Release into the environment of metals by two vascular salt marsh plants

Metals in contaminated salt marshes are mainly locked in the anaerobic layer of sediments, where they are tightly bound as sulfides and organic complexes. Vascular plants survive in saturated soils in part by pumping O2 into their root zones, changing their microenvironment to an oxic one. This, along with chelating exudates, mobilizes metals, allowing uptake by the roots. We compared the common reed Phragmites australis and cordgrass Spartina alterniflora in lab and field studies for ways in which they handle trace metals. Both plants store most of their metal burden in their roots, but some is transported to aboveground tissues. Spartina leaves contain approximately 2-3 x more Cr, Pb, and Hg than Phragmites leaves, but equivalent Cu and Zn. Furthermore, Spartina leaves have salt glands, so leaf excretion of all metals is twice that of Phragmites. In-depth studies with Hg indicate that Hg excretion correlates with Na release but not with transpiration, which is 2.2 x higher in Phragmites; and that more Hg accumulates in early-appearing leaves than in upper (i.e. later) leaves in both species. Spartina thus makes more metals available to salt marsh ecosystems than Phragmites by direct excretion and via dead leaves which will enter the food web as detritus.     

Distributions of dissolved and particulate biogenic thiols in the subartic Pacific Ocean

Dissolved and particulate concentrations of the biogenic thiols cysteine (Cys), arginine–cysteine (Arg–Cys), glutamine–cysteine (Gln–Cys), γ-glutamate–cysteine (γ-Glu–Cys) and glutathione (GSH) were measured in the subartic Pacific Ocean in the summer of 2003 using high performance liquid chromatography (HPLC) with precolumn derivatization as reported in previous work. In this study, a preconcentration protocol for the derivatized thiols was utilized to extend detection limits of dissolved thiols to picomolar levels. The measured concentrations of particulate and dissolved thiols were uncoupled, with distinctive depth profiles and large differences in the particulate to dissolved ratios between individual compounds. Glutathione was the most abundant particulate thiol whereas the most abundant dissolved thiol was γ-Glu–Cys, with concentrations as high as 15 nM. Given the relatively small pool of intracellular γ-Glu–Cys and the very low dissolved concentrations of GSH, we hypothesize that glutathione released from cells is rapidly converted to the potentially degradation resistant γ-Glu–Cys outside the cell. The relatively high concentrations of other dissolved thiols compared to particulate concentrations implies both biological exudation and slow degradation rates. Some thiols appear to vary with changes in nutrient availability but this effect is difficult to decouple from changes in community structure inferred from pigment analyses. Dissolved thiol concentrations also exceed typical metal concentrations in the subartic Pacific, supporting previous arguments that they may be important in metal speciation.     

An evaluation of metal bioaccessibility in estuarine sediments using the commercially available protein, bovine serum albumin

The bioaccessibility of metals (Al, Ca, Fe, Mn, Ag, Cd, Co, Cu, Ni, Pb, Sn, Zn) in oxic estuarine sediments has been evaluated using solutions of a commercially available protein (bovine serum albumin; BSA) that mimic the chemical conditions encountered in the gut environment of many deposit-feeding organisms. Over a 20 h incubation period with 5 g L^− 1 BSA, metal mobilisation was generally biphasic in that a relatively short period of rapid release was succeeded by more gradual release or approach to equilibrium, although in some cases metal readsorption was evident during the time-courses. Availability to BSA, defined as metal released after 20 h relative to metal extracted by boiling aqua regia, was greatest for Cd, Ni, Ca and Zn and lowest for Fe and Mn, and correlated well with, but was an order of magnitude lower than, metal digested by acidified hydrogen peroxide. Time-courses conducted in the absence of the protein revealed that significant quantities of Ca and Mn were water-soluble, reflecting the partial dissolution of carbonates and hydrous Mn oxides, respectively. Additional experiments indicated a net increase in metal release with increasing BSA concentration and, with the exception of Ca and Mn, a substantial increase in metal mobilisation after sediment organic matter had been digested by peroxidation. These observations suggest that, apart from Ca and Mn, metal release proceeds via complexation with component amino acids of the protein, denudation of organic host phases, and exposure of inorganic, metal-bearing minerals. Accordingly, the bioaccessibility of a metal is predicted to be dependent on its (i) affinity for proteinaceous ligands, (ii) association with components of digestible sediment organic matter, and (iii) degree of binding at relatively weak sites on sediment phases that are exposed or modified by the action of proteins and other chemical constituents of the gut environment.     

