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.     

Porewater evidence of metal (Cu, Ni, Co, Zn, Cd) mobilization in an acidic, ombrotrophic bog impacted by a smelter, Harjavalta, Finland and comparison with reference sites

Porewaters were collected from three Finnish peat bogs subjected to varying inputs of atmospheric trace metals: Hietaj?rvi (HIJ), a low-background site, Outokumpu (OUT), near a Cu-Ni mine, and Harjavalta (HAR), near a Cu-Ni smelter. Samples for metal analyses were collected at depths ranging from 10 to 70 cm using a purpose-built syringe-type sampler. Metal concentrations were determined using inductively coupled plasma-sector field-mass spectrometry (ICP-SF-MS). Porewater concentrations at HIJ and OUT (Cd <0.3 nM, Co <1.4 nM, Cu, Ni <8 nM, Zn <250 nM) are independent of metal concentrations in the solid phase (peat). At OUT there is a limited release of Ni to the porewaters, but concentrations in the aqueous phase are generally below 0.3% of the total concentration in any given peat sample. These data are consistent with the immobility of these metals after deposition from the air. In contrast, porewaters at HAR are enriched in trace metals compared to the other sites by a factor of 2 (Zn), 10 (Cd), 20 (Co), and 100 (Cu and Ni) with dissolved fractions of Cu and Ni accounting for ca. 20% of the metal inventories in the cores. The elevated release of metals from solid phases at HAR is consistent with the postdepositional migration of metals at this site and reflects the predominance of oxide phases supplied to the bog surface and the much lower pH values (<3.4). The elevated proton concentrations not only promote mineral dissolution but also compete with cation exchange processes and hinder the formation of metal complexes with organic ligands.     

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.     

Reaction-based model describing competitive sorption and transport of Cd, Zn, and Ni in an acidic soil

Predicting the mobility of heavy metals in soils requires models that accurately describe metal adsorption in the presence of competing cations. They should also be easily adjustable to specific soil materials and applicable in reactive transport codes. In this study, Cd adsorption to an acidic soil material was investigated over a wide concentration range (10(-8) to 10(-2) M CdCl2) in the presence of different background electrolytes (10(-4) to 10(-2) M CaCl2 or MgCl2 or 0.05 to 0.5 M NaCl). The adsorption experiments were conducted at pH values between 4.6 and 6.5 A reaction-based sorption model was developed using a combination of nonspecific cation exchange reactions and competitive sorption reactions to sites with high affinity for heavy metals. This combined cation exchange/specific sorption (CESS) model accurately described the entire Cd sorption data set. Coupled to a solute transport code, the model accurately predicted Cd breakthrough curves obtained in column transport experiments. The model was further extended to describe competitive sorption and transport of Cd, Zn, and Ni. At pH 4.6, both Zn and Ni exhibited similar sorption and transport behavior as observed for Cd. In all transport experiments conducted under acidic conditions, heavy metal adsorption was shown to be reversible and kinetic effects were negligible within time periods ranging from hours up to four weeks.     

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.     

Groundwater acidification and the mobilization of trace metals in a sandy aquifer

The acidification of groundwater due to acid rain impact and the mobilization of the trace metals Ni, Be, Cd and Co was studied in a noncalcareous sandy aquifer. The groundwater is acidified down to pH 4.4 in the upper 3-4 m of the saturated zone. There is a sharp acidification front and below that the pH increases to 5.2-6.5. The acid zone groundwater contains an Al concentration of approximately 0.2 mM. These observations could be explained by a reactive transport model for downward groundwater movement based on ion exchange and equilibrium with Al(OH)3. At the acidification front, the Al3+ in groundwater exchanges for sorbed Ca2+ and Mg2+ and the coupled dissolution of Al(OH)3 causes the pH to increase. The downward migration rate of the acidification front is 3.5-5.0 cm/yr. Trace metals (Ni, Be, Cd and Co) are found to accumulate near the acidification front. Downward moving, low pH, and trace metal containing groundwater passes the acidification front, and the trace metals adsorb as the pH increases. The acidification front moves downward at a slower rate, and in this process the heavy metals are desorbed. Accordingly, the acidification front functions as a geochemical trap where trace metals accumulate, and their amount will increase with time. Different surface complexation models were explored to explain the behavior of Ni. Neither a simple iron oxide surface complexation model nor ion exchange could explain the field observations of the Ni distribution. The sediment appeared, even at low pH, to have a much stronger affinity toward Ni than predicted by the iron oxide model. The discrepancy can be accounted for in the model by increasing the Ni binding strength constant in combination with an increased number of reactive sites.     

