Use of molecular composition and compound-specific isotope analysis for source appointment of PAHs in sediments of a highly industrialized area

Abstract

This study utilized both conventional molecular analysis and compound-specific isotopic techniques to identify the sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of Ulsan Bay, South Korea. The concentrations of 15 traditional and 11 emerging PAHs were determined in sediments from 21 source sites and 26 bay sites. The concentrations and compositions of traditional and emerging PAHs varied significantly, even at sites close to the source areas. The results obtained from diagnostic ratios and the positive matrix factorization model for source identification were inconsistent in adjacent source areas. The δ¹³C profiles of PAHs, such as phenanthrene (Phe), fluoranthene (Fl), pyrene (Py), and benz[a]anthracene (BaA) in the sediments showed distinct features depending on the surrounding sources. In urban sediments, lighter δ¹³C_Phe values were observed (mean: -25.1‰), whereas relatively heavier values of δ¹³C_Py were found in petroleum industry areas (mean: -23.4‰). The Bayesian isotope mixing model indicates that the predominant source of PAHs in Ulsan Bay sediments was the petroleum industry (45%), followed by the non-ferrous metals industry (30%), automobile industry (18%), and urban areas (6.3%). These results demonstrated the utility of stable isotopes in assessing the sources and contributions of PAHs in small-scale regions. However, there are still limitations in compound-specific isotope analysis of PAHs, including insufficient end-members for each source, difficulty in analysis, and the influence of non-point sources; thus, further study is needed to expand its application.

Keywords: Bayesian isotope mixing model; Compound-specific isotope analysis; PMF model; Sediments; Source identification.