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Eu(III)–Fulvic Acid Complexation: Evidence of Fulvic Acid Concentration Dependent Interactions by Time-Resolved Luminescence Spectroscopy

Yasmine Kouhail 1, 2 Marc F. Benedetti 2 Pascal E. Reiller 1, *
* Corresponding author
1 LANIE - Laboratoire de développement Analytique Nucléaire Isotopique et Elémentaire
SEARS - Service d'études analytiques et de réactivité des surfaces : DEN/DPC
Abstract : Europium speciation is investigated by time-resolved luminescence spectroscopy (TRLS) in the presence of Suwannee River fulvic acid (SRFA). From complexation isotherms built at different total Eu(III) concentrations, pH values, ionic strength, and SRFA concentrations, it appears that two luminescence behaviors of Eu(III) are occurring. The first part, at the lowest CSRFA values, is showing the typical luminescence evolution of Eu(III) complexed by humic substances—i.e. the increase of the asymmetry ratio between the 5 D0→ 7 F2 and 5 D0→ 7 F1 transitions up to a plateau—, and the occurrence of a bi-exponential decay—the first decay being faster than free Eu 3+. At higher CSRFA, a second luminescence mode is detected as the asymmetry ratio is increasing again after the previous plateau, and could correspond to the formation of another type of complex, and/or it can reflect a different spatial organization of complexed europium within the SRFA structure. The luminescence decay keeps on evolving but link to hydration number is not straightforward due to quenching mechanisms. The Eu(III) chemical environment evolution with CSRFA is also ionic strength dependent. These observations suggest that in addition to short range interactions—intra-particulate complexation—, there might be interactions at longer range—inter-particulate repulsion—between particles that are complexing Eu(III) at high CSRFA. These interactions are not yet accounted by the different complexation models.
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Yasmine Kouhail, Marc F. Benedetti, Pascal E. Reiller. Eu(III)–Fulvic Acid Complexation: Evidence of Fulvic Acid Concentration Dependent Interactions by Time-Resolved Luminescence Spectroscopy. Environmental Science & Technology, American Chemical Society, 2016, 50 (7), pp.3706-3716. ⟨10.1021/acs.est.5b05456⟩. ⟨cea-01299428⟩

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