A novel evaluation method for extrapolated retention factor in determination of n-octanol/water partition coefficient of halogenated organic pollutants by reversed-phase high performance liquid chromatography

Abstract: The retention factor corresponding to pure water in reversed-phase high performance liquid chromatography (RP-HPLC), k w , was commonly obtained by extrapolation of retention factor (k) in a mixture of organic modifier and water as mobile phase in tedious experiments. In this paper, a relationship between log k w and log k for directly determining k w has been proposed for the first time. With a satisfactory validation, the approach was confirmed to enable easy and accurate evaluation of k w for compounds in question with similar structure to model compounds. Eight PCB congeners with different degree of chlorination were selected as a training set for modeling the log k w −log k correlation on both silica-based C8 and C18 stationary phases to evaluate log k w of sample compounds including seven PCB, six PBB and eight PBDE congeners. These eight model PCBs were subsequently combined with seven structure-similar benzene derivatives possessing reliable experimental K ow values as a whole training set for log K ow −log k w regressions on the two stationary phases. Consequently, the evaluated log k w values of sample compounds were used to determine their log K ow by the derived log K ow −log k w models. The log K ow values obtained by these evaluated log k w were well comparable with those obtained by experimental-extrapolated log k w , demonstrating that the proposed method for log k w evaluation in this present study could be an effective means in lipophilicity study of environmental contaminants with numerous congeners. As a result, log K ow data of many PCBs, PBBs and PBDEs could be offered. These contaminants are considered to widely exist in the environment, but there have been no reliable experimental K ow data available yet. [Copyright &y& Elsevier]