil incubations decreased the DOC concentration and increased the CuMP, suggesting that most of the initially elevated DOM is less humified and has lower Cu affinity than DOM remaining after incubation. A significant positive correlation between the specific UV-absorption of DOM (indicating aromaticity) and CuMP was found for all DOM samples (R(2) = 0.58). It is concluded that the DOC concentration in soil is an insufficient predictor for the Cu mobilization and that DOM samples isolated from air-dried soils are distinct from those of soils kept moist.     

Solid-solution speciation and phytoavailability of copper and zinc in soils

The soil solution speciation and solid-phase fractionation of copper (Cu) and zinc (Zn) in 11 typical uncontaminated soils of South Australia were assessed in relation to heavy metal phytoavailability. The soils were analyzed for pH (4.9-8.4), soil organic matter content (3.5 to 23.8 g of C kg(-1)), total soil solution metal concentrations, Cu8 (49-358 microg kg(-1)) and Zn8 (121-582 microg kg(-1)), and dissolved organic matter (DOM) (69-827 mg of C L(-1)). The solid-liquid partition coefficient (Kd) ranged from between 13.9 and 152.4 L kg(-1) for Cu and 22.6 to 266.3 L kg(-1) for Zn. The phytoavailability of Cu and Zn could be predicted significantly using an empirical model with the solid-phase fractions of Cu and Zn, as obtained from selective sequential extraction scheme, as components. Phytoavailable Cu and Zn were found to significantly correlate with fulvic complex Cu (r= 0.944, P < 0.0001) and exchangeable Zn (r = 0.832, P = 0.002), respectively. The fulvic complex Cu was found to explain 89.2% of the variation in phytoavailable Cu, where as, the exchangeable Zn together with fulvic complex Zn could explain 78.9% of the variation in phytoavailable Zn. The data presented demonstrate the role of solid-phase metal fractions in understanding the heavy metal phytoavailability. The assessment of the role of solid-phase fractions in heavy metal phytoavailability is a neglected area of study and deserves close attention.     

Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.     

Chemical heterogeneity of organic soil colloids investigated by scanning transmission X-ray microscopy and C-1s NEXAFS microspectroscopy

Colloid release and deposition in soils and sorption of inorganic and organic pollutants to soil colloids are strongly influenced by the composition and chemical heterogeneity of colloidal soil particles. To investigate the chemical heterogeneity of organic soil colloids at the particle scale, we used synchrotron scanning transmission X-ray microscopy (STXM) and C-1s near-edge X-ray absorption fine structure (NEXAFS) spectroscopy on 49 individual particles isolated from the surface horizons of three forest soils. Stacks of 130 images of each particle were collected at different X-ray energies between 280 and 310 eV. From these image arrays, NEXAFS spectra were obtained for each pixel and analyzed by principle component analysis and cluster analysis (PCA-CA) to characterize the intraparticle heterogeneity of the organic components. The results demonstrate that the organic matter associated with water-dispersible soil colloids is chemically heterogeneous at the single-particle scale. PCA-CA identified at least two distinct regions within single particles. However, the spectral variations between these regions were much smaller than the variations of averaged NEXAFS spectra representing different particles from the same soil horizon, implying that interparticle heterogeneity is much larger than intraparticle heterogeneity. Especially the contents of aromatic and carboxyl carbon exhibited a large variability. Overall, the NEXAFS spectra of water-dispersible soil colloids were similar to the NEXAFS spectrum of the humic acid fraction, but differed clearly from the fulvic acid and dissolved organic matter fractions extracted from the same soil horizon using conventional techniques.     

