Partitioning Of Trace Metals Research Articles

Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River, SW France)

Abstract Mining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM–EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water–sediment interface of (i) dissolved SO4 promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe-oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), ∼6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary.

Transfer functions for solid‐solution partitioning of cadmium, copper, nickel, lead and zinc in soils: derivation of relationships for free metal ion activities and validation with independent data

Models to predict the solid‐solution partitioning of trace metals are important tools in risk assessment, providing information on the biological availability of metals and their leaching. Empirically based models, or transfer functions, published to date differ with respect to the mathematical model used, the optimization method, the methods used to determine metal concentrations in the solid and solution phases and the soil properties accounted for. Here we review these methodological aspects before deriving our own transfer functions that relate free metal ion activities to reactive metal contents in the solid phase. One single function was able to predict free‐metal ion activities estimated by a variety of soil solution extraction methods. Evaluation of the mathematical formulation showed that transfer functions derived to optimize the Freundlich adsorption constant (Kf), in contrast to functions derived to optimize either the solid or solution concentration, were most suitable for predicting concentrations in solution from solid phase concentrations and vice versa. The model was shown to be generally applicable on the basis of a large number of independent data, for which predicted free metal activities were within one order of magnitude of the observations. The model only over‐estimated free‐metal ion activities at alkaline pH (>7). The use of the reactive metal content measured by 0.43 m HNO3 rather than the total metal content resulted in a close correlation with measured data, particularly for nickel and zinc.

Co-transport of dissolved organic matter and heavy metals in soils induced by excessive phosphorus applications

To evaluate the effects of long-term applications of phosphorus fertilizers on mobility of dissolved organic matter (DOM) and heavy metals in agricultural soils, a sandy soil and a loamy soil were spiked with ammonium phosphate at application rates of 0, 25, 50, 100, 250, and 500 mg P per kilogram of soil. A series of 15-cm long soil columns were constructed by packing incubated soils of varying concentrations of P. The soil columns were consecutively leached by simulated rainfalls for six cycles. The contents of water extractable organic carbon in both sandy and loamy soils increased significantly with increasing rates of P applications. Relatively high rates of P applications could induce a marked increase in DOM concentrations in the leachates, the effects were larger with the sandy soil rather than with the loamy soil. Applications of P changed the partitioning of trace metals in the soil solids and the soil solutions. The increased P application rates also seemed to elevate the leaching of Cu, Cd, and Zn from soils. The concentrations of Cu, Cd, and Zn in the leachates were positively correlated with DOM, probably due to the formation of metal-DOM complexes. In contrast, Pb concentrations in the leachates were negatively correlated with DOM, and decreased with increasing rates of P applications. The boosted leaching of DOM induced by high rates of P applications was probably due to the added phosphate ions competing for adsorption sites in the soil solids with the indigenous DOM.

Metal intracellular partitioning as a detoxification mechanism for mummichogs (Fundulus heteroclitus) living in metal-polluted salt marshes

Intracellular partitioning of trace metals is critical to metal detoxification in aquatic organisms. In the present study, we assessed metal (Cd, Cu, Pb, and Zn) handling capacities of mummichogs (Fundulus heteroclitus) in metal-polluted salt marshes in New York, USA by examining metal intracellular partitioning. Despite the lack of differences in the whole body burdens, partitioning patterns of metals in intracellular components (heat-stable proteins, heat-denaturable proteins, organelles, and metal-rich granules) revealed clear differential metal handling capacities among the populations of mummichogs. In general, mummichogs living in metal-polluted sites stored a large amount of metals in detoxifying cellular components, particularly metal-rich granules (MRG). Moreover, only metals associated with MRG were consistently correlated with variations in the whole body burdens. These findings suggest that metal detoxification through intracellular partitioning, particularly the sequestration to MRG, may have important implications for metal tolerance of mummichogs living in chronically metal-polluted habitats.

