Heavy metal sorption at the muscovite (001)-fulvic acid interface

The role of fulvic acid (FA) in modifying the adsorption mode and sorption capacity of divalent metal cations on the muscovite (001) surface was evaluated by measuring the uptake of Cu(2+), Zn(2+), and Pb(2+) from 0.01 m solutions at pH 3.7 with FA using in situ resonant anomalous X-ray reflectivity. The molecular-scale distributions of these cations combined with those previously observed for Hg(2+), Sr(2+), and Ba(2+) indicate metal uptake patterns controlled by cation-FA binding strength and cation hydration enthalpy. For weakly hydrated cations the presence of FA increased metal uptake by approximately 60-140%. Greater uptake corresponded with increasing cation-FA affinity (Ba(2+) ≈ Sr(2+) < Pb(2+) < Hg(2+)). This trend is associated with differences in the sorption mechanism: Ba(2+) and Sr(2+) sorbed in the outer portion of the FA film whereas Pb(2+) and Hg(2+) complexed with FA effectively throughout the film. The more strongly hydrated Cu(2+) and Zn(2+) adsorbed as two distinct outer-sphere complexes on the muscovite surface, with minimal change from their distribution without FA, indicating that their strong hydration impedes additional binding to the FA film despite their relatively strong affinity for FA.     

Kinetic controls on Cu and Pb sorption by ferrihydrite

Metal partitioning in ferrihydrite suspensions may reach equilibrium only after a long reaction time. To determine key factors controlling the kinetics, we measured Cu and Pb uptake as a function of ferrihydrite morphology, reaction temperature, metal competition, and fulvic acid concentration over a period of 2 months. X-ray microscopy, which was used to probe ferrihydrite morphology in suspension, showed that drying irreversibly converted the gellike structure of fresh precipitate into dense aggregates. These dense aggregates sorbed Cu and Pb much slower than the gel. Temperature had a more pronounced effect on the kinetics of metal uptake by ferrihydrite gel than by dense ferrihydrite. Independently of treatment and time, Cu and Pb were bound to the ferrihydrite surface byformation of edge-sharing inner-sphere sorption complexes as confirmed by X-ray absorption fine-structure (XAFS) spectroscopy. This invariable binding mechanism, together with the observed effects of morphology and temperature, are in line with surface diffusion limiting the slow sorption process. The quantification of diffusion-limited surface sites in soils and sediments and the subsequent estimation of the effect of reaction time and temperature will be a challenge for properly predicting the fate of metals in the environment.     

Ion exchange model for reversible sorption of divalent metals on calcite: implications for natural environments

Most of the thermodynamic models available in the literature describing the speciation of the calcite surface do not predict a significant concentration of sorbed Ca(II), whereas previous electrokinetics studies clearly show that Ca(2+) is the main cation determining the potential of the calcite surface. This study proposes a new thermodynamic model based on ion-exchange theory that is able to describe the reversible sorption of Ca(2+) on calcite. To constrain the model, concentrations of Ca(II) sorbed reversibly on the mineral surface were obtained as a function of pH. Such experimental data were obtained using solutions in equilibrium with both calcite and fixed p(CO2(g)) values (from 10(-5) to 10(-2) atm). The concentration of (de)sorbed Ca(II) is almost constant in the [7-9.5] pH range, having a value of approximately 1.2 × 10(-6) ± 0.4 × 10(-7) eq·g(-1). Such a value agrees with total sorption site densities that were previously calculated by crystallography and is used to obtain a selectivity coefficient between H(+) and Ca(2+) species by fitting the experimental data. Then, selectivity coefficients between H(+) and different metallic cations (Zn(2+), Cd(2+), Pb(2+)) that are able to accurately describe previously published data are proposed. Finally, the model is used to predict the contribution of calcite in the overall sorption of Cd(II) on a natural and complex solid (calcareous aquifer sand).     