Metal complexation properties of freshwater dissolved organic matter are explained by its aromaticity and by anthropogenic ligands

Dissolved organic matter (DOM) in surface waters affects the fate and environmental effects of trace metals. We measured variability in the Cd, Cu, Ni, and Zn affinity of 23 DOM samples isolated by reverse osmosis from freshwaters in natural, agricultural, and urban areas. Affinities at uniform pH and ionic composition were assayed at low, environmentally relevant free Cd, Cu, Ni, and Zn activities. The C-normalized metal binding of DOM varied 4-fold (Cu) or about 10-fold (Cd, Ni, Zn) among samples. The dissolved organic carbon concentration ranged only 9-fold in the waters, illustrating that DOM quality is an equally important parameter for metal complexation as DOM quantity. The UV-absorbance of DOM explained metal affinity only for waters receiving few urban inputs, indicating that in those waters, aromatic humic substances are the dominant metal chelators. Larger metal affinities were found for DOM from waters with urban inputs. Aminopolycarboxylate ligands (mainly EDTA) were detected at concentrations up to 0.14 μM and partly explained the larger metal affinity. Nickel concentrations in these surface waters are strongly related to EDTA concentrations (R2=0.96) and this is underpinned by speciation calculations. It is concluded that metal complexation in waters with anthropogenic discharges is larger than that estimated with models that only take into account binding on humic substances.     

Understanding the effects of soil characteristics on phytotoxicity and bioavailability of nickel using speciation models

Acidity (pH) has been realized to be the most important soil characteristic that modulates bioavailability of heavy metals by affecting both the chemical speciation of metals in soil and the metal binding to the active sites on biota. In this work, we show that besides soil pH, metal bioavailability also depends to a certain extent on the type of soil. A better understanding of the role of soil type in regulating metal availability can be achieved with the analysis of soil composition and with calculations using chemical speciation models. Results of pot experiments, in which three different soils were spiked with nickel, show that the EC50 of total nickel in decreasing the biomass production of oats varies widely (0.7-22.5 mmol kg(-1) soil, more than 30 times). pH (4.7-7.0) is the most important factor, explaining up to a factor of 14 difference of nickel bioavailability in the soils. The remaining variation is caused by other differences in soil composition (soil type). The bioavailability and toxicity of nickel in the organic matter-rich soil studied is less than half of that in the sandy and clay soil studied at a similar pH. The chemical calculations using a multi-surface speciation model show that soil organic matter binds Ni much stronger than clay silicates and iron (hydr)oxides within the acidic pH range, which supports the experimental findings. In all three soils, the EC50 of Ni expressed in terms of Ni in 0.01 M CaCl2 soil extraction is rather stable (24-58 microM), suggesting the possibility to use this extraction as an estimation of metal availability in soil.     

