Determination of Free Cd,Cu and Zn Concentrations in Lake Waters by In Situ Diffusion Followed by Column Equilibration Ion-exchange

Combining in situ diffusion and column ion-exchange equilibration, we measured free metal ion concentrations (Cd, Cu and Zn) in water samples collected from the epilimnion of 14 lakes in the Rouyn-Noranda area (600 km north-west of Montreal, QC, Canada). Lakes were selected to represent a wide range of physico-chemical characteristics (hardness, pH, dissolved organic matter—DOM, degree of metal contamination), to determine the influence of these parameters on metal speciation. Total dissolved metal concentrations, as determined within the diffusion cells, varied over one to two orders of magnitude: [Cd] 0.19–2.9 nM; [Cu] 36–190 nM; [Zn] 7–2,800 nM. The proportion of total dissolved metal present as free Cd²⁺ and Zn²⁺ was relatively constant for the 14 selected lakes, despite the wide pH (4.5–8) and DOM (3–23 mg C/L) ranges, probably reflecting the inverse relationship observed between pH and DOM; this proportion did, however, vary with DOM and pH for Cu. Our experimental free metal ion concentrations were compared with those calculated with the thermodynamic models WHAM (Windermere Humic Aqueous Model VI) and ECOSAT 4.7 (incorporating the NICA-Donnan model). Measured and calculated values were in reasonable agreement for both Cd and Zn although measured values were generally slightly higher, i.e. less than one order of magnitude. For several lakes, measured free Cu concentrations were, however, much higher than the calculated values, suggesting that these models overestimate Cu complexation. The gap between measured and calculated free metal ion concentration becomes more important as the total metal concentration decreases and as pH increases.     

Metal–organic matter interaction: Ecological roles of ligands in oceanic DOM

The ecological roles of dissolved organic matter (DOM) in seawater have not been well understood. One definite function of DOM stems from its complexation ability with trace metals under the conditions of seawater. A chemical complexation model of the marine system was introduced in order to clarify the ecological roles of strong organic ligands in DOM related to the acquisition of bioactive metals (Cu, Fe and Zn) by phytoplankton, assuming that two types of strong organic ligands coexist in oceanic DOM and complexes with bioactive metals. The results reveal that the weaker organic ligand, rather than the stronger one, plays a significant role in the reduction of Cu toxicity for phytoplankton growth. It is suggested that the presence of reactions with Cu that are competitive to the strong organic ligand causes extremely low Fe concentrations in seawater and leads to Fe deficiency for phytoplankton growth. Therefore, it is concluded that the strong ligands in DOM play a chemical role in controlling free ion concentration levels of bioactive metals in the marine environment.     

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d’Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.     

Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Dissolved sulfides in the oxic water column of San Francisco Bay,California

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.     

Comparison of the Complexation of Cu and Cd by Humic or Fulvic Acids and by Ligands Observed in Lake Waters

The complexation of Cu and Cd by ligands observed in filtered unfractionated lakewaters is compared to the complexation by humic and fulvic acids. Complexation parameters (conditional stability constants and ligand concentrations) of Suwannee River fulvic acids (FA), purified peat humic acids (HA) and of ligands in lakewater samples have been determined using the same methods (ligand-exchange and CSV (cathodic stripping voltammetry) or ASV (anodic stripping voltammetry)), and the same titration ranges of Cu, Cd and organic carbon concentrations. The performance of the used techniques is first evaluated in FA and HA suspensions, and gives comparable results with the literature values for the same materials, according to published models (5-site model, NICA model) and parameters. Model calculations using the WHAM model for FA and HA (Tipping, 1994) are also presented. The comparison of titrations of FA and HA with Cu and Cd with those of lakewater samples indicates that stronger ligands than FA and HA are present at low concentrations in the lakewaters. Specific strong ligands occur in particular in eutrophic lake waters, whereas in a lake with higher metal concentrations and low biological productivity the ligands more closely match the fulvic acid characteristics.     

