Time Trends in Sources and Dechlorination Pathways of Dioxins in Agrochemically Contaminated Sediments

Although polychlorinated dibenzo-p-dioxins and dibezofurans (PCDD/Fs) are considered recalcitrant toward biotic and abiotic degradation processes, laboratory studies indicated lateral dechlorination pathways (removal of 2,3,7,8-substituted chlorines) as possible natural remediation strategies under highly reducing conditions prevailing in contaminated sediments. Previous principal component analysis (PCA) of PCDD/Fs in Japanese sediments left unidentified a factor characterized by penta- to octa- homologues fully chlorinated at 1,2,6,9-positions (1,2,6,9-pattern). In the present study, we reexamined PCDD/Fs in sediment cores from urban (Tokyo Bay) and remote (Lake Shinji) areas of Japan using positive matrix factorization (PMF) and revealed a lateral dechlorination fingerprint exhibiting the 1,2,6,9-pattern. Relative molar concentrations of putative lateral dechlorination products linearly increased with sediment depth, suggesting that decades of reaction resulted in the accumulation of hepta- and hexa- chlorinated lateral dechlorination products in the bottom sediment layers. Times required for in situ formation of dechlorination products were estimated to be at least 27.8 +/- 17.9 year(mole %)(-1) in Lake Shinji and 4.7 +/- 0.5 year(mole %)(-1) in Tokyo Bay (both for the formation of 1,2,3,4,6,7,9-HpCDD) and are significantly longer than the dechlorination pathways observed in the laboratory.