Trace metal species in fresh waters

A recently proposed trace metal speciation scheme was applied to the determination of the chemical forms of copper, lead, cadmium and zinc in four natural fresh waters and a tap water. Studies were also made on the reliability of the technique, and of the effect of various methods of storage on the speciation results. The measurements showed that (a) copper in the river and reservoir samples was associated mainly with organic matter, probably organic colloids; (b) lead was divided between stable inorganic and organic forms, but one particular inorganic lead species predominated; (c) cadmium existed almost entirely as labile ionic forms; (d) zinc was divided between labile ionic species and a stable inorganic form; very little zinc was associated with organic colloids, and (e) the trace metals were not combined with inorganic colloids. Samples stored in polyethylene containers for over three weeks at 25°C or 4°C showed little change in either total metal concentration or metal speciation. Freezing, however, caused some irreversible changes.     

In situ measurements of labile Cu, Cd and Mn in river waters using DGT

The technique of diffusive gradients in thin-films (DGT) has been trialed in two river systems for in situ trace metal speciation measurements. This paper presents results for cadmium, copper and manganese concentrations in fresh and estuarine waters and demonstrates for the first time the effectiveness of using DGT to measure labile metal concentrations in such waters. This work has shown that even with very simple deployment systems the technique is sensitive and reproducible. The precision of in situ DGT measurements was typically 11% or better when the precision of subsequent analysis was good. The in-built metal pre-concentration procedure of DGT allowed Cd to be measured at concentrations below the detection limit of a direct determination by GF-AAS. The theoretically predicted linear increase in mass with time was obtained in river deployments of up to 72 h, confirming steady state river conditions and indicating no adverse effects due to biofouling over this period. Concentrations of DGT-labile Cu and Cd were equal to dissolved (0.45 micron) metal concentrations for the Ring and Stitt Rivers indicating the absence of tightly bound organic complexes or colloidal species. DGT-labile Cu and Cd were approximately 50% of the dissolved metal in the Que River and DGT-labile Cu was approximately 30% of dissolved Cu in the Savage River. A concentration-depth profile of labile manganese was obtained in a stratified estuary by deployment of a string of DGT devices at 0.3-m intervals across the redoxcline. Results revealed a large spike (maximum concentration = 1.4 mg/l) of DGT-labile Mn at the base of the redoxcline and demonstrate the utility of DGT to determine vertical changes in metal speciation across redox boundaries in stratified estuarine systems. It is in such dynamic systems as this that the in situ capabilities of DGT are likely to be most useful. DGT records multiple metal species as they exist in situ, overcoming the considerable problems of contamination often associated with sample collection and handling.     

Comparison of diffusive gradients in thin films and equilibrium dialysis for the determination of Al, Fe(III) and Zn complexed with dissolved organic matter

The distinction between 'free' metals and organically complexed metals in aqueous solutions is important for research involving the mobility or bioavailability of metals in the environment. In this study, the applicability of equilibrium dialysis (molecular weight cut-off = 1000 Da) and diffusive gradients in thin films (DGT) to determine 'free' Al, Fe(III) and Zn in four forest soil solutions was compared. The 'free' metals as measured by both methods, consist of hydrated metal cations and soluble inorganic metal complexes. In addition, dialysis measures any organic complexes < 1000 Da and DGT measures a portion of smaller labile organic complexes. The four soil solutions were prepared by water extraction of an organic soil horizon (H) from a Fimic Anthrosol, and contained either 20 or 75 mg C/l dissolved organic matter at pH 4.0 and pH 7.0. To test the performance of both methods and optimize experimental volume and time, experiments using metal nitrate solutions were carried out. In the solutions at pH 4.0, no significant differences in average 'free' metal contents were found for Al, Fe(III) or Zn. This makes DGT a viable alternative for equilibrium dialysis for the study of the complexation of all three metals in acidic soils. At pH 7.0, again no significant difference between both methods were found for Al and Fe(III), but the DGT results for Zn were significantly higher. This was likely caused by labile organic complexes that were only detected by DGT.     