Slow formation and dissolution of Zn precipitates in soil: a combined column-transport and XAFS study

Recent spectroscopic studies have demonstrated the formation of layered double hydroxides (LDH) and phyllosilicates upon sorption of Zn2+, Ni2+, and Co2+ to clay minerals and aluminum oxides at neutral to alkaline pH and at relatively high initial metal concentrations (>1 mM). The intention of the present study was to investigate whether such phases also form in soil under slightly acidic conditions and at lower metal concentrations. Columns packed with a loamy soil were percolated with aqueous solutions containing 0.1 or 0.2 mM Zn, Ni, Co, and Cd in a 10 mM CaCl2 background at pH 6.5. Metal breakthrough curves indicated a rapid initial sorption step, resulting in retarded breakthrough fronts, followed by further slow metal retention during the entire loading period of 42 days (7000 pore volumes). Total metal sorption and the contribution of slow sorption processes decreased in the order Zn > Ni > Co > Cd. Leaching the reacted soil with 10 mM CaCl2 at pH 6.5 remobilized 8% of the total retained Zn, 15% of Ni, 21% of Co, and 77% of Cd. Subsequent leaching with acidified influent (pH 3.0) remobilized most of the remaining metals. X-ray absorption fine-structure (XAFS) spectroscopy revealed that slow Zn sorption was due to the formation of a Zn-Al LDH precipitate. Although Ni, Co, and Cd concentrations were too low for XAFS analysis, their leaching patterns suggest that part of Ni and Co were also incorporated in solid phases, while most sorbed Cd was still present as exchangeable sorption complex after 42 days. A small but significant percentage of the sorbed metals (2-5%) remained in the soil, even after leaching with more than 3000 pore volumes at pH 3.0, which may suggest micropore diffusion or incorporation into more stable mineral phases.     

Interactions between microbial iron reduction and metal geochemistry: effect of redox cycling on transition metal speciation in iron bearing sediments

Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respectto Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a -3x increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by approximately 12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These data suggest that in situ redox cycling may serve as an effective method for     

Uptake of metals during chelant-assisted phytoextraction with EDDS related to the solubilized metal concentration

The use of chelants to enhance phytoextraction is one method being tested to make phytoextraction efficient enough to be used as a remediation technique for heavy metal pollution in the field. We performed pot experiments with sunflowers in order to investigate the use of the biodegradable chelating agent SS-EDDS for this purpose. We used singly and combined contaminated soils (Cu, Zn) and multimetal contaminated field soils (Cu, Zn, Cd, Pb). EDDS (10 mmol kg(-10 soil) increased soil solution metals greatly for Cu (factor 840-4260) and Pb (factor 100-315), and to a lesser extent for Zn (factor 23-50). It was found that Zn (when present as the sole metal), Cu, and Pb uptake by sunflowers was increased by EDDS, butin multimetal contaminated soil Zn and Cd were not. EDDS was observed in the sunflower roots and shoots at concentrations equal to metal uptake. The different metal uptake in the various soils can be related to a linear relationship between Cu and Zn in soil solution in the presence of EDDS and plant uptake, indicating the great importance of measuring and reporting soil solution metal concentrations in phytoextraction studies.     

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.     

Effects of divalent cations on Halobacterium salinarum cell aggregation

Ca(2+) was found to be essential for initiating Halobacterium salinarum CCM 2090 cell aggregation. The floc formed from such aggregation could easily be dissociated without cellular lysis by sodium citrate. Cr(2+), Mn(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), and Zn(2+) could replace Ca(2+). However, Mg(2+), Sr(2+), Mo(2+), Cd(2+), Sn(2+), Hg(2+), and Pb(2+) induced no flocculation of cells of this halophilic archaeon. Mg(2+) acted antagonistically against Ca(2+)-induced aggregation. Such aggregation might be directly caused by the interaction of Ca(2+) and aggregation factors from 55 degrees C-treated cell extract.     

