Biodegradation pathways and products of tire-related phenylenediamines and phenylenediamine quinones in solution - a laboratory study.

Para-phenylenediamines (PPDs) are antioxidants added to tires to protect the rubber. They are released from tire and road wear particles (TRWP) but the extent of their aerobic microbial degradation and the transformation products (TPs) formed are not known. Therefore, aerobic microbial degradation of seven tire-related PPDs, parent compounds as well as known transformation products, was studied for up to 28 days. Half-lives ranged from 0.2 ± 0.1 days (N-(1,3-dimethylbutyl)-N'-phenyl-1,4-benzenediamine, 6-PPD) and 0.6 ± 0.1 days (N-isopropyl-N'-phenyl-1,4-phenylenediamine, IPPD) to 3 ± 0.1 days (N-(1,3-dimethylbutyl)-N'-phenyl-1,4-benzenediamine quinone, 6-PPDQ). A total number of 48 TPs was tentatively identified by liquid chromatography-high resolution-mass spectrometry for the seven study compounds. Of these TPs, only four did not decrease in concentration when the parent compounds were degraded completely. Biotransformation in aqueous solution forms several TPs not known for abiotic, photolytic or oxidative transformation. For the PPDs with aliphatic substituents (6-PPD, IPPD) hydrolysis to 4-HDPA was the major initial transformation. Formation of 6-PPDQ from 6-PPD was not detectable. For the fully aromatic DPPD aerobic microbial transformation, likely, proceeded via a quinone diimine intermediate, leading to products different to those of the aliphatic PPDs. From 6-PPDQ, 26 TPs were detected. A suspect screening for the TPs detected from the biodegradation experiments was performed in data of a soil degradation study over 23 months with TRWP and cryo-milled tire tread (CMTT) and in data from the influent and effluent of a municipal wastewater treatment plant during a rain event. In total, 10 TPs were found in those data with variable intensities, most of which originated from 6-PPDQ. While all seven test compounds were (primary) degraded under aerobic conditions, mineralization was not studied. A number of TPs remain as suspects to search for in the environment.