Characterization of how contaminants arise in a dredged marine sediment and analysis of the effect of natural weathering.

Millions of tons of contaminated sediments are dredged each year from the main harbors in France. When removed from water, these sediments are very reactive, therefore their geochemical behavior must be understood in order to avoid dispersion of contaminated lixiviates in the surrounding soils. In this objective, it is necessary to evaluate the principal physicochemical parameters, and also achieve advanced mineralogical characterization. These studied sediments are highly contaminated by metals, notably copper (1445 and 835mg/kg, in the unweathered and naturally-weathered sediments, respectively), lead (760 and 1260mg/kg, respectively), zinc (2085 and 2550mg/kg, respectively), as well as by organic contaminants (PAH, PCB) and organometallics (organotins). A high concentration of sulfide minerals was also observed both in the unweathered sediment preserved under water (3.4wt% of pyrite especially), and in the naturally weathered sediment (2wt% pyrite), and in particular framboïdal pyrite was observed in the two materials. The presence of reactive mineral species in the naturally-weathered sediment can be explained by the deposit of a protective layer, composed of sulfide and their oxidation products (sulfate and iron oxides), thus preventing oxygen from diffusing through to the sulfide minerals. Additionally, the presence of aluminosilicates aggregates coating the sulfide minerals could also explain their presence in the naturally-weathered sediment. As organic matter is one of the principal constituents of the sediments (5.8 and 6.3wt% total organic carbon in the unweathered and weathered sediment, respectively), the aggregates are probably partially constituted of refractory humic material. It therefore appears that the natural weathering has led to a significant decrease in PAHs and organotins, but not in PCBs. The evolution of the granulometric structure and the distribution of the metallic contaminants could therefore lead us to consider a treatment by size separation, and a possible valorization of the dredged sediments in civil engineering.

Environmental evaluation of dredged sediment submitted to a solidification stabilization process using hydraulic binders.

PURPOSE: Dredging of sediments, a requirement for harbor maintenance, removes millions of tons of mineral wastes, contaminated at varying degrees with trace metals, from the water. In previous investigations, Cu and Zn have been identified as highly concentrated trace metals associated to sulfides, mineral phases sensitive to oxidation. In order to ensure their sustainable management, the solidification/stabilization (S/S) and/or the valorization of contaminated sediments as secondary raw materials is a way to be promoted. Indeed, their reuse as a substitute of sand in cemented mortar formulation would allow combining both treatment and valorization of such wastes. METHODS: In the present study, the environmental assessment of mortars formulated with raw and weathered marine sediments (in particular contaminated with Cu, Pb and Zn), compared to sand reference mortars, was conducted through two kinetic leaching tests: weathering cell tests (WCTs), in which mortars were crushed and leached twice a week, and a tank monolith leaching test (MLT), in which leaching was performed on monolithic mortars with increasing leachate renewal time. RESULTS: In both leaching tests, calcium and sulfur were released continuously from sediment mortars, showing the oxidation-neutralization processes of sulfides and carbonates. In the MLT, Cu was released by sediment mortars through diffusion, particularly by weathered mortars, at low concentrations during 60 days of the test duration. With the more aggressive WCT, Cu concentrations were higher at the beginning but became negligible after 7 days of testing. Pb was released through diffusion mechanisms until depletion in both tests, whereas Zn was particularly well immobilized in the cemented matrices. CONCLUSIONS: The S/S process applied using hydraulic binders proved to be efficient in the stabilization of Cu, Pb, and Zn highly presents in studied sediments, and further valorization in civilian engineering applications could be considered.

An innovative coupling between column leaching and oxygen consumption tests to assess behavior of contaminated marine dredged sediments.

Contaminated dredged sediments are often considered hazardous wastes, so they have to be adequately managed to avoid leaching of pollutants. The mobility of inorganic contaminants is a major concern. Metal sulfides (mainly framboïdal pyrite, copper, and zinc sulfides) have been investigated in this study as an important reactive metal-bearing phase sensitive to atmospheric oxygen action. An oxygen consumption test (OC-Test) has been adapted to assess the reactivity of dredged sediments when exposed to atmospheric oxygen. An experimental column set-up has been developed allowing the coupling between leaching and oxygen consumption test to investigate the reactivity of the sediment. This reactivity, which consisted of sulfide oxidation, was found to occur for saturation degree between 60 and 90 % and until the 20th testing week, through significant sulfates releases. These latter were assumed to come from sulfide oxidation in the first step of the test, then probably from gypsum dissolution. Confrontation results of OC-Test and leachate quality shows that Cu was well correlated to sulfates releases, which in turn, leads to Ca and Mg dissolution (buffer effect). Cu, and mostly Zn, was associated to organic matter, phyllosilicates, and other minerals through organo-clay complexes. This research confirmed that the OC-Test, originally developed for mine tailings, could be a useful tool in the dredged sediment field which can allow for intrinsic characterization of reactivity of a material suspected to readily reacting with oxygen and for better understanding of geochemical processes that affect pollutants behavior, conversion, and transfer in the environment.