Dissolved and bioavailable contaminants in the Seine river basin

Diffusive Gradient in Thin Films (DGT) and Semi-Permeable Membrane Devices (SPMDs) were deployed in the Seine river basin in order to assess labile metals and truly dissolved Polycyclic Aromatic Hydrocarbons. We show that the tools are reliable in aquatic environments to assess the speciation of dissolved contaminants and hence provide a good insight into the potential bioavailability of contaminants. The deployment of the DGT and SPMDs in contrasting environments in the Seine river basin allowed distinction to be made of availability of contaminants between headwater streams and much more impacted river reaches and an assessment of bioavailability. At the stations under urban influence, the impact of dissolved organic matter on both copper and PAHs bioavailability is less pronounced than at upstream stations, where humic substances dominate.     

Assessment of copper bioavailability and toxicity in vineyard runoff waters by DPASV and algal bioassay

The aim of this study was to assess the toxicity of runoff waters in an agricultural multipollution context through an in-depth assessment of copper bioavailability and toxicity. Runoff waters were screened for major ions, metals and diuron. The potential environmental impact of these runoff waters was evaluated using the conventional 72-h growth inhibition test with the green alga Pseudokirchneriella subcapitata. The results suggested that the toxicity detected in the calcareous vineyard field was due to the presence of diuron, whereas the non-calcareous runoff waters were non-toxic. Chemical speciation modelling by MINEQL revealed that most of the copper present in the non-toxic natural runoff waters was complexed by organic matter. These samples were spiked with copper, and then the toxicity and the electrochemically bioavailable copper fraction were measured. Differential pulse anodic stripping voltammetry (DPASV) was used to detect labile complexes and free copper. This combined approach highlighted the presence of some labile copper complexes in samples reaching the EC10-these could have contributed to the copper toxicity.     

The determination of cadmium. lead, copper and zinc in ground water, estuarine water, sewage and sewage effluent by anodic stripping voltammetry

Anodic stripping voltammetry (ASV) using the thin-film mercury electrode was shown to be a successful technique for the determination of total (free plus complexed) trace metal concentrations in various types of aqueous sample. The method developed involved the minimum of sample treatment and required only simple and inexpensive equipment. The practical limit of sensitivity was about 0·1 μg I⁻¹ for cadmium, lead and copper. The determination of zinc was found to be complicated by the formation of an intermetallic compound with copper. Interference by other trace metals and by complexing agents was investigated. Photochemical oxidation for the decomposition of complexes of the metals with organic ligands in filtered sewage and sewage effluent was found to be successful, although the process is slower for cadmium than for the other metals. Good agreement with atomic absorption spectroscopy was obtained for all the types of aqueous sample investigated. Possible improvements of the ASV technique are discussed.     

Chemical partitioning and remobilization of heavy metals from sewage sludge dumped in Dublin Bay