Interactions of trace metals with hydrogels and filter membranes used in DET and DGT techniques

Equilibrium partitioning of trace metals between bulk solution and hydrogels/filter was studied. Under some conditions, trace metal concentrations were higher in the hydrogels or filter membranes compared to bulk solution (enrichment). In synthetic soft water, enrichment of cationic trace metals in polyacrylamide hydrogels decreased with increasing trace metal concentration. Enrichment was little affected by Ca and Mg in the concentration range typically encountered in natural freshwaters, indicating high affinity but low capacity binding of trace metals to solid structure in polyacrylamide gels. The apparent binding strength decreased in the sequence: Cu > Pb > Ni approximately to Cd approximately to Co and a low concentration of cationic Cu eliminated enrichment of weakly binding trace metal cations. The polyacrylamide gels also had an affinity for fulvic acid and/or its trace metal complexes. Enrichment of cationic Cd in agarose gel and hydrophilic polyethersulfone filter was independent of concentration (10 nM to 5 microM) but decreased with increasing Ca/ Mg concentration and ionic strength, suggesting that it is mainly due to electrostatic interactions. However, Cu and Pb were enriched even after equilibration in seawater, indicating that these metals additionally bind to sites within the agarose gel and filter. Compared to the polyacrylamide gels, agarose gel had a lower affinity for metal-fulvic complexes. Potential biases in measurements made with the diffusive equilibration in thin-films (DET) technique, identified by this work, are discussed.     

Extracellular polymeric substances from Bacillus subtilis associated with minerals modify the extent and rate of heavy metal sorption

Extracellular polymeric substances (EPS) are an important source of organic matter in soil. Once released by microorganisms, a portion may be sorbed to mineral surfaces, thereby altering the mineral?s ability to immobilize heavy metals. EPS from Bacillus subtilis were reacted with Ca-saturated bentonite and ferrihydrite in 0.01 M KCl at pH 5.0 to follow the preferential uptake of EPS-C, -N, and -P. The sorption kinetics of Pb(2+), Cu(2+), and Zn(2+) to the resulting EPS-mineral composites was studied in single and binary metal batch experiments ([metal](total) = 50 μM, pH 5.0). Bentonite sorbed much more EPS-C (18.5 mg g(-1)) than ferrihydrite (7.9 mg g(-1)). During sorption, EPS were chemically and size fractionated with bentonite favoring the uptake of low-molecular weight components and EPS-N, and ferrihydrite selectively retaining high-molecular weight and P-rich components. Surface area and pore size measurements by N(2) gas adsorption at 77 K indicated that EPS altered the structure of mineral-EPS associations by inducing partial disaggregation of bentonite and aggregation of ferrihydrite. Whereas mineral-bound EPS increased the extent and rate of Pb(2+), Cu(2+), and Zn(2+) sorption for bentonite, either no effect or a decrease in metal uptake was observed for ferrihydrite. The extent of sorption always followed the order Pb(2+) > Cu(2+) > Zn(2+), which also prevailed in binary Pb(2+)/Cu(2+) systems. In consequence, sorption of EPS to different minerals may have contrasting consequences for the immobilization of heavy metals in natural environments by inducing mineral-specific alterations of the pore size distribution and, thus, of available sorption sites.     

Molecular-scale speciation of Zn and Ni in soil ferromanganese nodules from loess soils of the Mississippi Basin

Determining how environmentally important trace metals are sequestered in soils at the molecular scale is critical to developing a solid scientific basis for maintaining soil quality and formulating effective remediation strategies. The speciation of Zn and Ni in ferromanganese nodules from loess soils of the Mississippi Basin was determined by a synergistic use of three noninvasive synchrotron-based techniques: X-ray microfluorescence (microXRF), X-ray microdiffraction (microXRD), and extended X-ray absorption fine structure spectroscopy (EXAFS). We show that Ni is distributed between goethite (alpha-FeOOH) and the manganese oxide lithiophorite, whereas Zn is bound to goethite, lithiophorite, phyllosilicates, and the manganese oxide birnessite. The selective association of Ni with only iron and manganese oxides is an explanation for its higher partitioning in nodules over the soil clay matrix reported from soils worldwide. This could also explain the observed enrichment of Ni in oceanic manganese nodules. The combination of these three techniques provides a new method for determining trace metal speciation in both natural and contaminated environmental materials.     