Relevance of intracellular partitioning of metals in prey to differential metal bioaccumulation among populations of mummichogs ( Fundulus heteroclitus)

Intracellular partitioning of trace metals is critical to metal tolerance in aquatic organisms and may also influence metal trophic transfer in ecosystems. In this study, we tested the relevance of metal (Cd, Cu, Pb, and Zn) intracellular partitioning in prey as an indicator of metal trophic availability to benthic forage fish, mummichogs ( Fundulus heteroclitus), in chronically metal-polluted salt marshes in New York, USA. Two common prey of mummichogs in the study area, Palaemonetes pugio and Nereis acuminata, generally stored increasingly higher proportions of non-essential metals (particularly Pb) in insoluble (less trophically available) cellular components, as the whole body burdens increased. In contrast, intracellular partitioning of essential metals (Cu and Zn) in invertebrate prey varied relatively little among sites. Differential Cd and Pb intracellular partitioning patterns within P. pugio among sites were significantly associated with Cd and Pb whole body burdens in mummichogs, respectively (i.e., prey-driven bioreduction of metals), while bioaccumulation of Cu and Zn in mummichogs was similar among populations. The findings in this study suggest that metal intracellular partitioning within prey may be partially responsible for metal trophic availability to a predator in metal-polluted habitats, while there was also evidence that some predator-dependent processes may offset differential trophic availabilities from prey.

Comparative study of the fate and mobility of metals discharged in mining and urban effluents using sequential extractions on suspended solids

The fate, bioavailability and environmental impacts of metals discharged in municipal and mining wastewater discharge will depend to a large extent on chemical speciation and distribution. Previous studies on metal bioaccumulation have shown that total metal concentrations are not a good predictor of bioavailability in the dispersion plumes of municipal effluents. The objective of this study was to determine the solid phase speciation of metals in surface waters receiving urban and mining effluents in order to assess their fate and relative mobility in the receiving environment. Suspended particulate matter was sampled using sediment traps at several sites downstream of effluent outfall plumes as well as at reference upstream sites. Particulate metal in operationally defined fractions--exchangeable/carbonates, reducible, oxidisable and residual--were determined in suspended particulate matter with a series of selective chemical extractions. Metal enrichment in suspended particles was generally observed in both mining and urban effluent discharges. When compared to its receiving environment, the mining effluent appeared to release more particulate metals (Cu, Fe, Zn) in the most reactive fractions (i.e. exchangeable/carbonates + reducible forms, 23-43%), while other released metals, such as Cd and Mn, were predominantly in the least reactive forms (i.e., oxidisable + residual, 73-97%). In contrast, the reactivity of all particulate metals, with the exception of Mn, from the urban effluent was much higher, with up to 65, 42, 30 and 43% for Cd, Cu, Fe and Zn, respectively, in the two most reactive fractions. As expected in effluent dispersion plumes, parameters such as the organic carbon, Fe oxide and carbonate contents have specific effects on the partitioning of several trace metals, particularly Cd, Cu and Zn. Our results indicated that the relative distributions of metals among geochemical fractions varied in the effluent receiving waters where organic carbon and Fe oxides appeared as the most important parameters. This could therefore decrease the exposure for aquatic organisms that are exposed to those contaminated sediments as well as the risk to human health.

Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

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.

Study of trace metal leaching from coals into seawater

The behaviour of three South African coals in water and, particularly in seawater, was examined. A sequential speciation procedure used to evaluate trace metal partitioning in coal has shown that trace metals will not be easily released from these coals into environmental ecosystems. Only a few trace elements are slightly leached from these coals into water or seawater at pH around 8. On the other hand, Mn is highly leached from these coals into water or seawater. It has been clearly shown that Mn concentrations are highly correlated to sulfate and calcium concentrations indicating that Mn is mainly solubilized into water simultaneously to gypsum; the leaching efficiency being severely reduced for coal having a high calcite content. The leaching percentage of Mn into seawater is enhanced by the presence of seawater salts that increases gypsum solubility. The leaching process of Mn from coal into water or seawater is governed by gypsum solubilization and is relatively rapid during the first thirty minutes, then very slow. In this study, it has been also shown that, depending on their physico-chemical properties, trace metals may be removed from seawater solutions in the presence of coal having a high calcite content. In this work, it has been also shown that some elements, particularly Fe, are greatly solubilized into seawater in the presence of a strong chelating agent like EDTA. Like for Mn, the leaching rate of metals from coal in the presence of EDTA is relatively rapid during the first 30 min then much slower, suggesting a solubilization process simultaneously to gypsum or/and calcite solubilization.