Metal Complexation with Different types of Soluble and Adsorbed Freshwater Ligands Followed by DPASV

In order to understand metal speciation in a polluted river (Este River, Northern Portugal) filtrate, freeze dried particles and organics desorbed from surfaces were titrated with Cd(II) and Zn(II), followed by differential pulse anodic stripping voltammetry (DPASV). The obtained results are compared with those previously published for Pb(II) and Cu(II). Due to the heterogeneity of the system, a continuous and a discrete ligand model were used to interpret the titration data. Two types of ligands could be detected and quantified by the discrete ligand model: small molecules with high affinities for cations such as Cd(II), Cu(I), and Zn(II) and macromolecules with higher affinities for Pb(II) and Cu(II). Small ligands were strongly adsorbed onto the particles, as inferred from the desorption of Zn(II) during titration with Pb(II) and Cd(II). The total concentrations of the different ligands and the complex formation constants with the different metals are reported.     

Contribution of organic complexation to Ni,Co and Cu speciation in surface waters: Implications for hydrogeochemicalsurveys

Organic materials dissolved in surface waters have long been implicated in metal binding and transport. In particular, fulvic and humic acids are considered to have a significant impact on speciation, total metal levels in solution and on the persistence of those metals. This work emphasizes the role played by dissolved organic matter (DOM) on the complexation of nickel, copper and cobalt and on its application to interpretation of surface water hydrogeochemical survey data. Waters from a number of well-known mining districts in Canada have been studied; in particular from Cobalt (Ontario), Sackville (New Brunswick) and Thetford Mines (Quebec). The diafiltration binding technique was used and shows that nickel, copper and cobalt are complexed significantly by DOM in natural waters. The tendency towards complexation was found to be Cu > Ni > Co. The binding functions determined were observed to be highly sensitive to pH and ligand:metal ratios; a gradation of binding site strength is evident.Data from some hydrogeochemical surveys conducted in the Kenora, Algoma and Ottawa districts of Ontario have been reinterpreted in the light of available data on the complexation behaviour of nickel, copper and cobalt. Occurrence of large water-borne anomalies unsupported by lake sediment loadings is most likely for cobalt and nickel and least likely for copper according to both field observations and experimental data. These studies provide good evidence for the formation of strong solution stable metal-organic species; the principal differences in persistence and migration behaviour are probably due to rates of coagulation and adsorption-precipitation processes which preferentially remove copper from solution. It is fair to conclude that these metals can be of use in mineral exploxation surveys using surface waters provided caution is exercised in interpretation of anomalies, especially in the absence of supporting sediment anomalies. Dissolved organic matter concentrations should always be determined when nickel, copper and cobalt are to be employed.     

Water toxicity and metal contamination assessment of a polluted river: the Upper Vistula River (Poland)

In aquatic systems, the bioavailability of an element to microorganisms is greatly influenced by its chemical speciation. The goal of this work was to assess metal toxicity to a green algae (Pseudokirchneriella subcapitata) and a bacterium (Vibrio fisheri) as a function of size fractionation and chemical speciation (using the program MINTEQA2) in contaminated water of the Upper Vistula River. Water samples were collected at 1 reference site, 4 polluted sites and one polluted site on the Vistula's main tributary, the Przemsza River. Toxicity measurements were performed on unfiltered samples and, total dissolved (<1.2 μm), and truly dissolved (<1 kDa) fractions. Trace metal (Cd, Co, Cr, Cu, Mn, Pb, Zn) concentrations were measured in these samples and also in the colloidal fraction (1 kDa–1.2 μm). At the reference site, the low metal concentrations were in agreement with the absence of measurable toxicity. In the polluted section of the river, free metal concentrations were largely below the potential toxic levels for bacteria, which was in agreement with the absence of toxicity. Although Zn²⁺ was at potentially toxic-level concentrations in total dissolved and truly dissolved fractions in the polluted riverine section, toxicity for algae was observed, only in truly dissolved fractions from two stations. The absence of toxicity in most samples was related to metal association with particles and with low molecular weight ligands as well as the presence of organic ligands (phenol). The reason for toxic effects in two ultrafiltered samples is not clear, but may be related to the elimination of the colloidal organic fraction and thus the eradication of its protective effect occurring in natural samples.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Short-term biogeochemical influence of a diatom bloom on the nutrient and trace metal concentrations in South San Francisco Bay microcosm experiments

