Comparison of EDTA and EDDS as potential soil amendments for enhanced phytoextraction of heavy metals

Phytoextraction has been proposed as an alternative remediation technology for soils polluted with heavy metals or radionuclides, but is generally conceived as too slow working. Enhancing the accumulation of trace pollutants in harvestable plant tissues is a prerequisite for the technology to be practically applicable. The chelating aminopolycarboxylic acid, ethylene diamine tetraacetate (EDTA), has been found to enhance shoot accumulation of heavy metals. However, the use of EDTA in phytoextraction may not be suitable due to its high environmental persistence, which may lead to groundwater contamination. This paper aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposes. A laboratory experiment was conducted to examine mobilisation of Cd, Cu, Cr, Ni, Pb and Zn into the soil solution upon application of EDTA or EDDS. The longevity of the induced mobilisation was monitored for a period of 40 days after application. Estimated effect half lives ranged between 3.8 and 7.5 days for EDDS, depending on the applied dose. The minimum observed effect half life of EDTA was 36 days, while for the highest applied dose no decrease was observed throughout the 40 day period of the mobilisation experiment. Performance of EDTA and EDDS for phytoextraction was evaluated by application to Helianthus annuus. Two other potential chelators, known for their biodegradability in comparison to EDTA, were tested in the plant experiment: nitrilo acetic acid (NTA) and citric acid. Uptake of heavy metals was higher in EDDS-treated pots than in EDTA-treated pots. The effects were still considered insufficiently high to consider efficient remediation. This may be partly due to the choice of timing for application of the soil amendment. Fixing the time of application at an earlier point before harvest may yield better results. NTA and citric acid induced no significant effects on heavy metal uptake.     

The effect of hydrological regime on the metal bioavailability for the wetland plant species Salix cinerea

The hydrological conditions on a site constitute one of the many factors that may affect the availability of potentially toxic trace metals for uptake by plants. Bioavailability of Cd, Mn and Zn in a contaminated dredged sediment-derived soil under different hydrological regimes was determined by measuring metal uptake by the wetland plant species Salix cinerea, both in field circumstances and in a greenhouse experiment. Longer submersion periods in the field caused lower Cd concentrations in leaves and bark. The wetland hydrological regime in the greenhouse experiment resulted in normal Cd and Zn concentrations in the leaves, while the upland hydrological regime resulted in elevated Cd and Zn concentrations in the leaves. Field observations and the greenhouse experiment suggest that a hydrological regime that creates or sustains a wetland is a potential management option that reduces metal bioavailability to willows. This would constitute a safe management option of metal-polluted, willow-dominated wetlands provided that wetland conditions can be maintained throughout the full growing season.     

Storage mediums affect metal concentration in woodlice (Isopoda)

Terrestrial invertebrates are becoming widely established as tools to assess heavy metal pollution at contaminated sites. A practical and time saving method to sample terrestrial invertebrates consist of pitfall traps, often filled with a 4% formaldehyde solution and some detergent. The reliability of metal concentrations based on organisms captured and stored in this solution might however be questioned and we therefore tested the effect of formaldehyde on Zn, Cu, Cd and Pb concentration experimentally in three isopod species. Our results showed that in many cases, significant decreases in Cu concentrations compared to animals stored in a freezer were observed that could be as high as 40%, while Zn, Cd and Pb concentrations increased. A regression analysis of individual dry weight on individual size revealed that formaldehyde decreases the dry weight substantially and in that way causes increased measurements of Zn, Cd and Pb concentrations. We conclude that pitfall traps with formaldehyde should better not be used to collect animals in which concentrations of heavy metals or other toxic substances will be determined.     

Mercury baseline levels in Flemish soils (Belgium)

It is important to establish contaminant levels that are normally present in soils to provide baseline data for pollution studies. Mercury is a toxic element of concern. This study was aimed at assessing baseline mercury levels in soils in Flanders. In a previous study, mercury contents in soils in Oost-Vlaanderen were found to be significantly above levels reported elsewhere. For the current study, observations were extended over two more provinces, West-Vlaanderen and Antwerpen. Ranges of soil Hg contents were distinctly higher in the province Oost-Vlaanderen (interquartile range from 0.09 to 0.43 mg/kg) than in the other provinces (interquartile ranges from 0.7 to 0.13 and 0.7 to 0.15 mg/kg for West-Vlaanderen and Antwerpen, respectively). The standard threshold method was applied to separate soils containing baseline levels of Hg from the data. Baseline concentrations for Hg were characterised by a median of 0.10mg Hg/kg dry soil, an interquartile range from 0.07 to 0.14 mg/kg and a 90% percentile value of 0.30 mg/kg. The influence of soil properties such as clay and organic carbon contents, and pH on baseline Hg concentrations was not important. Maps of the spatial distribution of Hg levels showed that the province Oost-Vlaanderen exhibited zones with systematically higher Hg soil contents. This may be related to the former presence of many small-scale industries employing mercury in that region.     

