Pathways and products of the degradation of PCBs by the sodium dispersion method

Noma, Y; Mitsuhara, Y; Matsuyama, K,; Sakai, S. (2007) Chemosphere, 68(5): 871-879

Nine polychlorinated biphenyl (PCB) congeners (2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 2,3,4-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl, 2,3',4,4',5-pentachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl, 2,2',4,4',5,5'-hexachlorobiphenyl, and decachlorobiphenyl) were dechlorinated by the sodium dispersion method (SID) at low temperature (60 degrees C). The dechlorination of 4-chlorobiphenyl was the fastest among the three monochlorobiphenyls. As for the other six congeners, we investigated the major dechlorination pathways. Although reaction selectivity was not very sensitive to the position of the chlorine substituent, the chlorines at the para position were slightly easier to dechlorinate than those at the ortho or meta positions. The decomposition rate increased with the total numbers of chlorine substituents. A chlorine situated between two other chlorines showed a high reactivity. When the numbers of chlorines on each of the phenyl rings were different, the reactions occurred on the more substituted ring. In the degradation of 4-chlorobiphenyl at elevated temperature (160 degrees C), we investigated the structures of the polymerized products and whether all the organic chlorinated compounds degraded finally or not. As for the dimers, p-quarterphenyl (QP) and mp-QP were detected but not o-QP, m-QP, o,p-QP, o,m-QP, or the mono- to tetra-chlorinated QPs. Compounds with a molecular weight of 534.4183 or 758.6713 were detected. They were considered to have C40H54 or C56H86 as their molecular formula. The compounds were most probably the polymerized products resulting from coupling of hexadecane or two hexadecanes and two phenylcyclohexadienes. It was thought the dechlorination and the polymerization were the main reactions. All of many detected compounds were hydrocarbons without chlorines, and no peaks originating from organic chlorinated compounds were observed by mass spectroscopic (XIS) methods.


degradation pathway; degradation rate; polymerized products; quarterphenyl; phenylcyclohexadiene; DECHLORINATION