Spatial and seasonal variations in depth profile of trace metals in saltmarsh sediments from Sapelo Island, Georgia, USA

This study was undertaken to elucidate the impact of early diagenetic processes on the accumulation of trace metals in Sapelo Island saltmarsh sediments as a function of time, space and sediment properties. Samples were collected from three sites in summer (May 1997) and winter (January 1998) along a transect from an unvegetated Creek Bank through a vegetated Tidal Levee to the vegetated midmarsh with evident lateral heterogeneity caused by hydrologic regime, macrophytes and microbial and macrofaunal activities. A suite of trace metals (As, Ba, Cr, Co, Cu, Cd, Mo, Ni, Pb, Th, Ti, U, V, Zn and Zr) was analyzed to obtain their depth-distribution at the three sites. Spatially marked differences were observed, that were primarily related to hydraulic flushing of trace metals away from the sites in high-energy regimes, rapid downward mixing and reworking of sediment via bioturbation, and below-ground degradation and production of Spartina biomass. Although sulfate reduction and the formation of acid volatile sulfide and pyrite were dominant processes throughout the marsh, the trace metal scavenging role of sulfides was not apparent. However, possible sulfurization of organic matter, leading to enhanced trapping of trace metals with organic carbon, may have played an important role in sequestration of trace metals. No similarity was observed visually between the depth trends of trace metals and sediment properties (grain size, iron-oxyhydroxide content, acid volatile sulfides and pyrite content) that are known to play a major role in trace metal partitioning. Only organic carbon content closely followed the trace metal profiles at all the three sites. Minor variation in depth-integrated sediment trace metal content was observed seasonally at each of the three sites. Furthermore, the depth trend of profiles of individual trace metals also did not vary significantly over the seasons either.

Monitoring of heavy metal partitioning in reef corals of Lakshadweep Archipelago, Indian Ocean

This paper focuses on the partitioning of trace metals in five selected coral species from Lakshadweep Archipelago, which remains as one of the least studied areas in the Indian Ocean. Based on the morphological features, selected coral species are classified as massive (Porites andrewsi), ramose or branching (Lobophyllia corymbosa, Acropora formosa and Psammocora contigua) and foliaceous (Montipora digitata). Relating trace metal concentrations with morphological features in skeleton, highest concentrations of all the trace metals (except Zn) were reported for the ramose type corals. In tissue, all the metals (essential as well as non essential) showed highest concentrations within the branching type corals. Irrespective of their growth characteristics/pattern, all species except P. contigua displayed higher concentrations of Pb, Ni, Mn and Cd within their skeleton compared to tissue which may exemplify a regulatory mechanism to avoid the build up of the concentrations of these metals in their bio-part, strikingly toxic metals like Cd and Pb. The concentrations of trace metals in the skeleton and tissues of these coral species were subjected to 3 way ANOVA based on non standardized original data and the results showed significant differences between metals and between species leading to high skeleton/ tissue - species interaction as well as skeleton/tissue - metal interaction. The significant values of student's t calculated are depicted in the form of Trellis diagrams.

A Flow Reactor Model Facsimile to the Trace Metal Partitioning in a Tropical Backwater System

This article attempts to focus on the development of a flow reactor model applicable to the partitioning of trace metals in a backwater system, called Kuttanad backwaters, a low-lying area located in the state of Kerala, on the southwest coast of the Indian Peninsula. Based on hydrographic parameters, mainly salinity characteristics, the study area (comprising of nine stations) is divided into three zones of geochemical entity. A multivariable model based on steady-state approach was formulated for the partitioning of trace metals in dissolved, sedimentary, and particulate compartments. The ratio between particulate and dissolved phases is taken as the state variable; using this variable auxiliary variables were obtained that are indicative of geochemical reactivity of trace metals in this tropical backwater system.

