Salt marsh plants (Juncus maritimus and Scirpus maritimus) as sources of strong complexing ligands

This work aimed to evaluate, in vitro, the capability of roots of salt marsh plants to release strong Cu-complexing ligands and to ascertain whether Cu contamination would stimulate ligands' exudation or not. The sea rush Juncus maritimus and the sea-club rush Scirpus maritimus, both from the lower Douro river estuary (NW Portugal), were used. Plants were collected seasonally, four times a year in 2004, during low tide. After sampling, plant roots were washed for removal of adherent particles and immersed for 2 h in a solution that matched salinity (3) and pH (7.5) of the pore water from the same location and spiked with Cu²⁺ in the range 0–1600 nM to obtain plant exudates. In the final solutions as well as in sediment pore water total dissolved Zn and Cu, Cu-complexing ligand concentrations and the respective conditional stability constants (K_CuL^′) values were determined by voltammetry. This study demonstrated that plants are able to release, in a short period of time, relatively high amounts of strong Cu-complexing ligands (56–265 nmol g_root⁻¹), which differed among plants and sampling site but were independent of the season. Cu contamination did not stimulate exudation of Cu-complexing ligands. On the other hand, in media contaminated with Cu both plants accumulated relatively high amounts (29–83%) of the initially dissolved Cu, indicating that they have alternative internal mechanisms for Cu detoxification. Cu exchange between roots and medium (either accumulation in contaminated medium or release in the absence of Cu) was more intense for S. maritimus than for J. maritimus. It was observed that exudate solutions obtained in the absence of added Cu and sediment pore water (the densities of roots observed inside the salt marsh where comparable to those used in the in vitro experiments), displayed similarities in terms of total dissolved metals, Cu-complexing ligands concentrations, values of K_CuL^′ (12 < log K_CuL^′ < 14), as well as patterns of variation among seasons (only observed for Zn). These results are novel and point out that salt marsh plants may be the source at least partially of the strong organic ligands found in the sediment pore water in shallow marginal areas. The capability of salt marsh plants to release strong organic ligands into the environment, conjugated with their known capacity to oxidize anaerobic sediment around roots, indicate that these plants can play a role in controlling metal speciation in the water/sediment interface.