During the disposal of sewage sludge to the marine environment, chemical changes may alter the mobility of trace elements, thus affecting their potential toxicity and availability to marine organisms. Primary sludge from the Ringsend treatment plant in Dublin receives both domestic waste and trade wastes which contain heavy metals, and approx. 250,000 tons per annum is periodically dumped in Dublin Bay. The purpose of this study was to determine changes which may occur in the chemical partitioning of heavy metals in the sludge during disposal. Samples of sludge were collected from the treatment plant in July 1987. Sequential chemical extraction of heavy metals (Cu, Pb, Cd, Zn, Fe, Mn) was carried out in a nitrogen-filled glove box using 1 M ammonium acetate, 1 M sodium acetate, 0.1 M hydroxylamine HCl (pH 2), 0.2 M ammonium oxalate (pH 3), 30% hydrogen peroxide and concentrated HNO₃. Seawater-extractable metal was determined by mixing subsamples of sludge with filtered seawater from Dublin Bay for 2 h. Chemical partitioning of heavy metals among solid phases in the sludge residue was redetermined by sequential chemical extraction. Both sludge and dumpsite sediments were analysed for total heavy metal content and organic content. The sludge was found to be only slightly anaerobic with a water content of 88% and significant concentrations of some metals, notably copper and zinc. Most of the non-residual copper, lead and cadmium was found in the organic/sulphidic fraction of the sludge (hydrogen peroxide extract), while the dominant phase for zinc was the moderately reducible fraction (ammonium oxalate extract) and only iron and manganese had substantial proportions of metal in more labile phases. Agitation with seawater mobilized cadmium and manganese to a significant extent (56 and 43%, respectively) but negligible amounts of copper or lead (0 and 2%, respectively). However, significant changes in solid-phase partitioning of lead and zinc occurred resulting in mobilization from stronglybound to more labile fractions. No deleterious effects were found at the dumpsite but localized effects are possibly due to the increased mobility of zinc, lead and particularly cadmium.     

Influence of the sediment on lead speciation in the Tagus estuary

The aim of this work is to study the influence of the Tagus estuarine sediment on lead speciation in the overlying natural water. The water sample in the presence of the sediment was contaminated three times with Pb(II) in a laboratory experiment. In different periods of time, at 1-7 days after each contamination, small volumes of water were titrated with lead. The titration was followed by anodic stripping voltammetry in differential pulse mode. Before and after contamination systematic analysis of the voltammetric parameters (peak current, peak potential and peak width) were carried out to get a clear picture of Pb(II) complexation in the soluble fraction in contact with the sediment. Two main types of organic ligands, macromolecular ligands and small compounds, were detected before contamination. Both of them form labile complexes (degree of lability within the timescale of some milliseconds). The small compounds, with a diffusion coefficient similar to that of the free metal ion, present a homogeneous behaviour in terms of Pb complexation. On the other hand macromolecular ligands, with a diffusion coefficient of 1.2 x 10(-6) cm2s(-1), can be described by two different binding groups, which might be of phenolic and carboxylic type as presented by humic matter. The sediment eliminated lead contamination (10(-6) moldm(-3) was the maximum concentration added) from 12 dm3 of water (surface of 8 dm2) within 2 days. It was also found that the sediment released organic ligands responsible for both labile and inert Pb complexes "seen" by voltammetry. The release of organic ligands that decreases the bioavailability of Pb(II) was clearly detected 1 week after contamination. Therefore, the sediment acts as a buffer for lead through two mechanisms against lead contamination: removing lead ions from the solution and releasing organic ligands to the water column. In a short period of time the sediment responds as a self-cleaning system for Pb(II) contamination in the estuarine water, which may have a very important influence in environmental pollution.     

Evaluation of trace metals bioavailability in Japanese river waters using DGT and a chemical equilibrium model

To develop efficient and effective methods of assessing and managing the risk posed by metals to aquatic life, it is important to determine the effects of water chemistry on the bioavailability of metals in surface water. In this study, we employed the diffusive gradients in thin-films (DGT) to determine the bioavailability of metals (Ni, Cu, Zn, and Pb) in Japanese water systems. The DGT results were compared with a chemical equilibrium model (WHAM 7.0) calculation to examine its robustness and utility to predict dynamic metal speciation. The DGT measurements showed that biologically available fractions of metals in the rivers impacted by mine drainage and metal industries were relatively high compared with those in urban rivers. Comparison between the DGT results and the model calculation indicated good agreement for Zn. The model calculation concentrations for Ni and Cu were higher than the DGT concentrations at most sites. As for Pb, the model calculation depended on whether the precipitated iron(III) hydroxide or precipitated aluminum(III) hydroxide was assumed to have an active surface. Our results suggest that the use of WHAM 7.0 combined with the DGT method can predict bioavailable concentrations of most metals (except for Pb) with reasonable accuracy.     

