pK(a) values of the monohydroxylated polychlorinated biphenyls (OH-PCBs), polybrominated biphenyls (OH-PBBs),...

The SPARC software program aqueous pK(a) prediction module was validated against corresponding experimental acidity constants for chlorinated and brominated phenols and the limited experimental aqueous pK(a) data sets for monohydroxylated polychlorinated biphenyls (OH-PCBs), polychlorinated diphenyl ethers (OH-PCDEs), and polybrominated diphenyl ethers (OH-PBDEs). pK(a) values were then estimated for all 837 monohydroxylated mono- through nona-halogenated congeners in each of the OH-PCB, OH-PCDE, and OH-PBDE classes, as well as for the monohydroxylated polybrominated biphenyls (OH-PBBs), giving a total of 3348 compounds. Large intrahomolog pK(a) variation by up to six units is expected within each contaminant class, with pK(a) values ranging from about 4 to 11 dependent on the degree and pattern of halogenation. Increasing halogenation generally decreased the average pK(a) within each homolog group. Significant intrahomolog differences in pK(a) values exist between OH-PCB, OH-PBB, OH-PCDE, and OH-PBDE congeners, including large acidity constant variation between isomers with equivalent halogenation patterns but varying location of the hydroxy moiety. Congener specific pH dependent investigations into the partitioning and degradation behaviors of these compounds are necessary, including greater consideration of analyte ionization effects during their extraction and analysis.