Correlations, partitioning and bioaccumulation of trace metals between different segments of Taylor Creek, southern Nigeria

Correlations between trace metals in dissolved and particulate phases, B. bayad and sediments were investigated in five selected sites along Taylor Creek, which lies between longitude 006°17I to 006°21I E and latitude 05°01I to 05°05I N. The degree of correlation between the various metals was different in each of the investigated segments. Between segments, not many significant correlations were recognized. Only Ni and Cd, Mn and Cd, Mn and Ni, and Mn and Pb are correlated in the sediments and in the particulate phase, Fe and Cr, Pb and Cd, and Zn and Ni are correlated, which suggests that the sources are not common for both compartments. Partitioning coefficients (Kd) of trace metals between dissolved and particulate phases are generally low, which is typical for fresh water ecosystems and fairly stable over Taylor Creek all through the seasons. Furthermore, the bio-concentration factors (BCF) of B. bayad were low unlike those of other natural waters. Cluster analysis showed that metal accumulation in the particulate phase differed from those observed in sediments, which also confirms that the pollution of the Creek might be from different sources.

Factors Controlling the Geochemical Partitioning of Trace Metals in Estuarine Sediments

The geochemical partitioning of trace metals in sediments is of great importance in risk assessment and remedial investigation. Selected factors that may control the partitioning behavior of Cu, Pb and Zn in non-sulfidic, estuarine sediments were examined with the use of combined sorption curve—sequential extraction analysis. This approach, which has not been previously used to examine estuarine sediments, allowed determination of sorption parameters for Cu, Pb and Zn partitioning to individual geochemical fractions. Partitioning behavior in sulfidic sediments was also determined by sequentially extracting Cu, Pb, and Zn from synthetic sulfide minerals and from natural sediment and pure quartz sand after spiking with acid-volatile sulfide (AVS). Trace metal sorption to the “carbonate” fraction (pH 5, NaOAc extraction) increased with metal loading due to saturation of sorption sites associated with the “Fe-oxide” (NH2OH·HCl extraction) and “organic” (H2O2 extraction) fractions in non-sulfidic sediments. Freundlich parameters describing sorption to the “Fe-oxide” and “organic” fractions were controlled by the sediment Fe-oxide and organic carbon content, respectively. Sequential extraction of Cu from pure CuS, AVS-spiked sediment and AVS-spiked quartz sand showed that AVS-bound Cu was quantitatively recovered in association with the “organic” fraction. However, some AVS-bound Pb and Zn were recovered by the NH2OH·HCl step (which has been previously interpreted as “Fe-oxide” bound metals) in the sequential extraction procedure used in this study. This indicates that the sequential extraction of Pb and Zn in sulfidic sediments may lead to AVS-bound metals being mistaken as Fe-oxide bound species. Caution should therefore be exercised when interpreting sequential extraction results for Pb and Zn in anoxic sediments.

Partitioning and mobility of trace metals in the Blesbokspruit: Impact assessment of dewatering of mine waters in the East Rand, South Africa

A suite of trace metals was analyzed in water and sediment samples from the Blesbokspruit, a Ramsar certified riparian wetland, to assess the impact of mining on the sediment quality and the fate of trace metals in the environment. Limited mobility of trace metals was observed primarily because of their high partition coefficient in alkaline waters. Nickel was most mobile with a mean K d of 10 3.28 L kg −1 whereas Zr was least mobile with a mean K d of 10 5.47 L kg −1. The overall trace metal mobility sequence, derived for the Blesbokspruit, in increasing order, is: Zr < Cr < Pb < Ba < V < Cu < Zn < Sr < Mn < U < Mo < Co < Ni. Once removed from the solution, most trace metals were preferentially associated with the carbonate and Fe–Mn oxide fraction followed by the exchangeable fraction of the sediments. Organic C played a limited role in trace metal uptake. Only Cu was primarily associated with the organic fraction whereas Ti and Zr were mostly found in the residual fraction. Compared to their regional background, Au and Ag were most enriched, at times by a factor of 20–400, in the sediments. Significant enrichment of U, Hg, V, Cr, Co, Cu and Zn was also observed in the sediments. The calculated geoaccumulation indices suggest that the sediments are very lightly to lightly polluted with respect to most trace metals and highly polluted with respect to Au and Ag. The metal pollution index (MPI) for the 20 sampled sites varied between 2.9 and 45.7. The highest MPI values were found at sites that were close to tailings dams. Sediment eco-toxicity was quantified by calculating the sediment quality guideline index (SQG-I). The calculated SQG-I values (0.09–0.69) suggest that the sediments at the study area have low to moderate potential for eco-toxicity.