Predicting the rate and extent of cadmium and copper desorption from soils in the presence of bacterial extracellular polymer

The movement of cationic transition metals through the subsurface is strongly retarded by sorption to the porous media. However, dissolved organic ligands can compete with soil surfaces by providing binding sites for metals in solution. An extracellular polymer produced by a bacterium isolated from soil was used in this study to observe and model the influence of a naturally occurring ligand on the release of adsorbed metals from two test soils. Experimental results show that the presence of dissolved extracellular polymer enhanced the rate and extent of desorptive release of soil-bound cadmium and copper. A kinetic model that uses a gamma distribution of rate constants to account for the physical and chemical heterogeneity of the soil matrix was employed to describe the release of cadmium and copper in batch experiments. Model parameters describing soil, metal and extracellular polymer interactions were obtained through separate experiments. With these parameters the model successfully predicted the influence of dissolved polymer on the rate and extent of release of cadmium and copper from soil in independent batch experiments. These results suggest that the presence of natural metal-binding ligands such as bacterial extracellular polymers can act to increase the driving force for desorption by lowering the aqueous concentration of free unbound metals in solution.     

Equilibrium chemical modelling of heavy metals in activated sludge

A chemical speciation distribution model of heavy metals, previously developed by Nelson et al. (J. Wat. Pollut. Control Fed. 53, 1323, 1981), was applied to cadmium in activated sludge from a full-scale wastewater treatment plant. In the model, cadmium adsorption to bacterial solids was quantified by the determination of conditional formation constants based on TOC. Adsorption of cadmium strongly pH-dependent. Soluble cadmium speciation was dominated by the free cadmium ion below pH 6, by cadmium-organic ligand complexation at pH 6 and 7 and by inorganic species at pH 8 and 9. Cadmium adsorbed by bacterial solids increased greatly with pH from near 30% at pH 4 to near 90% at pH 9. Cadmium speciation and distribution was also modelled in an indifferent electrolyte suspension of bacterial solids and in activated sludge using adsorption constants from the indifferent electrolyte medium.     

Removal of heavy metals from storm and surface water by slow sand filtration: the importance of speciation

The removal of heavy metals from storm and surface waters by slow sand filtration is described. The importance of speciation as a technique for exploring and improving the mechanisms of removal is identified. Laboratory-scale slow sand filters operating at conventional flow rate and depth were shown to be able to reduce concentrations of selected heavy metals (Cu, Cr, Pb and Cd) found in road runoff, surface water and sewage effluents to drinking water standard. Nitrogen, volatile solids and modified Stover speciation were used to differentiate between the potential mechanisms of removal, i.e. active biomass, organic adsorption and simple adsorption or precipitation on the surface of the sand. The data presented show that adsorption via organic ligands was the predominant mechanism for metal removal at the surface of the filter but chemical adsorption was the more important deeper in the filter. In the lower layers the adsorbed metals were more easily exchanged than the organically bound metals. The precise chemical ligands were not identified and varied from metal to metal. The most important operational factors affecting performance were therefore the concentration of organic matter, filter depth and the flow velocity.     

Toxic and essential trace metals in muscle, liver and kidney of bovines from a polluted area of Morocco

Toxic and essential trace metals were measured in muscle, bone, liver and kidney of bovine grazing on the municipal wastewater spreading field of Marrakech City (Morocco). Bovines were found to be seriously contaminated by toxic metals, for metal bioaccumulation. The high cadmium content seemed to contribute to a reduction in zinc and copper levels. The arithmetic mean concentrations of zinc, especially cadmium, and levels were higher in liver and kidney, specific target organs copper and cadmium in liver and kidney, were respectively: 126, 112 and 5.1 microg/g in liver; 89, 33 and 10.3 microg/g in kidney.     