Two laboratory microcosm experiments were conducted to mimic an annual spring diatom bloom in South San Francisco Bay by isolating the phytoplankton community from the benthic grazing pressure to induce a phytoplankton bloom. The purpose of these experiments was to isolate the impact of a spring diatom bloom on the nutrient and trace metal geochemical cycling. Microcosms were created in 2.5 L incubation bottles and subjected to one of 4 treatments (control, copper [Cu] addition, manganese [Mn] addition, and both Cu and Mn addition) to investigate the toxicity of Cu on the resident plankton and the potential antagonistic effects of Mn on reducing Cu toxicity. Dissolved macronutrient (nitrate + nitrite, phosphate, and silicate), and dissolved and particulate trace metal (Cu, Ni, Mn) concentrations were monitored in the grow-out incubations on a daily basis. Chlorophylla concentrations were also monitored over the course of the experiment and used to calculate diatom-specific growth rates. In the experiments containing ambient South San Francisco Bay surface waters, average specific growth rates were on the order of 1.1 d^?1. The induced diatom blooms resulted in significant removal of macronutrients from the microcosms over the course of the experiments. Our research supports previous suggestions that dissolved Ni and Cu concentrations in South San Francisco Bay have a very low biological availability as a result of organic chelation. Ni(EDTA)^2? has been found to be the dominant dissolved Ni species by other researchers and Cu speciation analyses from this study and others indicate that > 99% of the dissolved Cu in South San Francisco Bay is strongly chelated as CuL₁. The free cupric ion concentration was on the order of 10^?12 M. Marked removal of dissolved Mn was observed in the control treatments, well exceeding expected dissolved Mn removal by diatom uptake. Additions of 375 nM Cu resulted in the complete titration of the chelating ligand (L₁) concentrations. The elevated [Cu²⁺] (≈10^?8MM) appeared to have a toxic effect on the diatom community observed in the significant decreases in their specific growth rates (μ=0.4 d^?1). The suppression of dissolved Mn removal from solution was also observed in treatments spiked with high levels of dissolved Cu, providing support that Mn precipitation was due to biologically mediated oxidation not phytoplankton assimilation. The observed geochemical behavior in the concurrent Cu and Mn addition treatments provide evidence in support of Mn alleviation of Cu toxicity. The biological role in the ambient short-term biogeochemical cycling of Cu and Ni in South San Francisco Bay appears to be minimal due to the inert character of the organic ligand-metal complexes. A significant portion of the annual macronutrient and Mn cycling occurs as a result of spring diatom blooms in South San Francisco Bay.     

Effects of Soil Composition on Zn Speciation in Drainage Waters from Agricultural Soils

The influence of Zn speciation on Zn transport by drainage from different soils to surface water is examined in a stream catchment in an agricultural area. Drainage waters were collected from two types of soils, a mineral soil (MS) and a soil rich in organic matter (OS) by means of artificial drainage pipes. The speciation of dissolved Zn in the stream and the drainage waters was determined using ligand-exchange and voltammetry. About 50–95% of dissolved Zn is bound in strong complexes, and the free Zn²⁺ ion concentration is in the range of 1–16% of dissolved Zn. A substantial part of Zn is present in weaker organic or inorganic complexes. The simulated Zn speciation using the WHAM VI model is compared to the determined speciation. Free Zn²⁺ concentrations predicted by the WHAM VI model are generally higher than the analytically determined free Zn²⁺, but are mostly within the same order of magnitude. Effects of different soil organic matter content on Zn speciation and transport are discussed. Zn speciation in the drainage at the OS site is influenced by the distribution of organic matter between the solid and solution phase. The abundant organic Zn complexes in solution contribute to facilitate Zn transport from soil into surface waters, through the drainage at the OS site. Drainage from the OS site contributes about twice as much Zn input to the receiving water as the MS soil, as related to specific area. The mineral soil contains much lower organic matter, and a part of Zn bound with inorganic phases can hardly be released by dissolved organic ligands, leading to much higher Zn retention at the MS site.     