Modelling trace metal partitioning in forest floors of northern soils near metal smelters

Trace metal (TM) mobility and toxicity varies with changing soil conditions. Geochemical models can account for the influence of soil characteristics on TM behaviour. We tested the effectiveness of the Stockholm humic model (SHM), and the NICA–Donnan model (NDM) to estimate partitioning coefficients (log Kd) in 26 forest floor horizons of podzolic soils enriched in trace metals from deposition by metal smelters. We wanted to know if a consistent approach could be applied to model metal partitioning in forest floors without optimizing each individual soil. When optimized, the SHM reproduced the partitioning of Cd, Cu and Zn but not Pb. It was necessary to revise the affinity constants for the NDM to simultaneously simulate the partitioning of the four metals. Revised affinity constants for the NDM model based on a fixed definition of soil organic carbon, i.e., a fixed ratio of fulvic and humic acids per unit carbon, reproduced metal partitioning more effectively in an independent data set of 16 soils than the use of generic affinity constants available for these models. From the perspective of the applicability of these models to risk assessment, this result suggests geochemical models using affinity constants that have been verified and/or modified against multiple soils from a region can provide good estimates of metal partitioning on a regional scale.

Geochemistry and partitioning of trace metals in paddy soils affected by metal mine tailings in Korea

Soil solution samples were extracted from paddy soil near mine tailing dumps in an abandoned mine in Korea. Trace metals in the soil solution and soil solid (As, Cd, Cr, Cu, Ni, Pb and Zn) were analysed, along with the mineralogical composition of the soil, using XRD. Sequential extraction was also undertaken for speciation of different fractions bound to the soil solid. Kaolinite was the main clay minerals and the CEC value was relatively low, recording between 11.0 and 27.5 meq/100 g. Comparison of the paddy soil with the control soil samples collected from an uncontaminated area revealed that nearly all the paddy soil samples were enriched for trace metal contents. Cadmium, Pb and Zn concentrations exceeded the intervention values of the Dutch standards, which requires remediation action. Arsenic, Ni and Cr were below the values, indicating little or no contamination for these metals. The trace metal contents in the paddy varied with distance from the mine tailing site. In addition to the changes with distance, higher proportions of relatively easily releasable fractions, such as exchangeable forms, were found to be proportional to the total trace metal contents in the soil sample. Although most paddy soil samples were enriched with respect to some trace elements, concentrations of Cd, Cu, Ni and Pb in the solution were very low, recording maximum levels of up to only several milligrams per liter. Geochemical equilibrium modelling using PHREEQC indicates the presence of solubility controlling solid phases for Cd and Pb, whereas Zn and Cu seem to be controlled by adsorption/desorption processes. We presumed that either iron sulphides or oxides removed dissolved trace elements. Under reducing conditions, iron may be dissolved as Fe 2+ in the soil solution and then the reduced iron possibly would form iron sulphide precipitates with sulphur from the mine tailings. On the contrary, in an oxidizing condition, iron exists as the oxidised form, Fe 3+, and again forms iron oxides, which is a good adsorbent for trace elements in soil environments. A Cycle of dry and flooded conditions is characteristic for paddy fields. Therefore, either iron sulphide or iron oxide is believed to provide a good adsorbing site for trace metals and so explains the subsequent low concentrations in the soil solution. Despite the low trace metal concentrations in the soil solution, higher portions of the trace metals still exist as relatively easily available form in the soil solid. It should be stressed that controlling of the redox condition and pH would be important in managing the transport of trace metals in the paddy soil that was affected by the mine tailings.