Potential remediation of waters contaminated with Cr(III), Cu, and Zn by sorption on the organic polymeric fraction of olive mill wastewater (polymerin) and its derivatives

A study on the individual sorption of Cr(III), Cu, and Zn on polymerin, the humic-acid-like fraction of olive mill wastewater, and its derivatives, K-polymerin and an Fe(OH)x-polymerin complex, showed that these heavy metals were strongly sorbed on polymerin and K-polymerin in the order Cr(III) > Cu > Zn. The sorption on Fe(OH)x-polymerin was to a lower extent compared with that of the other two sorbents, but to a higher extent compared with ferrihydride [Fe(OH)x]. Combined atomic absorption spectrometry and diffuse reflectance infrared Fourier transform spectroscopy analyses showed that the selected heavy metals were individually sorbed on polymerin by means of a cation exchange mechanism, which was consistent with the replacement of Ca, Mg, K, and H bound to the carboxylate groups of the biosorbent and the concomitant chelation of the heavy metals by the OH groups of polymerin polysaccharide component. In binary combination and equimolar ratio, Cu was sorbed by polymerin more selectively than Zn. In ternary combination and equimolar ratio, Cr(III), Cu, and Zn were sorbed by polymerin in the order Cr(III) > Cu > Zn. The sorbing capacity of Zn and Cu was strongly influenced by Cr(III), whereas the sorbing capacity of Cr(III) was not affected bythe presence of the other two metals. The overall sorbing capacity of the binary and ternary mixtures of the three metals on polymerin proved to be considerable and much greater than that on Fe(OH)x-polymerin. Simulated wastewaters contaminated with Cu and Zn were purified after three sorption cycles by polymerin renewed at each cycle, whereas those containing a mixture of Cr(III), Cu, and Zn showed residues of Zn after five cycles. We briefly discuss environmental and industrial advantages for a possible exploitation of polymerin.     

Purification and characterization of a novel serine protease from the mushroom Pholiota nameko

A novel serine protease, with a molecular mass of 19 kDa and the N-terminal sequence of ARTPEAPAEV, was isolated from dried fruiting bodies of the mushroom Pholiota nameko. The purification protocol comprised ion exchange chromatography on DEAE-cellulose, Q-Sepharose and SP-Sepharose, and gel filtration on Superdex 75. It was unadsorbed on DEAE-cellulose and Q-Sepharose but adsorbed on SP-Sepharose. It exhibited an optimum temperature at 50°C, an optimum pH at pH 8.8, a Km of 5.64 mg/mL and a Vmax of 0.98 μmol/min/mL against substrate casein. A number of metal ions inhibited the enzyme including Pb(2+), Mn(2+), Ca(2+), Hg(2+), Zn(2+), Cu(2+), Co(2+), Fe(3+) and Al(3+), with the inhibition of the last two cations being the most potent. K(+) and Mg(2+) slightly enhanced, while Li(+) moderately potentiated the activity of the protease. The protease was strongly inhibited by phenylmethylsulfonyl fluoride (PMSF), suggesting that it is a serine protease.     

X-ray absorption spectroscopy study of the effects of pH and ionic strength on Pb(II) sorption to amorphous silica

Pb(III) sorption to hydrous amorphous SiO2 was studied as a function of pH and ionic strength using XAS to characterize the sorption products formed. Pb sorption increased with increasing pH and decreasing ionic strength. The XAS data indicated that the mechanism of Pb(II) sorption to the SiO2 surface was pH-dependent. At pH < 4.5, a mononuclear inner-sphere Pb sorption complex with ionic character dominated the Pb surface speciation. Between pH 4.5 and pH 5.6, sorption increasingly occurred via the formation of surface-attached covalent polynuclear Pb species, possibly Pb-Pb dimers, and these were the dominant Pb complexes at pH > or = 6.3. Decreasing ionic strength from I = 0.1 to I = 0.005 M NaClO4 significantly increased Pb sorption but did not strongly influence the average local coordination environment of sorbed Pb at given pH, suggesting that the formation of mononuclear and polynuclear Pb complexes at the surface were coupled; possibly, Pb monomers control the formation of Pb polynuclear species by diffusion along the surface, or they act as nucleation centers for additional Pb uptake from solution. This study shows that the effectiveness of SiO2 in retaining Pb(II) is strongly dependent on solution conditions. At low pH, Pb(II) may be effectively remobilized by competition with other cations, whereas sorbed Pb is expected to become less susceptible to desorption with increasing pH. However, unlike for Ni(II) and Co(II), no lead phyllosilicates are formed at these higher pH values; therefore, SiO2 is expected to be a less effective sink for Pb immobilization than for these other metals.     

