Biodegradation pathway and products of tire-related phenylenediamines and phenylenediamine quinones in solution – a laboratory study

IF 11.4 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Water Research Pub Date : 2025-07-15 DOI:10.1016/j.watres.2025.124235

Limei Han, Bettina Seiwert, Emily Lichtenwald, Steffen Weyrauch, Daniel Zahn, Thorsten Reemtsma

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Abstract

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 tentative 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.

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轮胎相关苯二胺和苯二胺醌在溶液中的生物降解途径和产物-实验室研究

对苯二胺（PPDs）是添加到轮胎中保护橡胶的抗氧化剂。它们是从轮胎和道路磨损颗粒（TRWP）中释放出来的，但它们的好氧微生物降解程度和形成的转化产物（TPs）尚不清楚。因此，对7种轮胎相关PPDs、母体化合物以及已知转化产物的好氧微生物降解进行了长达28天的研究。半衰期为0.2±0.1天（N-（1,3-二甲基丁基）-N′-苯基-1,4-苯二胺，6-PPD）和0.6±0.1天（N-（1,3-二甲基丁基）-N′-苯基-1,4-苯二胺醌，6-PPDQ）。采用液相色谱-高分辨率-质谱联用技术对7个化合物进行了初步鉴定，共鉴定出48个TPs。在这些TPs中，只有4种在母体化合物被完全降解后浓度没有下降。在水溶液中的生物转化会形成几种不为非生物、光解或氧化转化所知的TPs。对于具有脂肪取代基的ppd (6-PPD， IPPD)，水解为4-HDPA是主要的初始转化。未检测到6-PPD生成6-PPDQ。对于全芳香DPPD，好氧微生物转化可能是通过醌二亚胺中间体进行的，从而产生与脂肪族ppd不同的产物。从6-PPDQ中检测到26个TPs。对从生物降解实验中检测到的TPs进行了可疑筛选，筛选对象是使用TRWP和冷磨轮胎胎面（CMTT）进行的为期23个月的土壤退化研究数据，以及在降雨期间来自城市污水处理厂的进料和出水数据。在这些数据中共发现了10个不同强度的tp，其中大部分来自6-PPDQ。虽然所有七种测试化合物在有氧条件下（初级）降解，但没有研究矿化。在环境中仍有一些TPs作为嫌疑人有待搜索。

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来源期刊

Water Research 环境科学-工程：环境

CiteScore

20.80

自引率

9.40%

发文量

1307

审稿时长

38 days

期刊介绍： Water Research, along with its open access companion journal Water Research X, serves as a platform for publishing original research papers covering various aspects of the science and technology related to the anthropogenic water cycle, water quality, and its management worldwide. The audience targeted by the journal comprises biologists, chemical engineers, chemists, civil engineers, environmental engineers, limnologists, and microbiologists. The scope of the journal include: •Treatment processes for water and wastewaters (municipal, agricultural, industrial, and on-site treatment), including resource recovery and residuals management; •Urban hydrology including sewer systems, stormwater management, and green infrastructure; •Drinking water treatment and distribution; •Potable and non-potable water reuse; •Sanitation, public health, and risk assessment; •Anaerobic digestion, solid and hazardous waste management, including source characterization and the effects and control of leachates and gaseous emissions; •Contaminants (chemical, microbial, anthropogenic particles such as nanoparticles or microplastics) and related water quality sensing, monitoring, fate, and assessment; •Anthropogenic impacts on inland, tidal, coastal and urban waters, focusing on surface and ground waters, and point and non-point sources of pollution; •Environmental restoration, linked to surface water, groundwater and groundwater remediation; •Analysis of the interfaces between sediments and water, and between water and atmosphere, focusing specifically on anthropogenic impacts; •Mathematical modelling, systems analysis, machine learning, and beneficial use of big data related to the anthropogenic water cycle; •Socio-economic, policy, and regulations studies.