Trace Metal Sequestration Research Articles

Schwertmannite and Fe oxides formed by biological low-pH Fe(II) oxidation versus abiotic neutralization: Impact on trace metal sequestration

Three low-pH coal mine drainage (CMD) sites in central Pennsylvania were studied to determine similarities in sediment composition, mineralogy, and morphology. Water from one site was used in discontinuous titration/neutralization experiments to produce Fe(III) minerals by abiotic oxidative hydrolysis for comparison with the field precipitates that were produced by biological low-pH Fe(II) oxidation. Even though the hydrology and concentration of dissolved metals of the CMD varied considerably between the three field sites, the mineralogy of the three iron mounds was very similar. Schwertmannite was the predominant mineral precipitated at low-pH (2.5–4.0) along with lesser amounts of goethite. Trace metals such as Zn, Ni and Co were only detected at μmol/g concentrations in the field sediments, and no metals (other than Fe) were removed from the CMD at any of the field sites. Metal cations were not lost from solution in the field because of unfavorable electrostatic attraction to the iron mound minerals. Ferrihydrite was the predominant mineral formed by abiotic neutralization (pH 4.4–8.4, 4 d aging) with lesser amounts of schwertmannite and goethite. In contrast to low-pH precipitation, substantial metal removal occurred in the neutralized CMD. Al was likely removed as hydrobasaluminite and Al(OH) 3, and as a co-precipitate into schwertmannite or ferrihydrite. Zn, Ni and Co were likely removed via adsorption onto and co-precipitation into the freshly formed Fe and Al solids. Mn was likely removed by co-precipitation and, at the highest final pH values, as a Mn oxide. Biological low-pH Fe(II) oxidation can be cost-effectively used to pre-treat CMD and remove Fe and acidity prior to conventional neutralization techniques. A further benefit is that solids formed under these conditions may be of industrial value because they do not contain trace metal or metalloid contaminants.

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.

Abundance and fractionation of Al, Fe and trace metals following tidal inundation of a tropical acid sulfate soil

Abstract Tidal inundation was restored to a severely degraded tropical acid sulfate soil landscape and subsequent changes in the abundance and fractionation of Al, Fe and selected trace metals were investigated. After 5 a of regular tidal inundation there were large decreases in water-soluble and exchangeable Al fractions within former sulfuric horizons. This was strongly associated with decreased soil acidity and increases in pH, suggesting pH-dependent immobilisation of Al via precipitation as poorly soluble phases. The water-soluble fractions of Fe, Zn, Ni and Mn also decreased. However, there was substantial enrichment (2–5×) of the reactive Fe fraction (FeR; 1 M HCl extractable) near the soil surface, plus a closely corresponding enrichment of 1 M HCl extractable Cr, Zn, Ni and Mn. Surficial accumulations of Fe(III) minerals in the inter-tidal zone were poorly crystalline (up to 38% FeR) and comprised mainly of schwertmannite (Fe8O8(OH)6SO4) with minor quantities of goethite (α-FeOOH) and lepidocrocite (γ-FeOOH). These Fe (III) mineral accumulations provide an effective substrate for the adsorption/co-precipitation and accumulation of trace metals. Arsenic displayed contrary behaviour to trace metals with peak concentrations (∼60 μg g−1) near the redox minima. Changes in the abundance and fractionation of the various metals can be primarily explained by the shift in the geochemical regime from oxic–acidic to reducing-circumneutral conditions, combined with the enrichment of reactive Fe near the soil surface. Whilst increasing sequestration of trace metals via sulfidisation is likely to occur over the long-term, the current abundance of reactive Fe near the sediment–water interface favours a dynamic environment with respect to metals in the tidally inundated areas.