Sorption and desorption of Cd2+ and Zn2+ ions in apatite-aqueous systems

As a low-soluble phosphate mineral capable of binding various metal ions, apatite can be used to immobilize toxic metals in soils and waters. In the present research the factors affecting sorption and desorption of Cd2+ and Zn2+ ions on/from apatites are investigated. Batch experiments were carried out using synthetic hydroxy-, fluoride-, and carbonate-substituted apatites having various specific surface area (SSA). Apatite sorption capacity was found to depend mainly on its SSA, ranging from 16 to 78 and from 11 to 79 mmol per 100 g of apatite for Cd2+ and Zn2+, respectively. The solution composition (pH, and presence of Cl- and NO3- ions) had no essential impact on sorption. Desorption of bound cations depended both on the sorption level and solution composition. The amount of desorbed Cd2+ and Zn2+ increased proportionally to the amount of sorbed cations. However, apatites having higher sorption capacity release relatively less sorbed cations. Desorption increases with increasing Ca2+ concentration in the solution, reaching 8-20% of sorbed Cd2+ in 0.002 M, 10-35% in 0.01 M, and 33-45% in 0.05 M Ca(NO3)2 solution. Compared to nitrate solutions, the presence of Cl- ions in the solution promotes the release of bound cations. Desorption of Zn2+ is slightly higher than that of Cd2+. The desorption mechanism was assumed to include both ion-exchange and adsorption of Ca2+ ions on apatite surface.     

The effects of plants on the mobilization of Cu and Zn in soil columns

Whereas metal effects on plants have been well studied, much less is known about plant effects on metal mobilization in soils. We investigated metal mobilization and speciation with a resolution of a few cm in soil columns planted with willows (Salix viminalis). In the presence of plants, the concentration profiles of dissolved organic carbon (DOC), major ions (e.g., Ca), Cu, and Zn exhibited more variation than in the absence of plants, and both smaller and larger concentrations were observed, indicative of strong local effects. The Cu concentration in the absence and presence of plants was controlled by DOC mobilization and could be described by the same relationship. Zn mobilization was controlled by DOC and Ca in the plant-free system and by pH and Ca in the presence of plants. Cu2+ and labile Zn were reasonably well predicted by the NICA-Donnan model and were influenced by the plant-induced changes of the soil solution composition. Plant uptake reduced the dissolved Zn concentration and transpiration reduced Cu and Zn leaching.     

Desorption kinetics of Cd, Zn, and Ni measured in soils by DGT

DGT (diffusive gradients in thin films) was used to measure the distribution and rates of exchange of Zn, Cd, and Ni between solid phase and solution in five different soils. Soil texture ranged from sandy loam to clay, pH ranged from 4.9 to 7.1, and organic carbon content ranged from 0.8% to 5.8%. DGT devices continuously remove metal to a Chelex gel layer after passage through a well-defined diffusion layer. The magnitude of the induced remobilization flux from the solid phase is related to the pool size of labile metal and the exchange kinetics between dissolved and sorbed metal. DGT devices were deployed over a series of times (4 h to 3 weeks), and the DIFS model (DGT induced fluxes in soils) was used to derive distribution coefficients for labile metal (Kdl) and the rate at which the soil system can supply metal from solid phase to solution, expressed as a response time. Response times for Zn and Cd were short generally (<8 min). They were so short in some soils (<1 min) that no distinction could be made between supply of metal being controlled by diffusion or the rate of release. Generally longer response times for Ni (5-20 min) were consistent with its slow desorption. The major factor influencing Kdl for Zn and Cd was pH, but association with humic substances in the solid phase also appeared to be important. The systematic decline, with increasing pH, in both the pool size of Ni available to the DGT device and the rate constant for its release is consistent with a part of the soil Ni pool being unavailable within a time scale of 1-20 min. This kinetic limitation is likely to limit the availability of Ni to plants.     

Sorption of veterinary pharmaceuticals in soils: a review

Veterinary pharmaceuticals (VPs) are used in large amounts in modern husbandry. Due to their use pattern, they possess a potential for reaching the soil environment. To assess their mobility in soil, the literature on sorption of chemicals used as VPs is reviewed and put into perspective of their physicochemical properties. The compilation of sorption coefficients to soil solids (Kd,solid) demonstrates that these chemicals display a wide range of mobility (0.2 < Kd,solid < 6,000 L/kg). Partition coefficients for association of tetracycline and quinolone carboxylic acid VPs to dissolved organic matter (Kd,DOM) vary between 100 and 50,000 L/kg. The variation in Kd,solid for a given compound in different soils can be significant. For most of the compounds, the variation is not considerably lower for the organic carbon-normalized sorption coefficient Koc. In addition, prediction of log Koc by log Kow leads to significant underestimation of log Koc and log Kd,DOM values. This suggests that mechanisms other than hydrophobic partitioning play a significant role in sorption of VPs. A number of hydrophobicity-independent mechanisms such as cation exchange, cation bridging at clay surfaces, surface complexation, and hydrogen bonding appear to be involved. These processes are not accounted for by organic carbon normalization, suggesting that this data treatment is conceptually inappropriate and fails to describe the sorption behavior. Moreover, prediction of log Koc based on the hydrophobicity parameter log Kow is not successful.     