Sediment budget-based estimates of trace metal inputs to a Chesapeake estuary

This article evaluates whether a sediment budget for the South River, Maryland, can be coupled with metals data from sediment cores to identify and quantify sources of historic metal inputs to marsh and subtidal sediments along the estuary. Metal inputs to estuarine marsh sediments come from fluvial runoff and atmospheric deposition. Metal inputs to subtidal sediments come from atmospheric deposition, fluvial runoff, coastal erosion, and estuarine waters. The metals budget for the estuary indicates that metal inputs from coastal erosion have remained relatively constant since 1840. Historical variations in metal contents of marsh sediments have probably resulted primarily from increasing atmospheric deposition in this century, but prior to 1900 may reflect changing fluvial sources, atmospheric inputs, or factors not quantified by the budget. Residual Pb, Cu, and Zn in the marsh sediments not accounted for by fluvial inputs was low to moderate in 1840, decreased to near zero circa 1910, and by 1987 had increased to levels that were one to ten times greater than those of 1840. Sources of variability in subtidal cores could not be clearly discerned because of geochemical fluxes, turbulent mixing, and bioturbation within the cores. The sediment-metal budgeting approach appears to be a viable method for delineating metal sources in small, relatively simple estuarine systems like the South River and in systems where recent deposition (for example, prograding marshes) prevents use of deep core analysis to identify background levels of metal. In larger systems or systems with more variable sources of sediment and metal input, however, assumptions and measurement errors in the metal budgeting approach suggest that deep core analysis and normalization techniques are probably preferable for identifying anthropogenic impacts.Field and laboratory research conducted at the Department of Geography, University of Maryland, College Park, Maryland, 20742, USAField and laboratory research conducted at the Marine and Estuarine Environmental Science Program, University of Maryland, College Park, Maryland, 20742, USA     

Effects of enhanced zinc and copper in drinking water on spatial memory and fear conditioning

Ingestion of enhanced zinc can cause memory impairments and copper deficiencies. This study examined the effect of zinc supplementation, with and without copper, on two types of memory. Rats raised pre- and post-natally on 10 mg/kg ZnCO₃ or ZnSO₄ in the drinking water were tested in a fear-conditioning experiment at 11 months of age. Both zinc groups showed a maladaptive retention of fearful memories compared to controls raised on tap water. Rats raised on 10 mg/kg ZnCO₃, 10 mg/kg ZnCO₃ + 0.25 mg/kg CuCl₂, or tap water, were tested for spatial memory ability at 3 months of age. Significant improvements in performance were found in the ZnCO₃ + CuCl₂ group compared to the ZnCO₃ group, suggesting that some of the cognitive deficits associated with zinc supplementation may be remediated by addition of copper.     

Stabilisation/solidification and bioaugmentation treatment of petroleum drill cuttings

Petroleum drill cuttings are usually treated by techniques suitable for particular contaminant groups. The significance of this study consists in the development of a treatment technology that can simultaneously handle the hydrocarbon and metal constituents of drill cuttings. Bioaugmentation is combined with stabilisation/solidification (S/S), within S/S monoliths and in granulated S/S monoliths. Portland cement was used for S/S treatment at 30% binder dosage. Bioaugmentation treatment involved two bacterial densities of a mixed culture bio-preparation. The effects of inclusion of compost, fertiliser and activated carbon were also evaluated. After 28 days, the combined S/S and bioaugmentation treatments recorded up to 15% higher total petroleum hydrocarbon (TPH) loss than control S/S treatment without bioaugmentation. Embedding fertiliser, activated carbon and higher bacterial density within S/S monoliths resulted in the highest (99%) TPH reduction but higher concentrations of metals. The addition of compost and lower bacterial density to granulated S/S monoliths led to similar (98%) TPH degradation and lower amounts of metals. The results suggest that with better mixture optimisation, combining S/S and bioaugmentation could engender more sustainable treatment of drill cuttings.     

