Reconstruction of historical 2,3,7,8-tetrachlorodibenzo-p-dioxin discharges from a former pesticide manufacturing plant to the Lower Passaic River.

Based on chemical fingerprinting and other lines of scientific evidence, a former pesticide manufacturing plant in Newark, New Jersey (U.S.A.) has been implicated in numerous journal articles as the major source of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the sediments of the Lower Passaic River (LPR). Although the site has been extensively studied for over three decades, no previous study has identified a pathway capable of discharging an amount of 2,3,7,8-TCDD comparable to the mass estimates made for 2,3,7,8-TCDD in the sediments of the LPR and Newark Bay, or examined the timing of specific manufacturing processes at the site in relation to 2,3,7,8-TCDD concentrations in dated sediment cores. A reconstruction of the historical operations at this site was performed, supporting it as the major source of 2,3,7,8-TCDD to the LPR. A 2,4,5-trichlorophenol purification process, utilized prior to September 1954, was specifically identified as a significant source of 2,3,7,8-TCDD to the LPR. This purification process generated a dioxin-rich sludge that was discharged to the river prior to September 1954. Annual 2,4,5-trichlorophenol production, coupled with modeling to predict concentrations of 2,3,7,8-TCDD, indicate that 2,3,7,8-TCDD discharges to the LPR from this one process (20-80 kg) are consistent with mass estimates of 2,3,7,8-TCDD in the river (30-50 kg). 2,3,7,8-TCDD and cesium-137 data from nearby sediment cores support this purification process as a major pathway by which 2,3,7,8-TCDD entered the river.

Halogenated indigo dyes: a likely source of 1,3,6,8-tetrabromocarbazole and some other halogenated carbazoles in the environment.

In recent years, a number of halogenated carbazoles have been detected in environmental samples. These emerging contaminants have been shown to be persistent and possess dioxin-like toxicological potential. The goal of this research was to examine the literature to determine likely anthropogenic origin(s) of halogenated carbazoles in the environment. The scientific literature indicated a number of pathways by which 1,3,6,8-tetrabromocarbazole could form in the manufacture of 5,5',7,7'-tetrabromoindigo. The U.S. production history of 5,5',7,7'-tetrabromoindigo correlates well with the concentration rise, decline, and disappearance of 1,3,6,8-tetrabromocarbazole in dated Lake Michigan sediments. Additionally, other halogenated carbazoles that have been found in environmental sediments can be explained by the production of other halogenated indigo dyes. 1,8-dibromo-3,6-dichlorocarbazole can be accounted for by the manufacture of 7,7'-dibromo-5,5'-dichloroindigo, while 1,3,6,8-tetrachlorocarbazole was found at relatively high concentration near the outfall of a U.S. manufacturer of 5,5',7,7'-tetrachloroindigo. Carbazoles containing an iodo-substituent can be explained by the use of iodine as a catalyst in the manufacture of halogenated indigo dyes. 3,6-Dichlorocarbazole measured in soils and dibromocarbazoles measured in more recently deposited sediments are not easily rationalized on the basis of an indigo related source and may be related to other anthropogenic sources or natural origins.

2,4,6,8-Tetrachlorodibenzothiophene in the Newark Bay Estuary: the likely source and reaction pathways.

Historic industrial activity along the Newark Bay Estuary has resulted in pollution from a number of contaminants; one of which is 2,4,6,8-tetrachlorodibenzothiophene (2,4,6,8-TCDT), a unique chemical contaminant whose origins have not been adequately explained. This research demonstrates that the probable source of 2,4,6,8-TCDT was the chlorination of phenol produced via the sulfonation method. Thiophenol, the major impurity in this type of phenol, was likely converted to 2,4,6,8-TCDT through one or more pathways during the production of 2,4-dichlorophenol, 2,4-dichlorophenoxyacetic acid (2,4-D), or 2,4,6-trichlorophenol. From a mass balance standpoint, production of these chemicals at an industrial plant along the Passaic River could account for the 2,4,6,8-TCDT in the Newark Bay Estuary.