Linking solid phase speciation of Pb sequestered to birnessite to oral Pb bioaccessibility: implications for soil remediation

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of lead-contaminated soils. In this study, Pb was sorbed to a model soil mineral, birnessite, and was placed in a simulated gastrointestinal tract (in vitro) to simulate the possible effects of ingestion of a soil contaminated with Pb. The changes in Pb speciation were determined using extended X-ray absorption fine structure and X-ray absorption near edge spectroscopy. Birnessite has a very high affinity for Pb with a sorption maximum of 0.59 mol Pb kg(-1) (approximately 12% Pb sorbed by mass) in which there was no detectable bioaccessible Pb (< 0.002%). Surface speciation of the birnessite Pb was determined to be a triple corner sharing complex in the birnessite interlayer. Lead sorbed to Mn oxide in contaminated media will have a very low (approximately equal to 0) Pb bioaccessibility and present little risk associated with incidental ingestion of soil. These results suggest that birnessite, and other Mn oxides would be powerful remediation tools for Pb-contaminated media because of their high affinity for Pb.     

Nickel sequestration in a kaolinite-humic acid complex

Incorporation of first row transition metals into stable surface precipitates can play an important role in reducing the bioavailability of these metals in neutral and alkaline soils. Organic coatings may interfere with this sorption mechanism by changing the surface characteristics and by masking the mineral surface from metal sorptives. In this study, kinetic sorption and desorption experiments were combined with extended X-ray absorption fine structure (EXAFS) spectroscopy to elucidate the effect of humic acid (HA) coatings on the formation and stabilization of nickel precipitates at the kaolinite-water interface. Initial Ni uptake (pH 7.5, [Ni]i = 3 mM, and I = 0.02 M NaNO3) increased with greater amounts of HA coated onto the kaolinite surface. Ni uptake continued over an extended period of time without reaching an apparent equilibrium. EXAFS analysis of the Ni sorption complex structures formed over time (up to 7 months) revealed the formation of a Ni-Al layered double hydroxide (LDH) precipitate at the kaolinite surface in the absence of HA. HA alone formed an inner-sphere complex with Ni (with 2 carbon atoms at an average radial distance of 2.85 A). A Ni-Al LDH precipitate phase was formed at the kaolinite surface in the presence of a 1 wt % HA coating. However, with 5 wt % HA coated at the kaolinite surface, the formation of a surface precipitate was slowed significantly, and the precipitate formed was similar in structure to Ni(OH)2(s). The Ni(OH)2 precipitate was not resistant to proton dissolution, while the Ni-Al LDH precipitate was. These results augment earlier findings that the incorporation of Ni and other first row transition metals into stable surface precipitates is an important sequestration pathway for toxic metals in the environment, despite the presence of ubiquitous coating materials such as humic acids.     

Effect of soil fulvic acid on nickel(II) sorption and bonding at the aqueous-boehmite (gamma-AIOOH) interface

The influence of soil-derived fulvic acid (SFA) on Ni(II) sorption and speciation in aqueous boehmite (gamma-AIOOH) suspensions was evaluated using a combination of sorption experiments and Ni K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy measurements. Co-sorption of SFA at the aqueous-boehmite interface modifies both the extent of Ni(II) sorption as well as the local structure of the sorbing Ni(II) ions. In SFA-free suspensions, Ni(II) sorbs by forming inner-sphere bidentate mononuclear complexes with surface aluminol groups. Addition of SFA increases Ni(II) sorption at pH conditions below the sorption edge observed in SFA-free suspensions and diminishes Ni(II) sorption at pH above the SFA-free sorption edge. When SFA is co-sorbed to boehmite, Ni(II) sorbs by forming both ligand-bridging ternary surface complexes (Ni(II)-SFA-boehmite) as well as surface complexes in which Ni(II) remains directly bonded to aluminol groups, that is, binary Ni(II)-boehmite or metal-bridging ternary surface complexes (SFA-Ni(II)-boehmite). The relative contribution of the individual sorption complexes depends heavily on geochemical conditions; the concentration of ligand-bridging complexes increases with increasing SFA sorption and decreasing pH. The local structure of sorbed Ni(II) does not change with increasing reaction time even though the extent of sorption continues to increase. This supports a slow uptake mechanism where surface or intraparticle diffusion processes are rate-limiting. This work demonstrates that the association of humic constituents with soil minerals can significantly modify the mechanisms controlling trace metal sorption and transport in heterogeneous aquatic environments.     