Complexation of trace metals by adsorbed natural organic matter

The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu²⁺ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter.     

Fractionation of dissolved organic matter affected by polyvalent metal cations

The purpose of the study was to evaluate the influence of polyvalent cations known to form complexes with natural organic substances on the operational fractionation of dissolved organic matter (DOM) using XAD-8 adsorber resin. Dissolved organic matter solutions from a forest floor were treated with increasing concentrations of polyvalent metal cations (Ca²⁺, Al³⁺, Fe³⁺) at different pH levels. Then the concentrations of total dissolved organic carbon (DOC) and the distribution between hydrophilic and hydrophobic DOC were determined. The concentrations of total DOC decreased slightly when the C/metal ratio was less than 10, especially for Al and Fe. Hydrophilic DOC increased and hydrophobic DOC decreased with increasing concentrations of metal cations. Effects increased in the order Ca<Al<Fe and were more pronounced at low DOC concentrations and high pH values. The reason for the reduction of the DOC concentrations seemed to be the formation of insoluble metal–DOM complexes, while soluble metal–DOM complexes may induce an alteration of the distribution between hydrophilic and hydrophobic DOC. Thus, the polyvalent cations and their concentration need to be considered when DOM fraction distributions, determined with XAD-8 resin, of different waters are compared, especially at low DOC contents and high pH.     

Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation

Published experimental data for Al(III) and Fe(III) binding by fulvic and humic acids can be explained approximately by the Humic Ion-Binding Model VI. The model is based on conventional equilibrium reactions involving protons, metal aquo ions and their first hydrolysis products, and binding sites ranging from abundant ones of low affinity, to rare ones of high affinity, common to all metals. The model can also account for laboratory competition data involving Al(III), Fe(III) and trace elements, supporting the assumption of common binding sites. Field speciation data (116 examples) for Al in acid-to-neutral waters can be accounted for, assuming that 60-70 % (depending upon competition by iron, and the chosen fulvic acid : humic acid ratio) of the dissolved organic carbon (DOC) is due to humic substances, the rest being considered inert with respect to ion binding. After adjustment of the model parameter characterizing binding affinity within acceptable limits, and with the assumption of equilibrium with a relatively soluble form of Fe(OH)₃, the model can simulate the results of studies of two freshwater samples, in which concentrations of organically complexed Fe were estimated by kinetic analysis.The model was used to examine the pH dependence of Al and Fe binding by dissolved organic matter (DOM) in freshwaters, by simulating the titration with Ca(OH)₂ of an initially acid solution, in equilibrium with solid-phase Al(OH)₃ and Fe(OH)₃. For the conditions considered, Al, which is present at higher free concentrations than Fe(III), competes significantly for the binding of Fe(III), whereas Fe(III) has little effect on Al binding. The principal form of Al simulated to be bound at low pH is Al³⁺, AlOH²⁺ being dominant at pH >6; the principal bound form of Fe(III) is FeOH²⁺ at all pH values in the range 4-9. Simulations suggest that, in freshwaters, both Al and Fe(III) compete significantly with trace metals (Cu, Zn) for binding by natural organic matter over a wide pH range (4-9). The competition effects are especially strong for a high-affinity trace metal such as Cu, present at low total concentrations (∼1 nM). As a result of these competition effects, high-affinity sites in humic matter may be less important for trace metal binding in the field than they are in laboratory systems involving humic matter that has been treated to remove associated metals.     

