Fluorescence Quenching and Energy Transfer Phenomena Associated with the Interactions of Terbium Ion and Humic Acid

Abstract

Fluorescence of the hydrophobic acid fraction (HPOA) of Suwannee River natural organic matter and Tb³⁺ excitation spectra were measured in tandem using the instantaneous and time-resolved emission modes. The intensity of HPOA fluorescence decreased in the presence of Tb³⁺, while the intensity of the emission from Tb³⁺ cations bound by HPOA increased by up to several orders of magnitude due to energy transfer (ET) from HPOA to Tb³⁺ ions. To determine intrinsic ET and fluorescence quenching (FQ) coefficients, NICA–Donnan modeling was carried. It showed that phenolic groups in HPOA dominated both the ET and FQ processes and that the binding of Tb³⁺ by HPOA could be described using the non-ideality parameter n_Tb, median binding constant log \(\tilde{K}_{\text{Tb}}\) for the phenolic sites and intrinsic ET and FQ coefficients (denoted as η_TbΦ and α_TbΦ), and were 0.48, 8.5, 1385 and 0.12, respectively. The high value of the energy transfer coefficient of Tb³⁺ ions bound by the phenolic groups in HPOA is indicative of both the match between the electronic levels of the donor and acceptor, and the short distance between them. The deviation of the data of Nica–Donnan modeling of the ET and FQ dependence of versus [Tb]_total for a 1.0?M ionic strength highlights the need to quantify the distribution of donor–acceptor distances in HPOA molecules in more detail.