Metal solubility as a function of pH in a contaminated, dredged sediment affected by oxidation

The solubility as a function of pH for metals in a reduced dredged sediment, subjected to different redox conditions, was studied in a laboratory experiment. The redox conditions imposed simulated (i) the undisturbed sediment (flooded), (ii) a dredged material stored in a confined pond (aerated once and then flooded), (iii) an upland stored dredged material (drained and dried), and (iv) an upland stored sediment subjected to tillage (drained, dried and mixed). Minor differences in the solubility as a function of pH were observed between the treatments after two weeks. After three months, the solubility of Cd, Cu, Pb and Zn increased strongly in the oxidized sediments. Leachability of Fe decreased, while Mn, Ni and Co were mostly unaffected. Both short- and long-term mobility of metals (except Fe) is expected to be lowest when a reduced sediment remains in reduced conditions. Studying the solubility as a function of pH may provide additional information on the chemical association of metals in sediments.     

The potential of foliar treatments for enhanced phytoextraction of heavy metals from contaminated soil

Phytoextraction is the plant‐based removal of inorganic contaminants from the soil by root absorption and subsequent translocation to harvestable plant parts. The efficiency of this technique is limited by the phytoavailability of these contaminants in the soil and the root‐to‐shoot transport. To enhance the phytoextraction efficiency, the use of soil amendments has been widely investigated. Potential risks such as increased ecotoxicological effects and leaching of mobilized contaminants caution against the use of persistent mobilizing agents. The potential use of foliar amendments to enhance mineral absorption and/or translocation offers prospects for complementing or substituting soil amendments for enhanced phytoextraction purposes. This study presents an explorative screening to evaluate the feasibility of this approach. Helianthus annuus giganteus plants were grown in moderately contaminated dredged sediment for ten weeks, with daily foliar treatments from week six onward: (1) distilled water (control), (2) magnesium‐ethylenediaminetetraacetic acid (Mg‐EDTA), (3) diethylenetriaminepentaacetic acid (DTPA), (4) nitrilotriacetic acid (NTA), (5) citric acid, (6) oxalic acid, (7) calcium acetate, (8) ammonium thiocyanate (NH₄SCN), and (9) cystein. Applied doses varied between treatments based on plant tolerance: 15 μmol per plant for cystein, 60 μmol per plant for DTPA and NH₄SCN, 180 μmol per plant for Mg‐EDTA and NTA and 400 μmol per plant for the organic acids. At the end of the experiment, shoot accumulation of cadmium, chromium, copper, iron, manganese, nickel, lead, and zinc was evaluated. © 2004 Wiley Periodicals, Inc.     

Metals in marine environment (mollusc Patella sp., fish Labrus bergylta, crustacean Cancer pagurus, beach sand) in a nuclear area, the North Cotentin (France)

The results of a 1-year long survey of trace metals concentrations (Al, Cd, Cr, Co, Cu, Fe, Mn, Hg, Ni, Pb, Zn) measured in beach sand, limpets and, occasionally, in fish and shellfish from the North Cotentin area (France), where nuclear industries are implanted, are presented. The objective of these study was to provide useful data for the validation of models predicting the impact of these industries on the marine environment. Even if differences were noted between sites for various metals, the levels are consistent with existing data published for similar site and do not appear to give evidence of contamination by industrial sites.     

Diffusive gradient in thin FILMS (DGT) compared with soil solution and labile uranium fraction for predicting uranium bioavailability to ryegrass

The usefulness of uranium concentration in soil solution or recovered by selective extraction as unequivocal bioavailability indices for uranium uptake by plants is still unclear. The aim of the present study was to test if the uranium concentration measured by the diffusive gradient in thin films (DGT) technique is a relevant substitute for plant uranium availability in comparison to uranium concentration in the soil solution or uranium recovered by ammonium acetate. Ryegrass (Lolium perenne L. var. Melvina) is grown in greenhouse on a range of uranium spiked soils. The DGT-recovered uranium concentration (C_DGT) was correlated with uranium concentration in the soil solution or with uranium recovered by ammonium acetate extraction. Plant uptake was better predicted by the summed soil solution concentrations of UO₂²⁺, uranyl carbonate complexes and UO₂PO₄⁻. The DGT technique did not provide significant advantages over conventional methods to predict uranium uptake by plants.     

Cu sorption on Phragmites australis leaf and stem litter: a kinetic study

Decaying organic matter plays an important role in the cycling of metals in wetland ecosystems. Sorption kinetics of Cu(II) on Phragmites australis leaf and stem litter were studied. Fresh leaf and stem litter was sampled from a surface flow wetland at the end of the growing season. The effect of decomposition stage was studied with litter that had been decomposing for a period of 5 months. The Lagergren pseudo-first-order model, the pseudo-second-order model, the Elovich equation and two diffusion models based on spherical intra-particle diffusion were fitted to the experimental data. The sorption capacity was significantly affected by the decomposition of the litter. The sorption process was best described by the pseudo-second-order kinetics (R(2) approximately 0.99) but the rate constant was strongly dependent on the initial Cu concentration. The intra-particle diffusion model fitted the data only slightly less (R(2)>0.95) than the pseudo-second-order model. A theoretical comparison revealed that the good fit with the pseudo-second-order kinetics could be indicative of intra-particle diffusion. Sorption kinetics observed for the leaf and stem litter at different metal concentrations showed a fast initial sorption followed by a slow sorption phase.