Physicochemical and biological characterisation of different dredged sediment deposit sites in France

A cross-disciplinary research project has been implemented because of increased awareness of the potential environmental effects caused by dispersion of metals from external applications into the environment. The work comprises a 4-year (1998-2002) field exposure of grades 304 and 316 stainless steels, and a laboratory percolation study simulating 20-25 years of chromium and nickel containing runoff water interactions with soil. Total metal annual release rates varied between 0.2 and 0.7 mg m-² yr-¹ for Cr, between 0.1 and 0.8 mg m-² yr-¹ for Ni and between 10 and 200 mg m-² yr-¹ for Fe. Most Cr and Ni is present in an ionic form as a result of the limited presence of organic matter at the immediate release situation. Metal ion concentrations in the runoff water are far below reported ecotoxic concentrations. Studies of the environmental interaction between runoff water from stainless steel and soil show the majority of released Cr and Ni to be retained and their concentrations in percolation water to be very low (0.5-1 μg L-¹ and 1-5.5 μg L-¹ for Cr and Ni, respectively). Speciation calculations showed Cr to be primarily complexed to dissolved organic carbon while Ni also was present in an ionic form in the solution phase. Soil extractions showed Cr and Ni to be very strongly retained within the soil.

Microorganisms are responsible for the bulk of transformations that occur in surficial sediments. They are most active at redox boundaries where they can benefit from access to various oxidants and reductants generated during redox cycling events. To illustrate the dynamics of microbially mediated processes, especially those involving sulfur and metal cycles, processes were compared in habitats either bioturbated by a capitellid worm or inhabited by a salt marsh grass. The presence of macrofauna and macroflora greatly altered the three-dimensional array of redox gradients in sediments, but the type and form of reductants and oxidants provided varied greatly; clastic sedimentary infauna subducted solid phase organic material and iron oxides, whereas plant roots released dissolved organic matter and oxygen. These differences resulted in a bioturbated system that exhibited a rapid sulfur cycle (residence time of minutes), but a slower iron cycle (days), whereas vegetation caused a slow sulfur cycle and rapid iron cycle. Alteration of sediments by higher life forms also greatly affected the composition and relative abundances of sedimentary bacteria, even on short time scales. Although redox cycling at interfaces can be somewhat predictable, variations in response to biological and physical perturbations demonstrated wide differences in the dynamics of redox-mediated processes.

The feasibility of degrading 16 USEPA priority polycyclic aromatic (PAH) hydrocarbons (PAHs) with heat and Fe(II)-EDTA catalyzed persulfate oxidation was investigated in the laboratory. The experiments were conducted to determine the effects of temperature (i.e. 20 [composite function (small circle)]C, 30 [composite function (small circle)]C and 40 [composite function (small circle)] C) and iron-chelate levels (i.e., 250 mg/L-, 375 mg/L- and 500 mg/L-Fe(II)) on the degradation of dissolved PAHs in aqueous systems, using a series of amber glass jars as the reactors that were placed on a shaker inside an incubator for temperature control. Each experiment was run in duplicate and had two controls (i.e., no persulfate in systems). Samples were collected after a reaction period of 144 hrs and measured for PAHs, pH and sodium persulfate levels. The extent of degradation of PAHs was determined by comparing the data for samples with the controls. The experimental results showed that persulfate oxidation under each of the tested conditions effectively degraded the 16 target PAHs. All of the targeted PAHs were degraded to below the instrument detection limits (~4 μ/L) from a range of initial concentration (i.e., 5 μ/L for benzo(a)pyrene to 57 μ/L for Phenanthrene) within 144 hrs with 5 g/L of sodium persulfate at 20 [composite function (small circle)] C, 30 [composite function (small circle)]C and 40 [composite function (small circle)]C. The data indicated that the persulfate oxidation was effective in degrading the PAHs and that external heat and iron catalysts might not be needed for the degradation of PAHs. The Fe(II)-EDTA catalyzed persulfate also effectively degraded PAHs in the study. In addition, the data on the variation of persulfate concentrations during the experiments indicated that Fe(II)-EDTA accelerated the consumption of persulfate ions. The obtained degradation data cannot be used to evaluate the influence of temperature and Fe(II) levels on the PAH degradation because the PAHs under each of the tested conditions were degraded to below the instrument detection limit within the first sampling point. However, these experiments have demonstrated the feasibility of degrading PAHs in aqueous systems with persulfate oxidation. Additional tests are being conducted to evaluate the effectiveness of treating PAHs in soils and obtaining the rate of degradation of PAHs with persulfate oxidation. Two sets of laboratory experiments were conducted to evaluate the ability of sodium persulfate in oxidizing real world PAH-contaminated soils collected from a Superfund site in Connecticut. The first set of soil sample were treated only with persulfate and to the second batch, mixture of persulfate and Fe(II)-EDTA solutions were added. The results of the second test showed that within 24 hours, 75% to 100% of the initial concentrations of seven PAH compounds detected in the soil samples were degraded by sodium persulfate mixed with FE(II)-EDTA.