Slopes and intercepts from log-log correlations of gas/particle quotient and octanol-air partition coefficient (vapor-pressure) for semi-volatile organic compounds: II. Theoretical predictions vs. monitoring

The logarithm of gas/particle (G/P) partition quotient (logK_P) has been found to have a linear relationship with logK_OA (octanol-air partition coefficient) with slope m_o and intercept b_o and logP_L (subcooled liquid vapor pressure) with slope m_p and intercept b_p. In the sister paper of the present work, analytical equations to predict the slope m_o and intercept b_o based on logK_OA and predict the slope m_p and intercept b_p based on logP_L are developed using steady state theory. In this work, the equations are evaluated using world-wide monitoring data (262 pairs for m_o and b_o values and 292 pairs for m_p and b_p values produced from more than 10,000 monitiring data worldwide) for selected seven groups of semi-volatile organic compounds (SVOCs), including polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins and polychorinated dibenzofurans (PCDD/Fs), polyclorinated biphenyl (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated naphthalenes (PCNs), organochlorinated pesticides (OCPs), novel brominated flame retardants (NBFRs), and other selected halogenated flame retardants. The slopes and intercepts predicted by the steady state equations reproduce the trends observed in monitoring regression results for the seven SVOC groups, with 44.4% of the variation of monitoring m_o values accounted for by logK_OA and 48.2% of the variation of monitoring m_p values accounted for by logP_L. Theoretically, the values of m_o can be any value between 0 and 1 dependent on the values of K_OA, and are not constrained to 1 as in equilibrium theory. Likewise, the values of m_p can be any value between 0 and -1 dependent on the values of P_L, and not constrained to −1 predicted by the equilibrium theory. The influence of sampling artifacts on the G/P partitioning of SVOCs has most likely been overemphasized by the equilibrium theory. Thus, the equilibrium approach should be abandoned in favor of the steady state approach for calculating the G/P partition quotients for SVOCs with high K_OA values (>10^11.38) or low P_L values (<10^−4.92).