Synthetic Phytochelatin Surface Display in Cupriavidus metallidurans CH34 for Enhanced Metals Bioremediation

This work describes the effects of the cell surface display of a synthetic phytochelatin in the highly metal tolerant bacterium Cupriavidus metallidurans CH34. The EC20sp synthetic phytochelatin gene was fused between the coding sequences of the signal peptide (SS) and of the autotransporter β-domain of the Neisseria gonorrhoeae IgA protease precursor (IgAβ), which successfully targeted the hybrid protein toward the C. metallidurans outer membrane. The expression of the SS-EC20sp-IgAβ gene fusion was driven by a modified version of the Bacillus subtilis mrgA promoter showing high level basal gene expression that is further enhanced by metal presence in C. metallidurans. The recombinant strain showed increased ability to immobilize Pb(2+), Zn(2+), Cu(2+), Cd(2+), Mn(2+), and Ni(2+) ions from the external medium when compared to the control strain. To ensure plasmid stability and biological containment, the MOB region of the plasmid was replaced by the E. coli hok/sok coding sequence.     

Lead sorption onto ferrihydrite. 1. A macroscopic and spectroscopic assessment

In this research, traditional macroscopic studies were complemented with XAS analyses to elucidate the mechanisms controlling Pb(II) sorption onto ferrihydrite as a function of pH, ionic strength, and adsorbate concentrations. Analyses of XANES and XAFS studies demonstrate that Pb(II) ions predominantly sorb onto ferrihydrite via inner-sphere complexation, not retaining their primary hydration shell upon sorption. At higher pH values (pH > or = 5.0), edge-sharing bidentate complexes are mainly formed on the oxide surface with two Fe atoms located at approximately 3.34 A. In contrast, XAS studies on Pb(II) sorption onto ferrihydrite, at pH 4.5, reveal two distinct Pb-Fe bond average radial distances of 3.34 and 3.89 A, suggestive of a mixture of monodentate and bidentate sorption complexes present at the oxide surface. Interestingly, at constant pH, the configuration of the sorption complex is independent of the adsorbate concentration. Hence, Pb(II) sorption to a highly disordered adsorbent such as ferrihydrite can be described by one average type of mechanism. Overall, this information will aid scientists and engineers in improving the current models that predict and manage the fate of toxic metals, such as Pb(II), in the aquatic and soil environments.     

Solid- and solution-phase organics dictate copper distribution and speciation in multicomponent systems containing ferrihydrite, organic matter, and montmorillonite

Copper retention by ferrihydrite, leaf compost, and montmorillonite was studied over 8 months in systems that emulate a natural soil where different solid phases compete for Cu through a common solution in a compartmentalized batch reactor. Copper speciation in solution (total dissolved, DPASV-labile, and free) and exchangeable and total Cu in individual solid phases were determined. Organic carbon in solution (DOC) and that retained by the mineral phases were also determined. Cu sorption reached steady-state after 4 months and accounted for 80% of the Cu initially added to the system (0.15 mg L(-1)). The remaining 20% stayed in solution as nonlabile (82.8%), labile (17%), and free (0.2%) Cu species. Copper sorption followed the order organic matter > silicate clays > iron oxides. Within each solid phase, exchangeable Cu was < or = 10% of the total Cu sorbed. DOC reached steady state (22 mg L(-1)) after 4 months and seemed to control Cu solubility and sorption behavior by the formation of soluble Cu-DOC complexes and by sorbing onto the mineral phases. DOC sorption onto ferrihydrite prevented Cu retention by this solid phase. Using a multicomponent system and 8 months equilibrations, we were able to capture some of the more important aspects of the complexity of soil environments bytaking into account diffusion processes and competition among solid- and solution-phase soil constituents in the retention of a metal cation.     