Polyethylenimine-modified fungal biomass as a high-capacity biosorbent for Cr(VI) anions: sorption capacity and uptake mechanisms

Heavy metal pollution in the aqueous environment is a problem of global concern. Biosorption has been considered as a promising technology for the removal of low levels of toxic metals from industrial effluents and natural waters. A modified fungal biomass of Penicillium chrysogenum with positive surface charges was prepared by grafting polyethylenimine (PEI) onto the biomass surface in a two-step reaction. The presence of PEI on the biomass surface was verified by FTIR and X-ray photoelectron spectroscopy (XPS) analyses. Due to the high density of amine groups in the long chains of PEI molecules on the surface, the modified biomass was found to possess positive zeta potential at pH below 10.4 as well as high sorption capacity for anionic Cr(VI). Using the Langmuir adsorption isotherm, the maximum sorption capacity for Cr(VI) at a pH range of 4.3-5.5 was 5.37 mmol/g of biomass dry weight, the highest sorption capacity for Cr(VI) compared to other sorbents reported in the literature. Scanning electronic microscopy (SEM) provided evidence of chromium aggregates formed on the biomass surface. XPS results verified the presence of Cr(III) on the biomass surface in the pH range 2.5-10.5, suggesting that some Cr(VI) anions were reduced to Cr(III) during the sorption. The sorption kinetics indicated that redox reaction occurred on the biomass surface, and whether the converted Cr(III) ions were released to solution or adsorbed on the biomass depended on the solution pH. Sorption mechanisms including electrostatic interaction, chelation, and precipitation were found to be involved in the complex sorption of chromium on the PEI-modified biomass.     

Critical evaluation of desorption phenomena of heavy metals from natural sediments

In natural sediments, the majority of heavy metal ions are generally associated with the solid phase. To become bioavailable, the metal ions must desorb from the solid. Numerous studies of heavy metals in sediments have suggested that sorption and desorption exhibit hysteresis (i.e., the two processes are not reversible), while other studies have suggested that desorption hysteresis does not exist. In this study, sorption/desorption hysteresis of lead (Pb) and cadmium (Cd) was evaluated over the following range of conditions: (i) desorption induced by replacing the supernatant liquid with contaminant-free electrolyte solution; (ii) desorption induced by lowering the solution pH with mineral acid; and (iii) desorption induced by sequestration with EDTA. Given the importance of dissolved organic and inorganic ligands in regulating heavy metal behavior in nature sediments, sorption/desorption experiments were conducted on both untreated and prewashed sediments. Prewashing treatment increases the sorption potential of Cd but not Pb. Desorption hysteresis is observed in both the untreated and the prewashed sediments using the replaced supernatant method, and the desorption hysteresis appears to increase with aging time. Hysteresis is not observed when desorption is initiated by lowering the solution pH. A large fraction of the sorbed heavy metal ions can be easily desorbed by EDTA; between 0.04 and 1.2 mmol/kg Cd and Pb ions are resistant to desorption.     

Study of the interaction of Ni2+ and Cs+ on MX-80 bentonite; effect of compaction using the "capillary method"