Influence of EDDS on metal speciation in soil extracts: measurement and mechanistic multicomponent modeling

The use of the [S,S]-isomer of EDDS to enhance phytoextraction has been proposed for the remediation of heavy metal contaminated soils. Speciation of metals in soil solution in the presence of EDDS and dissolved organic matter (DOM) received, however, almost no attention, whereas metal speciation plays an important role in relation to uptake of metals by plants. We investigated the influence of EDDS on speciation of dissolved metals in batch extraction experiments using fourfield-contaminated soils with pH varying between 4.7 and 7.2. Free metal concentrations were determined with the Donnan membrane technique, and compared with results obtained with the chemical speciation program ECOSAT and the NICA-Donnan model using a multicomponent approach. Addition of EDDS increased total metal concentrations in our soil extracts by a factor between 1.1 and 32 (Al), 2.1-48 (Cu), 1.1-109 (Fe), 1.1-5.5 (Ni), and 1.3-17 (Zn). In general, Al, Cu, Fe, and Zn had the largest total concentrations in the EDDS-treated extracts, but the contribution of these metals to the sum of total metal concentrations varied significantly between our soils. Free metal concentrations varied between 7.0 and 8.9 (pCd2+), 3.9-9.9 (pCu2+), 6.3-10.2 (pNi2+), and 5.2-7.0 (pZn2+). Addition of EDDS decreased free metal concentrations by a factor between 1.4 and 1.9 (Cd), 3.4-216 (Cu), 1.3-186 (Ni), and 1.3-3.3 (Zn). Model predictions of free metal concentrations were very good, and predicted values were mostly within 1 order of magnitude difference from the measured concentrations. A multicomponent approach had to be used in our model calculations, because competition between Fe and other metals for binding with EDDS was important. This was done by including the solubility of metal oxides in our model calculations. Multicomponent models can be used in chelant-assisted phytoextraction experiments to predict the speciation of dissolved metals and to increase the understanding of metal uptake by plants.     

Solution speciation controls mercury isotope fractionation of Hg(II) sorption to goethite

The application of Hg isotope signatures as tracers for environmental Hg cycling requires the determination of isotope fractionation factors and mechanisms for individual processes. Here, we investigated Hg isotope fractionation of Hg(II) sorption to goethite in batch systems under different experimental conditions. We observed a mass-dependent enrichment of light Hg isotopes on the goethite surface relative to dissolved Hg (ε(202)Hg of -0.30‰ to -0.44‰) which was independent of the pH, chloride and sulfate concentration, type of surface complex, and equilibration time. Based on previous theoretical equilibrium fractionation factors, we propose that Hg isotope fractionation of Hg(II) sorption to goethite is controlled by an equilibrium isotope effect between Hg(II) solution species, expressed on the mineral surface by the adsorption of the cationic solution species. In contrast, the formation of outer-sphere complexes and subsequent conformation changes to different inner-sphere complexes appeared to have insignificant effects on the observed isotope fractionation. Our findings emphasize the importance of solution speciation in metal isotope sorption studies and suggest that the dissolved Hg(II) pool in soils and sediments, which is the most mobile and bioavailable, should be isotopically heavy, as light Hg isotopes are preferentially sequestered during binding to both mineral phases and natural organic matter.     

