Widespread Occurrence and Transport of p -Phenylenediamines and Their Quinones in Sediments across Urban Rivers, Estuaries, Coasts, and Deep-Sea Regions.

p -Phenylenediamines (PPDs) are widely used as antioxidants in tire rubber, and their derived quinone transformation products (PPD-Qs) may pose a threat to marine ecosystems. A compelling example is N -(1,3-dimethylbutyl)- N '-phenyl- p -phenylenediamine (6PPD)-derived quinone, called 6PPD-Q, as the causal toxicant for stormwater-linked acute mortality toward coho salmon. However, the knowledge of the co-occurrences of PPDs and PPD-Qs and their transport from freshwater to oceanic waterbodies on a large geographical scale remains unknown. Herein, we performed the first large-scale survey of these chemicals in sediments across urban rivers, estuaries, coasts, and deep-sea regions. Our results demonstrated that seven PPDs and four PPD-Qs are ubiquitously present in riverine, estuarine, and coastal sediments, and most of them also occur in deep-sea sediments. The most dominant chemicals of concern were identified as 6PPD and 6PPD-Q. Total sedimentary concentrations of PPDs and PPD-Qs presented a clear spatial trend with decreasing levels from urban rivers (medians: 39.7 and 15.2 ng/g) to estuaries (14.0 and 5.85 ng/g) and then toward coasts (9.47 and 2.97 ng/g) and deep-sea regions (5.24 and 3.96 ng/g). Interestingly, spatial variation in the ratios of 6PPD to 6PPD-Q ( R 6PPD/6PPD-Q ) also presented a clear decreasing trend. Our field measurements implied that riverine outflows of PPDs and PPD-Qs may be an important route to transport these tire rubber-derived chemicals to coastal and open oceans.