A Screening Procedure for Heavy Metals in Soil Extracts by Alcohol Dehydrogenase and Urease Inhibition Eine Screening-Methode für Schwermetalle in Extrakten aus Bodenproben,basierend auf der Inhibierung der Enzyme Alkoholdehydrogenase und Urease

A screening method for heavy metals in aqueous extracts of soil is presented which is based on inhibition of the enzymes urease and alcohol dehydrogenase. The method is suitable to detect cupric and mercury ions in concentrations below 0.01 mg/L and several other heavy metal ions in 1000 fold higher concentration. It is shown that the test may be used for screening of mercury ion concentrations exceeding 0.03 mg/L in aqueous solution when copper chelators are added to the test system. The usefulness of the presented tests to detect heavy metals eluted from soil was verified with samples from ore mining waste. The concentration of copper, lead, and zinc eluted from these samples to different amount was determined by atomic absorption spectrometry and was in good agreement with the enzyme inhibition data obtained with these samples.     

Physical and chemical characteristics of a metal-contaminated overbank deposit,west-central South Dakota,U.S.A.

A metal-contaminated overbank deposit in west-central South Dakota resulted from the discharge of a large volume of mine tailings into a river system between the late 1800s and 1977. The deposit along the Belle Fourche River is typically up to 2 m thick and extends about 90 m away from the channel along the insides of meander bends. The sediments contain above-background levels of copper, iron, manganese, zinc, and particularly arsenic, which is commonly two orders of magnitude above background level in the contaminated sediments. Carbonate minerals in the deposit limit the desorption of arsenic by preventing acid formation. Arsenic concentrations provide a measure of the dilution of mine tailings by uncontaminated sediment. The arsenic appears to have been transported and deposited as arsenopyrite, but is now at least partially associated with iron oxides and hydroxides. Within individual samples, arsenic concentration has an inverse relation with grain size that results from the more efficient accumulation of arsenic on the greater surface area of the smaller particles. Arsenic concentration is inversely related to the sample weight percent finer than 16 μm, however, as a consequence of the dilution of the contaminated sediments by uncontaminated sediment with a finer grain-size distribution. Dilution by uncontaminated sediment from tributaries cause arsenic concentrations to decrease by a factor of 3 along 100 km of floodplain. An influx at high streamflow of uncontaminated sediment from terraces and the premining floodplain as well as from tributaries causes arsenic concentrations in parts of the contaminated deposit that are farthest away from the channel to be two to three times less than arsenic concentrations in overbank sediment that is immediately adjacent to the channel.     

Floodplain storage of mine tailings in the belle fourche river system: A sediment budget approach

Arsenic-contaminated mine tailings that were discharged into Whitewood Creek at Lead, South Dakota, from 1876 to 1978, were deposited along the floodplains of Whitewood Creek and the Belle Fourche River. The resulting arsenic-contaminated floodplain deposit consists mostly of overbank sediments and filled abandoned meanders along White-wood Creek, and overbank and point-bar sediments along the Belle Fourche River. Arsenic concentrations of the contaminated sediments indicate the degree of dilution of mine tailings by uncontaminated alluvium. About 13 per cent of the 110 × 10⁶ Mg of mine tailings that were discharged at Lead were deposited along the Whitewood Creek floodplain. Deposition of mine tailings near the mouth of Whitewood Creek was augmented by an engineered structure. About 29 per cent of the mine tailings delivered by Whitewood Creek were deposited along the Belle Fourche River floodplain. About 60 per cent of that sediment is contained in overbank deposits. Deposition along a segment of the Belle Fourche River was augmented by rapid channel migration. The proportions of contaminated sediment stored along Whitewood Creek and the Belle Fourche River are consistent with sediment storage along the floodplains of perennial streams in other, similar sized watersheds.