Impact of metal sorption and internalization on nitrification inhibition

The goal of this study was to explore the relationship between metal extracellular sorption, intracellular accumulation, and nitrification inhibition. Metal sorption on nitrifying biomass was rapid and could be described by linear partitioning with partition coefficients (Kp) of 20.3 +/- 0.1, 0.4 +/- 0.0, 0.1 +/- 0.0, and 0.2 +/- 0.0 L/g biomass chemical oxygen demand for Cu, Zn, Ni, and Cd, respectively. On the other hand, intracellular Zn, Ni, and Cd concentrations continued to increase with time beyond 12 h after metal addition, whereas intracellular Cu attained equilibrium after 4 h. Metal internalization kinetics could be described by an intraparticle diffusion model, with characteristic diffusion time constants (td) of 9.4, 64.6, 80.5, and 66.1 h for Cu, Zn, Ni, and Cd, respectively. Ultimate internalized percentages of the total cell-associated metal were 1.4 +/- 0.0, 4.3 +/- 0.5,7.6 +/- 1.0, and 2.7 +/- 0.2% for Cu, Zn, Ni, and Cd, respectively. Nitrification inhibition was not a function of the sorbed metal fraction but correlated well with intracellular Zn, Ni, or Cd fractions. An intraparticle diffusion model coupled with a saturation-type biological toxicity model fit the inhibition data for varying initial Cd concentrations and exposure periods. In contrast, no relationship between intracellular or sorbed Cu concentrations and nitrification inhibition was observed. In the presence of 1 mM Cu, less than 13.3 +/- 10.5% cells remained viable as compared to 72.8 +/- 7.5,104.8 +/- 1.7, and 84.7 +/- 7.0% (assumed 100% viable cells in metal-free control) in the presence of 1 mM Zn, Ni, and Cd, respectively. Hence, the observations that inhibition by metals such as Zn, Ni, and Cd is related to their intracellular fraction and the slow kinetics of metal internalization indicate that metal inhibition can easily be underpredicted from short-term batch assays. Furthermore, the inhibitory mechanism of Cu was very different from Zn, Ni, and Cd and may involve rapid loss of membrane integrity.     

Copper(II) and cadmium(II) sorption onto ferrihydrite in the presence of phthalic acid: some properties of the ternary complex

Copper, cadmium, and phthalic acid (H2Lp) adsorption by ferrihydrite was examined for binary and ternary systems. In binary systems adsorption was well reproduced using the diffuse layer model (DLM), and H2Lp adsorption was analogous to that of inorganic diprotic acids in terms of the relationship between the adsorption constants and acidity constants. In ternary systems H2Lp caused both the enhancement (due to ternary complexformation) and inhibition (due to solution complex formation) of Cu2+ and Cd2+ sorption depending on the conditions. The DLM could only describe the effect of H2Lp on metal ion sorption by including ternary complexes of the form [triple bond]FeOHMLp (0), where [triple bond]FeOH is a surface site and M is Cu or Cd. The relationship between binary metal adsorption constants and the ternary complex adsorption constants from this and previous studies suggest several properties of ternary complexes. First, ternary complex structures on both ferrihydrite and goethite are either the same or similar. Second, those cations having large adsorption constants also have large equilibrium constants for ternary complex formation. Third, ligands forming stronger solution complexes with cations will also form stronger surface ternary complexes though, because of the strong solution complex, they will not necessarily enhance cation adsorption.     

Characterization of sorption sites on Pilayella littoralis and metal binding assessment using 113Cd and 27Al nuclear magnetic resonance

Metal interactions with the cellular structures of the marine alga Pilayella littoralis have been investigated to better understand how biomaterials sorb dissolved metals. Algae metal binding capacity at pH 5.0 was 2000, 850, 430, and 560 micromol g(-1) of dried material for Al(III), Cu(II), Cd(II), and Co(II), respectively. Binding site characterization was assessed by 1H and 13C nuclear magnetic resonance spectroscopy. Also, Fourier Transform Infrared spectroscopy (FTIR) provided some information about the types of functional groups that appear to be present in the algal material. The results suggested the presence of carboxylate, ether, amino, and hydroxyl groups. Investigation of metal competition for the alga binding sites was performed using 27Al and 113Cd NMR spectroscopy, which proved to be a valuable technique for Al and Cd sorption assessment. Aluminum and Cu were efficiently sorbed by the alga sites, and the binding affinity order of these metals was Al(III) > Cu(II) > Cd(II) > Co(II).     