Spectroscopic investigation of ciprofloxacin speciation at the goethite-water interface

We investigated ciprofloxacin (a fluoroquinolone antibiotic) speciation as a function of pH in aqueous solution and in the presence of dissolved ferric ions and goethite using ATR-FTIR and UV-vis spectroscopy. The presence of dissolved and surface bound ferric species induced the deprotonation of the ciprofloxacin carboxylic acid group at pH < pKa1. The resultant ciprofloxacin zwitterions appeared to interact via both carboxylate oxygens to form bidentate chelate and bridging bidentate complexes within colloidal iron oxide-ciprofloxacin precipitates and bidentate chelates on the goethite surface. However, the structure of the aqueous ferric-ciprofloxacin complexes remains unclear. Our evidence for bidentate chelates (involving only the carboxylate oxygens) on the goethite surface was distinct from previous IR studies of fluoroquinolone sorption to metal oxides that have proposed surface complexes involving both the keto and the carboxylate groups. We find that the distinct ciprofloxacin surface complex proposed at the goethite-water interface may be a result of differences in metal oxide mineralogy or assignment of the carboxylate antisymmetric stretch in the metal oxide-fluoroquinolone spectra.     

Dissolved organic matter conformation and its interaction with pyrene as affected by water chemistry and concentration

Water chemistry and concentration of dissolved organic matter (DOM) have been reported to affect DOM conformation and binding properties with hydrophobic organic contaminants (HOCs). However, relationship between DOM conformation and its binding properties remains unclear. We designed a multibag equilibration system (MBES) to investigate the variation of carbon-normalized sorption coefficients (K(DOC)) of pyrene at different DOM concentrations based on an identical free solute concentration at different pHs and in the presence of Al ions. In addition, we studied the conformation of DOM under different conditions via atomic force microscopy (AFM) imaging, dynamic light scattering, and zeta potential measurements. Zeta potential measurements indicated that intra- and intermolecular interaction was facilitated at low pH or with the presence of Al ions, and a more organized molecular aggregate (such as a micelle-like structure) could form, thus, enhancing K(DOC). As DOM concentration increased, DOM molecular aggregation was promoted in a way reducing K(DOC). This research is a first attempt to correlate DOM conformation with K(DOC). Aggregation of DOM molecules resulting from increased zeta potential (less negative) generally led to an increased K(DOC). Further study in this area will provide valuable information on HOC-DOM interactions, thus, leading to more accurate predictions of K(DOC).     

Hydrophilic and hydrophobic sorption of organic acids by variable charge soils: effect of chemical acidity and acidic functional group

Sorption of organic acids by variable-charge soil occurs through both hydrophilic and hydrophobic sorption. In this study, the effect of chemical acidity and the type of acidic functional group on the relative contribution of hydrophilic and hydrophobic processes to sorption by a gibbsite-dominated and a kaolinite-dominated variable-charge soils was quantified by measuring sorption isotherms from different electrolytes (CaCl2, Ca(H2PO4)2, and KCl). The A1 soil is dominated by gibbsite whereas the DRC soil is primarily kaolinite. The organic acids investigated include five chlorinated phenols (pentachlorophenol, 2,3,4,6-tetrachlorophenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, and 2,4-dichlorophenol) with pKa values ranging from 4.69 to 7.85 and two acidic herbicides (2,4-D (pKa = 2.8) and prosulfuron (pKa = 3.76)) that contain carboxyl and urea functional groups, respectively. Anion exchange of chlorinated phenols and prosulfuron on both variable-charge soils as well as 2,4-D sorption on the A1 soil was linearly correlated to chemical acidity. The effective positive surface charge [AEC/(AEC + CEC)] and the anionic fraction of the organic acid in solution, which are both pH-dependent, were sufficient to estimate the contribution of anion exchange to organic acid sorption except for 2,4-D sorption by DRC soil. The latter was much greater than would be predicted from the pKa of 2,4-D. Calcium bridging between silanol edge group and 2,4-D was hypothesized and corroborated by differences in sorption measured from KCl and CaCl2 solutions. For predicting contributions from hydrophobic processes, a log-log linear relationship between pH-dependent octanol-water (Kow(pH)) and organic carbon-normalized sorption coefficients (Koc(pH)) appeared adequate.