Residual heavy metal removal by an algae-intermittent sand filtration system

A laboratory scale study was undertaken to determine the feasibility of using algae growing in wastewater lagoons to absorb residual heavy metals for subsequent complete removal by intermittent sand filtration of the metal laden algae. In semi-continuous cultures the mixed algal flora native to wastewater lagoons absorbed 70–90% of the cadmium and copper from the wastewater media. Chromium absorption was less by ratio (20% was absorbed), but the mass of chromium removed was much greater as high levels of chromium were added. Only one alga (Oscillatoria sp.) which was extremely resistant to chromium grew in the chromium exposed cultures. Nearly total removal of the cadmium and copper was achieved by the algae-intermittent sand filter system. The net chromium removal agreed with the accumulation analyses.The technical feasibility of removing certain heavy metals from wastewater with such a system was established. However, in depth laboratory and field studies must be conducted to maximize system efficiency, demonstrate tactical limitations, and establish design specifications.     

Comparison of methods for the determination of conditional stability constants of heavy metal-fulvic acid complexes

Conditional stability constants and complexation capacities of complexes between fulvic acid and lead, cadmium and copper have been determined by ion selective electrodes, dialysis and differential pulse anodic stripping voltammetry. Most information was obtained from the ion selective electrodes which indicated that all three metals formed two types of complex with the fulvic acid. Weak cadmium complexes were undetectable when dialysis was used to separate bound and free metal. Only the stronger complexes of copper and cadmium were detected by polarography. The stability constant of the copper complex determined by polarography was lower than the equivalent values obtained from the other techniques, suggesting partial lability, while the lead complex was completely undetectable.     

Dissolved iron and its speciation in a shallow eutrophic lake and its inflowing rivers

It has been suggested that iron is a limiting factor on bloom-forming cyanobacteria in lake water. Although the availability of iron for phytoplankton depends significantly on its speciation, little is known about iron speciation in natural lake water. We investigated the horizontal distribution and temporal variation of dissolved iron and its chemical speciation in Lake Kasumigaura and its two inflowing rivers. Concentrations of dissolved iron and its organic ligands, determined by cathodic stripping voltammetry, clearly decreased as lake water flowed from the river entry points toward the center of the lake, indicating their riverine origin. The fraction of iron occurring in organic complexes tended to increase with the water flow. These results suggest that most of the dissolved iron in river water forms unstable soluble species, such as inorganic iron; thus, these unstable iron species may be scavenged in the mouths of rivers, and stable organic complexes of iron may flow to the center of the lake. Furthermore, most of the dissolved iron (88.2-99.9%) was present as organic complexes, and the inorganic iron level in Lake Kasumigaura (pFe' value=7.8-13.6) was similar to that observed in the open ocean. This result suggests that iron is an important factor determining the structure of the phytoplankton community in Lake Kasumigaura.     

Size charge fractionation of metals in municipal solid waste landfill leachate

Municipal solid waste landfill leachates from 9 Norwegian sites were size charge fractionated in the field, to obtain three fractions: particulate and colloidal matter >0.45microm, free anions/non-labile complexes <0.45microm and free cations/labile complexes <0.45microm. The fractionation showed that Cd and Zn, and especially Cu and Pb, were present to a large degree (63-98%) as particulate and colloidal matter >0.45microm. Cr, Co and Ni were on the contrary present mostly as non-labile complexes (69-79%) <0.45microm. The major cations Ca, Mg, K, and Mn were present mainly as free cations/labile complexes <0.45microm, while As and Mo were present to a large degree (70-90%) as free anions/non-labile complexes <0.45microm. Aluminium was present mainly as particulate and colloidal matter >0.45microm. The particulate and colloidal matter >0.45microm was mainly inorganic; indicating that the metals present in this fraction were bound as inorganic compounds. The fractionation gives important information on the mobility and potential bioavailability of the metals investigated, in contrast to the total metal concentrations usually reported. To study possible changes in respective metal species in leachate in aerated sedimentation tanks, freshly sampled leachate was stored for 48h, and subsequently fractionated. This showed that the free heavy metals are partly immobilized during storage of leachate with oxygen available. The largest effects were found for Cd and Zn. The proportion of As and Cr present as particulate matter or colloids >0.45microm also increased.     

