Transformation Products of Tire Rubber Antioxidant 6PPD in Heterogeneous Gas-Phase Ozonation: Identification and Environmental Occurrence.

6PPD, a tire rubber antioxidant, poses substantial ecological risks because it can form a highly toxic quinone transformation product (TP), 6PPD-quinone (6PPDQ), during exposure to gas-phase ozone. Important data gaps exist regarding the structures, reaction mechanisms, and environmental occurrence of TPs from 6PPD ozonation. To address these data gaps, gas-phase ozonation of 6PPD was conducted over 24-168 h and ozonation TPs were characterized using high-resolution mass spectrometry. The probable structures were proposed for 23 TPs with 5 subsequently standard-verified. Consistent with prior findings, 6PPDQ (C18H22N2O2) was one of the major TPs in 6PPD ozonation (∼1 to 19% yield). Notably, 6PPDQ was not observed during ozonation of 6QDI (N-(1,3-dimethylbutyl)-N'-phenyl-p-quinonediimine), indicating that 6PPDQ formation does not proceed through 6QDI or associated 6QDI TPs. Other major 6PPD TPs included multiple C18H22N2O and C18H22N2O2 isomers, with presumptive N-oxide, N,N'-dioxide, and orthoquinone structures. Standard-verified TPs were quantified in roadway-impacted environmental samples, with total concentrations of 130 ± 3.2 µg/g in methanol extracts of tire tread wear particles (TWPs), 34 ± 4 µg/g-TWP in aqueous TWP leachates, 2700 ± 1500 ng/L in roadway runoff, and 1900 ± 1200 ng/L in roadway-impacted creeks. These data demonstrate that 6PPD TPs are likely an important and ubiquitous class of contaminants in roadway-impacted environments.

Biotransformation of Current-Use Progestin Dienogest and Drospirenone in Laboratory-Scale Activated Sludge Systems Forms High-Yield Products with Altered Endocrine Activity.

Dienogest (DIE) and drospirenone (DRO) are two fourth-generation synthetic progestins widely used as oral contraceptives. Despite their increasing detection in wastewaters and surface waters, their fate during biological wastewater treatment is unclear. Here, we investigated DIE and DRO biotransformation with representative activated sludge batch incubations and identified relevant transformation products (TPs) using high-resolution mass spectrometry. DIE exhibited slow biotransformation (16-30 h half-life) and proceeded through a quantitative aromatic dehydrogenation to form TP 309 (molar yields of ∼55%), an aromatic TP ∼30% estrogenic as 17ß-estradiol. DRO experienced more rapid biotransformation (<0.5 h half-life), and 1,2-dehydrogenation formed the major TP 364 (molar yields of ∼40%), an antimineralocorticoid drug candidate named as spirorenone. Lactone ring hydrolysis was another important biotransformation pathway for DRO (molar yields of ∼20%) and generated pharmacologically inactive TP 384. Other minor pathways for DIE and DRO included hydroxylation, methoxylation, and 3-keto and C4(5) double-bond hydrogenation; distinct bioactivities are plausible for such TPs, including antigestagenic activity, antigonadotropic activity, and pregnancy inhibition effects. Thus, biotransformation products of DIE and DRO during wastewater treatment should be considered in environmental assessments of synthetic progestins, especially certain TPs such as the estrogenic TP 309 of DIE and the antimineralocorticoid spirorenone (TP 364) of DRO.