Sorption of anionic metsulfuron-methyl and cationic difenzoquat on peat and soil as affected by copper

The effect of cationic copper (Cu2+) on the sorption of anionic metsulfuron-methyl (Me) and cationic difenzoquat (DZ) to peat and soil was studied using a batch equilibration method. The results showed that Cu2+ increased the sorption of Me but diminished the sorption of DZ. The adsorption of Cu2+ on the surface of peat and soil neutralizes the negative charge, making the zeta potential (zeta) of peat and soil less negative, consequently decreasing the repulsion between the surface of peat or soil and Me and increasing the sorption of Me. Cu2+ may additionally form Cu-Me complexes in aqueous solution, which was preferentially sorbed to peat and soil over the anionic Me. In contrast, the decreased negative surface charge of soil and peat does not favor the sorption of cationic DZ. Fourier transform infrared showed that DZ may be sorbed through interaction with -OH or -COOH groups of peat and soil and that surface complexes of Cu2+ may form through these groups. A competitive sorption between Cu2t and DZ for the same sorption sites is indicated, leading to mutual sorption inhibition of both cations.     

Effect of alcohols on the retention mechanisms of Cd and Zn on Wyoming bentonite and illite

The effects of ethanol- and methanol-water mixtures on Zn and Cd sorption onto bentonite and illite were investigated at low initial metal concentration (< or =10(-5) M) and low ionic strength (2.5 mM Ca(NO3)2). For all cosolvent fractions, the percent coverage of Zn and Cd to clay minerals was low (<5%) and independent of the solution dielectric constant, epsilon, except for Zn at 10 microM. Cadmium sorption to bentonite and illite was independent of epsilon. Zinc sorption varied significantly between clay types, cosolvent type, and cosolvent fraction. The partitioning of Zn to bentonite increased from 0 to 10% alcohol-water fraction and decreased after 10%. The same pattern was observed for the partitioning of Zn on illite in methanol-water mixtures. In ethanol-water mixtures, Kf for Zn on illite increased continuouslyfrom 0 to 50% ethanol. The decreased partitioning and hence mobility of Zn to bentonite and illite after 10% alcohol (only in methanol-water mixtures for illite) suggests a potential environmental threat resulting from increased transport of this metal in subsurface environments where these cosolvents are present.     

Chemical speciation of Zn,Cd, Cu,and Pb in pore waters of agricultural and contaminated soils using Donnan dialysis

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. Numerous analytical methods have been utilized for determining trace metal speciation in aqueous environmental matrixes; however, most of these methods suffer from significant interferences. The Donnan dialysis membrane technique minimizes these interferences and has been used in this study to determine free Zn2+, Cd2+, Cu2+, and Pb2+ activities in pore waters from 15 agricultural and 12 long-term contaminated soils. The soils vary widely in their origin, pH, organic carbon content, and total metal concentrations. Pore water pM2+ activities also covered a wide range and were controlled by soil pH and total metal concentrations. For the agricultural soils, most of the free metal activities were below detection limit, apart from Zn2+ for which the fraction of free Zn2+ in soluble Zn ranged from 2.3 to 87% (mean 43%). Five of the agricultural soils had detectable free Cd2+ with fractions of free metal ranging from 59 to 102% (mean 75%). For the contaminated soils with detectable free metal concentrations, the fraction of free metal as a percentage of soluble metal varied from 9.9 to 97% (mean 50%) for Zn2+, from 22 to 86% (mean 49%) for Cd2+, from 0.4 to 32.1% (mean 5%) for Cu2+, and from 2.9 to 48.8% (mean 20.1%) for Pb2+. For the contaminated soils, the equilibrium speciation programs GEOCHEM and WHAM Model VI provided reasonable estimates of free Zn2+ fractions in comparison to the measured fractions (R2 approximately 0.7), while estimates of free Cd2+ fractions were less agreeable (R2 approximately 0.5). The models generally predicted stronger binding of Cu2+ to DOC and hence lower fractions of free Cu2+ as compared with the observed fractions. The binding of Cu2+ and Pb2+ to DOC predicted by WHAM Model VI was much strongerthan that predicted by GEOCHEM.