Speciation of trace metals in leachate from a MSWI bottom ash landfill

Trace metal concentrations and speciation were determined in leachate from a municipal solid waste incinerator bottom ash landfill both experimentally and by thermodynamic model calculations. Total dissolved Cr, Sb and W concentrations determined directly by ICP-MS were up to two orders of magnitude higher than that determined upon preconcentration by anin-situ solid phase extraction technique based on 8-HQ cation exchanger which indicates oxyanion complex formation of these metals in the leachates. Speciation modeling suggests that a similar difference for Cu is caused by organic complexation. Lead and Zn concentrations determined by both methods were fairly comparable but very low, in the range 4–60 nmol l⁻¹. The low mobility of both metals can be modeled by assuming adsorption onto Fe-oxyhydroxides oxycoprecipitation with Ca-silicate hydrate phases. The resulting high retardation coefficients between 500 and 800 indicate that scavenging by these secondary weathering products in the MSWI bottom ash deposit can cause an efficient immobilization of both Pb and Zn.     

Effect of organic complexation on the toxicity of Cu to the earthworm Eisenia fetida

The relationship between Cu speciation in solution and mortality and tissue Cu concentrations in Eisenia fetida was investigated. E. fetida were exposed to solutions containing 0.009, 0.049 and 0.125 mg Cu L⁻¹and 0, 0.15, 0.35 and 50 mg EDTA L⁻¹. Mortalities of 100, 60, 50 and 25% were recorded in the 0.125 mg Cu L⁻¹ solutions containing 0, 0.15, 0.35 and 50 mg EDTA L⁻¹, respectively. Similarly tissue body burden decreased with increasing EDTA concentration. Complexation capacity of the solution increased with EDTA concentration. In the 0.125 mg Cu L⁻¹ solution labile Cu concentration decreased with increasing EDTA concentration. These trends are attributed to complexation of free Cu ions with EDTA molecules, and the non-bioavailable nature of the resultant Cu–EDTA complex.     

Multi-metal contaminant dynamics in temporarily flooded soil under sulfate limitation

In many river basins, floodplain soils have accumulated a variety of metal contaminants, which might be released during periods of flooding. We investigated the dynamics of copper, cadmium, lead, zinc, and nickel in a contaminated freshwater floodplain soil under a realistic sulfate-limited flooding regime in microcosm experiments. We found that most contaminants were initially mobilized by processes driven by the reductive dissolution of Fe(III) and Mn(IV, III) (hydr)oxides. Subsequently, bacterial sulfate respiration resulted in the transformation of the entire available sulfate (2.3 mmol/kg) into chromous reducible sulfur (CRS). Cu K-edge X-ray absorption fine structure (XAFS) spectroscopy revealed that the soil Cu speciation changed from predominantly Cu(II) bound to soil organic matter (SOM) intermittently to 14% metallic Cu(0) and subsequently to 66% copper sulfide (Cu_xS). These Cu_xS precipitates accounted for most of the formed CRS, suggesting that Cu_xS was the dominant sulfide phase formed in the flooded soil. Sequential metal extractions, in agreement with CRS results, suggested that easily mobilizable Cd was completely and Pb partially sequestered in sulfide precipitates, controlling their dissolved concentrations to below detection limits. In contrast, Zn and Ni (as well as Fe) were hardly sequestered into sulfide phases, so that micromolar levels of dissolved Zn and Ni (and millimolar dissolved Fe(II)) persisted in the reduced soil. The finding that Cu, Cd, and Pb were sequestered (but hardly any Zn, Ni, and Fe) is consistent with the thermodynamically predicted sulfide ladder following the increasing solubility products of the respective metal sulfides. The observation that Cd and Pb were sequestered in sulfides despite the presence of remaining SOM-bound Cu(II) suggested that the kinetics of Cu(II) desorption, diffusion, and/or Cu_xS precipitation interfered with the sulfide ladder. We conclude that the dynamics of multiple metal contaminants are intimately coupled under sulfate limitation by the relative thermodynamic stabilities and formation kinetics of the respective metal sulfides.     

