New insights in the slow ligand exchange reaction between Cr(III)-EDTA and Fe(III), and direct analysis of free and complexed EDTA in tannery wastewaters by liquid chromatography - Tandem mass spectrometry.

EDTA and soluble Cr(III) are usually both present in wastewaters coming from treatment plants handling tannery effluents. A well-established method to determine EDTA is based on the conversion of free and complexed EDTA into its Fe(III) complex. This procedure gives inconsistent data when Cr(III)-EDTA is present. This fact was here demonstrated by studying the kinetics of the exchange reaction between Fe(III) and Cr(III)-EDTA at 90 °C and various pH values, from acidic to neutral. The reaction is very slow (several weeks); the slow kinetics of conversion of Cr(III)-EDTA to Fe(III)-EDTA is even more accentuated at room temperature and the low concentrations of reactants in wastewaters. The presence of EDTA complexes of Fe(III) and Cr(III) was demonstrated in industrial effluents and wastewaters by developing a selective method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS), which was able to detect free and complexed EDTA at concentration levels <1 µM. A systematic underestimation of the EDTA expressed as Fe(III) complex was demonstrated in samples containing Cr(III)-EDTA. Cr(III)-EDTA was identified for the first time as a component of wastewater samples at a concentration level of about 2 µM and turned out to be an inert species that significantly contributes to the final soluble Cr amount. This study gives new insights into the inertness of Cr(III) toward metal exchange equilibria of EDTA complexes, resolves a bias in the analysis of total EDTA in samples containing Cr(III)-EDTA, allowing the direct determination of free and complexed EDTA by LC-MS.

Chromium removal from a real tanning effluent by autochthonous and allochthonous fungi.

Heavy metals represent an important ecological and health hazard due to their toxic effects and their accumulation throughout the food chain. Conventional techniques commonly applied to recover chromium from tanning wastewaters have several disadvantages whereas biosorption has good metal removal performance from large volume of effluents. To date most studies about chromium biosorption have been performed on simulated effluents bypassing the problems due to organic or inorganic ligands present in real industrial wastewaters that may sequestrate the Cr(III) ions. In the present study a tanning effluent was characterized from a mycological point of view and different fungal biomasses were tested for the removal of Cr(III) from the same tanning effluent in which, after the conventional treatments, Cr(III) amount was very low but not enough to guarantee the good quality of the receptor water river. The experiments gave rise to promising results with a percentage of removed Cr(III) up to 40%. Moreover, to elucidate the mechanisms involved in biosorption process, the same biomasses were tested for Cr(III) removal from synthetic aqueous solutions at different Cr(III) concentrations.