Study of trace metal partitioning between soil–EDTA extracts and Chelex-100 resin

The partitioning of Cu, Cd and Pb in EDTA leachates from a variety of soils, to Chelex-100 resin was investigated. A series of experiments was conducted to optimise method for the trace element sorption on Chelex-100 in 13 unpolluted soils from Burgundy, France. The extraction efficiency of Chelex-100 varied depending on soil carbonate contents. The largest percentage of trace metals was transferred to the resin in non-calcareous samples, while the resin was used in its Ca form. This technique was able to trap up to 98% of Cu, 72% of Cd and 28% of Pb in non-calcareous soil leachates. The fraction of metal transferred to the Chelex-100 in calcareous soil extracts was 40% less than those in non-calcareous ones. Besides, a kinetic procedure was developed to study the kinetic of cation exchange from soil–EDTA leachates onto solid-phase resin. The soil calcium content was found to be a controlling factor in the Cu sorption on the Ca–Chelex. Two different kinetic behaviours were observed in calcareous and non-calcareous soils. The dissociation rate of Cu in non-calcareous soil extracts was 10 times higher than that in calcareous ones. Application of kinetic model indicated the presence of two components associated to Cu in non-calcareous samples. This was discussed in terms of metal sorption mechanism from soil solution onto chelating resin.

Trace metals in seawater and copepods in the ocean outfall area off the northern Taiwan coast

The distribution, partitioning and concentrations of trace metals (Cd, Cr, Cu, Fe, Mn, Pb and Zn) in seawater, including dissolved and particulate phases, and in copepods in the ocean outfall area off the northern coast of Taiwan were investigated. Normalization of metal concentrations to the background metal concentration to yield relative enrichment factors (EF), which were used to evaluate the contamination of dissolved and particulate trace metals in seawater around the ocean outfall. The EF results indicated that the outfall area was significantly contaminated by dissolved Fe and Zn, and by particulate Fe, Cr, Cu, Pb and Zn. In addition, most trace metals were chiefly in the particulate phase. The average percentage of total metal concentrations (dissolved plus particulate phases) bound by suspended particulate matter followed the sequence Al(95%) = Mn(95%) > Pb(88%) > Cu(86%) > Fe(72%) > Zn(32%) > Cr(17.5%) > Cd(3.4%). Therefore, metal contamination is better evaluated in solid phase than in the dissolved phase. The concentration ranges of trace metals in the copepods, Temora turbinata, Oncaea venusta and Euchaeta rimana, near the outfall were: Cd, 0.23-1.81 microg g(-1); Cr, 16.5-195 microg g(-1); Cu, 14-160 microg g(-1); Fe, 256-7255 microg g(-1); Mn, 5.5-80.8 microg g(-1); Pb, 2.6-56.2 microg g(-1); Zn, 132-3891 microg g(-1); and Al, 0.21-1.13%. Aluminum, and probably Fe, seemed to be the major elements in copepods. The concentrations of trace metals in copepods, especially Temora turbinata, near the outfall were generally higher than those obtained in the background station. The mean increase in bioconcentration factor of metals in copepods ranged from 4 to 7 and followed the sequence Al(6.4) > Cu(6.2) > Fe(6.0) > Zn(5.7) > Pb(5.6) > Cr(5.5) > Cd(5.1) > Mn(4.7). Therefore, marine copepods in the waters of northern Taiwan can accumulate trace metals over background concentrations and act as contamination indicators.

Solid state partitioning of trace metals in suspended particulate matter from a river system affected by smelting-waste drainage

The partitioning of particulate trace metals was investigated during one year of monthly sampling of suspended particulate matter (SPM) at eight sites along the Lot–Garonne fluvial system, known for its polymetallic pollution. The chemical partitioning in five operationally defined fractions (exchangeable/carbonate, Fe/Mn oxides, organic matter/sulfides, acid soluble, residual) was determined using a multiple single extraction approach. This approach showed that Cd, Zn, Pb and Cu were mainly associated with acid soluble phases (84–95%, 65–88%, 61–82% and 55–80% of the respective total metal content), and therefore showed a high mean potential of mobilization and bioavailability. In the Riou-Mort River, draining the smelting-wastes, Zn, Cd and Mn showed high mobility as they were little associated with the residual fraction (1–2%) and mainly bound to the ‘exchangeable’ fraction of SPM (60–80%), probably weakly adsorbed on amorphous freshly-precipitated sulfide and/or oxide phases. Upstream and downstream of the anthropogenic source of metallic pollution, Mn and Cd, and Zn to a lesser extent, remained highly reactive. The other trace metals were mainly associated with the residual fraction and thus less mobile. However, the multiple single extraction scheme revealed that the most reactive transport phases were non-selectively extracted by the conventional extractants used here. These selectivity problems could not have been observed if sequential extraction was used.