The goal of the paper is to assess the applicability of sorption models to describe the retention of contaminants on clay materials, both in dispersed and compacted states. A batch method is used to characterize the sorption equilibria between Cs, Ni, and MX-80 bentonite for solid-to-liquid ratios varying from 0.5 to 4200 kg/m3. For compacted bentonite (dry density of 1100 kg/m3), a new method is presented where the material compaction is performed in PEEK capillaries. Sorption edges and isotherms were measured in the presence of a synthetic groundwater. A model considering cation exchange reactions with interlayer cations and surface complexation reactions with edge sites was used for the dispersed state. Montmorillonite was shown to be the dominant interacting phase in MX-80 bentonite. The applicability of the model to compacted bentonite was tested. The results indicate that under conditions where the cation exchange mechanism is dominant, there is no difference between the dispersed and compacted states. For the degree of compaction studied, all exchange sites are available for sorption. For Ni, when surface complexation is the dominant sorption mechanism, a decrease of the Kd values by a factor of about 3 was observed (pH 7-8, trace concentrations). This could be explained quantitatively by a diminution of the conditional interaction constant between Ni and the edge surface site in the compacted state. One consequence of this decrease is that the contribution of the organic matter content of MX-80 bentonite to the total sorption becomes significant.     

Structural study of the incorporation of heavy metals into solid phase formed during the oxidation of EDTA by permanganate at high pH

Properties of solid phases formed during the oxidation of EDTA by permanganate in a high-pH, high-ionic strength solution, and the retention of Cu2+, Ni2+, and Zn2+ by them were examined. Morphologically, the solids were agglomerates of particles with sizes <100 nm. X-ray absorption spectroscopy (XAS) analysis indicated that these particles were birnessite. Its precipitation was accompanied by the removal of Zn2+ and Cu2+ released as a result of the breakdown of their complexes with EDTA. However, Ni2+ was not removed from the supernatant. Cu2+ was strongly bound by birnessite and exhibited little mobility in the pH range from 3 to 14. Zn2+ was more mobile, especially at pH > 12. XAS showed that Cu2+ binding sites were located within MnO6 octahedra-comprised sheets that constitute birnessite while Zn2+ was positioned between them.     

Ni uptake by a green alga. 2. Validation of equilibrium models for competition effects

It is generally admitted that the presence of major cations and H+ can attenuate trace metal uptake. Recent models such as the biotic ligand model (BLM) aim to quantify and predict this effect by determining stability constants for each of the major competitors for any given interaction of a trace metal with a biological organism. In this study, short-term Ni internalization fluxes (J(int)) were used to quantitatively assess the binding of H+, Mg2+, Ca2+ (K(H-Rs), K(Mg-Rs), K(Ca-Rs)), and trace metals to transport sites (R(s)) leading to Ni biouptake by Chlamydomonas reinhardtii. H+ and Mg2+ are shown to compete directly for the entry of Ni with affinity constants that are of the same order of magnitude (K(Mg-Rs) = 10(5.1) M(-1); K(H-Rs) = 10(5.3) M(-1)) as that measured for Ni (K(Ni-Rs) = 10(5.1) M(-1)). The Ni internalization fluxes were also strongly linked to the Mg cell status. In contrast, the role of Ca2+ could not be explained by a simple competitive equilibrium with the Ni transport sites. Aluminum (K(Al-Rs) = 10(8) M(-1)), Zn (K(Zn-Rs) = 10(6.5) M(-1)), and Cu (K(Cu-Rs) = 10(6.6) M(-1)) were all shown to compete strongly with Ni for uptake. In addition to the determination of uptake constants, these studies provide insight into the transport mechanisms of Ni by the green alga, C. reinhardtii.     

Probing the surface structure of divalent transition metals using surface specific solid-state NMR spectroscopy

Environmental and geochemical systems containing paramagnetic species could benefit by using nuclear magnetic resonance (NMR) spectroscopy due to the sensitivity of the spectral response to small amounts paramagnetic interactions. In this study, we apply commonly used solid-state NMR spectroscopic methods combined with chemometrics analysis to probe sorption behavior of the paramagnetic cations Cu(2+) and Ni(2+)at the amorphous silica surface. We exploit the unique properties of paramagnets to derive meaningful structural information in these systems at low, environmentally relevant cation surface loadings by comparing the NMR response of sorption samples to paramagnetic free samples. These data suggest that a simple sorption model where the cation sorbs as inner sphere complexes at negatively charged, deprotonated silanol sites is appropriate. These results help constrain sorption models that are used to describe metal fate and transport.