Transformation of metals speciation in a combined landfill leachate treatment

Landfill leachate was treated by a combined sequential batch reactor (SBR), coagulation, Fenton oxidation and biological aerated filter (BAF) technology. The metals in treatment process were fractionated into three fractions: particulate and colloidal (size charge filtration), free ion/labile (cation exchange) and non-labile fractions. Fifty percent to 66% Cu, Ni, Zn, Mn, Pb and Cd were present as particulate/colloidal matter in raw leachate, whereas Cr was present 94.9% as non-labile complexes. The free ion/labile fractions of Ni, Zn, Mg, Mn, Pb and Cd increased significantly after treatment except Cr. Fifty-nine percent to 100% of Al was present mainly as particulate/colloidal matter > 0.45 μm and the remaining portions were predicted as non-labile complexes except in coagulation effluent. The speciation of Fe varied significantly in various individual processes. Visual MINTEQ simulation showed that 95-100% colloidal species for Cu, Cd and Pb were present as metal-humic complexes even with the lower dissolved organic carbon. Optimum agreements for the free ion/labile species were within acidic solution, whereas under-estimated in alkaline effluents. Overestimated particulate/colloidal fraction consisted with the hypothesis that a portion of colloids in fraction < 0.45 μm were considered as dissolved.     

Displacement of five metals sorbed on kaolinite during treatment with modified Fenton's reagent

The displacement of sorbed metals during the treatment of soils and groundwater with modified Fenton's reagent was investigated using five common metal contaminants (cadmium, copper, lead, nickel, and zinc) and kaolinite as a model sorbent. Modified Fenton's conditions included three H(2)O(2) concentrations (0.9, 1.8, 2.7 M) and two catalysts: soluble iron (III) at pH 3 and iron (III)-NTA chelate at pH 6. Iron (III)-catalyzed Fenton's reactions released significant amounts of zinc, cadmium, and copper. Modified Fenton's reactions catalyzed by iron (III)-NTA released zinc, cadmium, copper, and lead, and resulted in greater amounts of metals release than the iron (III)-catalyzed reactions. Metals release may have been mediated by transient oxygen species, such as superoxide, generated by propagation reactions, which become dominant at the relatively high hydrogen peroxide concentrations used. Metals release from kaolinite was undetectable when sufficiently low hydrogen peroxide concentrations were maintained to minimize propagation reactions. These results indicate that using dilute concentrations of hydrogen peroxide for Fenton's ISCO may minimize potential metals mobility when treating contaminated soils and groundwater containing a mixture of organic and metal contaminants.     

The effect of pH and hardness metal ions on the competitive interaction between trace metal ions and inorganic and organic complexing agents found in natural waters

The effect of pH and hardness metal ions on the interactions between trace metals and both inorganic and organic complexing agents has been studied under conditions simulating natural aquatic conditions, by employing anodic stripping voltammetric titration techniques. The complexation of Bi(III), Cd(II), Cu(II), Pb(II), and Tl(I) with the hydroxo- and carbonato-ligands found in a carbonate medium has been observed to generally increase with increasing pH. Both labile and nonlabile interactions have been observed. Nonlabile interactions are predominant at low pH and labile interactions generally increase with increasing pH. Neither calcium nor magnesium affects these interactions. The complexation of humic acids with trace metals in a carbonate medium was found to be more intense than metal ion-inorganic complexation. Both labile and nonlabile complexation was found; however, no generalizations can be made concerning the type and extent of complexation because of the individual nature of the interactions of each trace metal. Calcium was found to be more effective than magnesium in inhibiting trace metal-organic complexation. The effect of calcium is to inhibit labile complexation and is most pronounced with the cadmium-humic acid system.