Fate and transport of metals in H2S-rich waters at a treatment wetland

The aqueous geochemistry of Zn, Cu, Cd, Fe, Mn and As is discussed within the context of an anaerobic treatment wetland in Butte, Montana. The water being treated had a circum-neutral pH with high concentrations of trace metals and sulfate. Reducing conditions in the wetland substrate promoted bacterial sulfate reduction (BSR) and precipitation of dissolved metal as sulfide minerals. ZnS was the most common sulfide phase found, and consisted of framboidal clusters of individual spheres with diameters in the submicron range. Some of the ZnS particles passed through the subsurface flow, anaerobic cells in suspended form. The concentration of "dissolved" trace metals (passing through a 0.45 μm filter) was monitored as a function of H₂S concentration, and compared to predicted solubilities based on experimental studies of aqueous metal complexation with dissolved sulfide. Whereas the theoretical predictions produce "U-shaped" solubility curves as a function of H₂S, the field data show a flat dependence of metal concentration on H₂S. Observed metal concentrations for Zn, Cu and Cd were greater than the predicted values, particularly at low H₂S concentration, whereas Mn and As were undersaturated with their respective metal sulfides. Results from this study show that water treatment facilities employing BSR have the potential to mobilize arsenic out of mineral substrates at levels that may exceed regulatory criteria. Dissolved iron was close to equilibrium saturation with amorphous FeS at the higher range of sulfide concentrations observed (>0.1 mmol H₂S), but was more likely constrained by goethite at lower H₂S levels. Inconsistencies between our field results and theoretical predictions may be due to several problems, including: (i) a lack of understanding of the form, valence, and thermodynamic stability of poorly crystalline metal sulfide precipitates; (ii) the possible influence of metal sulfide colloids imparting an erroneously high "dissolved" metal concentration; (iii) inaccurate or incomplete thermodynamic data for aqueous metal complexes at the conditions of the treatment facility; and (iv) difficulties in accurately measuring low concentrations of dissolved sulfide in the field.     

Spatial Variation in the Optical Properties of Dissolved Organic Matter (DOM) in Lakes on the Canadian Precambrian Shield and Links to Watershed Characteristics

In the present study, we explored the use of various optical parameters to detect differences in the composition of the dissolved organic matter (DOM) in a set of lakes that are all located on the Canadian Precambrian Shield, but within which Cu and Ni speciation predictions were previously shown to diverge from measured values in some lakes but not in others. Water samples were collected with in situ diffusion samplers in 2007 (N = 18 lakes) and 2008 (N = 8 lakes). Significant differences in DOM quality were identified between the sampling regions (Rouyn-Noranda, Québec and Sudbury, Ontario) and among lakes, based on dissolved organic carbon concentrations ([DOC]), specific UV absorbance (SUVA₂₅₄), fluorescence indices (FI), and excitation–emission matrix (EEM) fluorescence measurements. Parallel factor analysis (PARAFAC) of the EEM spectra revealed four components, two of which (C3, oxidized quinone fluorophore of allochthonous origin, and C4, tryptophan-like protein fluorescence of autochthonous origin) showed the greatest inter-regional variation. The inter-lake differences in DOM quality were consistent with the regional watershed characteristics as determined from satellite imagery (e.g., watershed-to-lake surface area ratios and relative percentages of surface water, rock outcrops vegetative cover and urban development). Source apportionment plots, built upon PARAFAC components ratios calculated for our lakes, were used to discriminate among DOM sources and to compare them to sources identified in the literature. These results have implications for other areas of research, such as quantifying lake-to-lake variations in the influence of organic matter on the speciation of trace elements in natural aquatic environments.