Carbon isotopic fractionation during biodegradation of phthalate esters in anoxic condition

Here we evaluate the quantitative relationship between carbon isotopic fractionation and anoxic biodegradation of phthalate esters (PAEs), a kind of endocrine disruptors. The stable carbon isotope delta values (δ(13)C) of 4 PAEs, i.e. di-methyl phthalate (DMP), di-ethyl phthalate (DEP), di-n-butyl phthalate (DBP), and di-iso-butyl phthalate (DiBP), were analyzed during biodegradation by a pure bacteria strain isolated from the shallow aquifer sediment in anoxic condition. Results showed that the carbon isotopic fractionation in the initial degradation of PAEs was well-described by the Rayleigh equation model with R(2) from 0.8885 to 0.9821. The carbon isotopic fractionation (ε) for DMP and DEP were -4.6±0.4‰ and -2.9±0.1‰, respectively, while DBP and DiBP showed limited isotopic fractionation. A linear relationship between ε values and the total carbon atoms present in straight-carbon-chain PAE molecules with R(2) of 0.9918. The apparent kinetic isotope effects (AKIEs) were calculated for proposed 4 initial transformation pathways of PAEs. The high carbon AKIEs of 1.048 and 1.036 were obtained for single enzymatic hydrolysis of DMP and DEP, respectively, and fell in the expected KIE range of 1.03-1.09. However, the intrinsic carbon isotope effects for enzymatic hydrolysis of DBP and DiBP might be masked.