ABSTRACT
Polychlorinated dibenzo-p-dioxins and dibenzofurans in the sediments of aquatic systems are a persistent global problem that poses serious health risks. Identifying the sources of dioxins in natural water systems and the extent of their contributions to observed sediment concentrations is important from a health advisory and mitigation perspective. This paper proposes novel distribution-based qualitative and quantitative methods as source apportionment techniques and alternatives to conventional source attribution methods. Using sampled data, air, runoff, industrial effluent, and industrial paper and pulp wastes were identified as four distinct dioxin contributors to concentrations found in the sediments of the test bed region: the Houston Ship Channel-San Jacinto River-Galveston Bay (HSC-SJR-GB) estuarine system that also includes 2 Superfund sites with dioxin contamination. Two qualitative methods, the Kullback-Leibler divergence (K-L divergence) and the Bhattacharya measure (BM), and a quantitative method, the L2 norm, were used to investigate the spatial and temporal sourcing patterns of dioxins in the system sediments. The results indicated a global contribution from air and runoff sources across the estuarine system and over time with more localized impacts of the Superfund sites and the industrial sources. The results using the developed methodologies were compared with the output from the more conventional positive matrix factorization (PMF) method. Statistically significant correlations were observed among source contributions from the proposed methods and the PMF method, with Spearman's ρ ranging between - 0.596 to - 0.963 and 0.652 to 0.719, demonstrating the utility of the sourcing approaches used in the study. Additionally, the proposed methods were found to be rigorous in terms of elucidating spatial and temporal changes in the sourcing of dioxin to the estuary, indicating their suitability for use for other contaminants and other estuarine systems.