Trace lead impacts biomineralization pathways during bacterial iron reduction

Dissimilatory Iron Reduction (DIR) is often implicated in both the remobilization of trace metals from sediments, and in the sequestration of trace metals into secondary mineral products. However, the factors controlling the extent of dissolution versus solid-phase redistribution have been elusive. We have made the following observations after incubating pure and Pb-substituted Fe (hydr)oxides with Shewanella putrefaciens 200R over 1200 h: 1) Pb substitution at a molar ratio of Pb:Fe = 5.19 × 10 − 4 inhibited Fe reduction; 2) the presence of Pb enhanced Fe dissolution and inhibited biologically induced magnetite formation; 3) Pb dissolved incongruently with Fe and accumulated to 190 nmol l − 1 in the aqueous phase; and 4) the residual solid-phase Pb was partitioned between an unresolved poorly reducible phase and weak acid extractable (surface sorbed or carbonate) phases. The presence of trace metals and Pb in soils and sediments could partially explain the apparent absence of magnetite in many Fe-reducing environments and its paucity in the sedimentary record. Organic matter degradation rates in Pb contaminated ecosystems may be reduced because of the inhibition of DIR by Pb. We assert that Pb should be largely immobile under Fe-reducing conditions due to its incorporation into refractory secondary minerals.

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.

Soluble polymeric ligands for metal complexation and catalyst recovery

AbstractSoluble polymers that bind metals and that in turn can be separated from other components of a reaction mixture are described. The polymers used include derivatives of acrylamides, acrylates, polystyrene and other polymers. Both sequestration of trace metals and recovery of homogeneous catalysts is discussed. Separation methods using liquid/liquid mixtures that are monophasic during a reaction but biphasic during a separation are emphasized.

The Influence of Varying Algal Biomass On Contaminant Exposure in Benthic-Planktonic Mesocosms: Copper (Ii)

A series of mesocosms was exposed to a suite of light treatments and nutrient enrichment in order to generate algal communities of varying biomass. the influence of this biomass on the speciation of copper (II) was studied. Distribution coefficients ( Kd,Lkg−1) were relatively high (log Kd = 5 to 7), indicative of robust trace metal sequestration, and were likely controlled by the particulate organic carbon content (foc). Differences in Kd over time and among treatments were significant, as was the relationship between Kd and foc. Fluorescence quenching was used to determine binding capacities ( Lt , M) and their associated binding constants ( Kcond ,M−1) in order to model the solid phase copper speciation. the Kcond ranged between 2.1 and 5.2 × 1012M−1, indicating a very strong copper-ligand complex, and was higher in mesocosms that received more light. the light Lt increased over time, dramatically after the nutrient enrichment, but did not vary systematically among light treatments. Lt ranged from 7.2 × 10− 7 to 4.9 × 10− 5 M. the large magnitudes of Kd , Kcond and Lt ensured that greater than 97% of total copper in the mesocosms was complexed by organic matter. the total copper concentration ([Cu]T, M) needed to reach a target dissolved copper concentration of 10−12.5 M (pCu = 12.5) was determined for each mesocosm over time. [Cu]T was between 8.02 × 10−5 and 3.41 × 10−2 M, and increased over time. the [Cu]T normalized to the target pCu (Effective Dose Ratio, EDR) increased directly with increases in algal biomass, indicating a direct link between system productivity and copper exposure. Approximately 45% of the variance in EDR was explained by variance in total biomass, while the residual variance in EDR was due likely to differences in the strengths of particle associations and magnitude of binding capacities.

Strategies of trace metal sequestration in aquatic organisms

A brief review is presented of strategies for the sequestration of trace metals by aquatic biota, emphasising invertebrates. Existing strategies probably evolved through a need to detoxify and (at times) store major ions such as calcium, and metals of vital physiological function such as copper, iron and zinc. Several types of strategies exist in different phyla and species, and organisms lie on a continuum from ‘regulators’ of metals to ‘non-regulators’. Regulators balance metal excretion and influx over a large range in ambient availabilities. Metals are stored by partial regulators in soluble forms such as metallothioneins, found principally in the hepato-pancreas and kidneys. By contrast, non-regulators rely more on insoluble granules for metal storage. Such sequestration strategies are important in defining both the toxicities of metals to aquatic biota and the use of organisms as bio-monitors of aquatic pollution by trace elements.