Interdependence of the slopes and intercepts from log-log correlations of measured gas-particle paritioning and vapor pressure—I. theory and analysis of available data

Abstract

Gas-particle partitioning is examined using a partitioning constant K_p = (F/TSP)/A, where F (ng m⁻³) and A (ng m⁻³) are the particulate-assiociated and and concentrations, respectively, and TSP is the total suspended particulate matter level (μg m⁻³). At a given temperature and for a given sample of particulate matter, compound-dependent values of K_p tend to be correlated with the sub-cooled liquid vapor pressure (p_L⁰, toor according to log K_p = m_r log p_L⁰+b_m. Theory predicts that b_r values should be somewhat similar, and that m_r values should be near −1. This is supported by field and laboratory work. However, there is still noticeable variability in reported m_r and b_r values, even when obtained by the same researchers sampling in the same location. Three possible thermodynamic sources of variability include variability in the compound-to-compound differences in the thermodynamics of adsorption, event-to-event variability in the specific surface area of the aerosol and event-to-event variability in the ambient temperature. Non-thermodynamic sources of variability include sorption of gaseous analytes to the filters used in differentiating between F and A, the presence of non-exchangeable component in the measured F values, within-event adsorption/desorption kinetics, within-event changes in contaminant levels, and within-event changes in temperature. Each of these sources of variability operate in their own way to cause variability in m_r and b_r. In general, one can expect there to be a correlation in the obseved m_r and b_r of the form b_r = m_sm_r+b_s. For the study of Yamasaki et al. (1982, Envir. Sci. Technol. 16, 189–194), one obtains m_s = 5.77 and b_s = −2.18, with r² = 0.91. In the presence of such a correlation, one can expect that all log (F/TSP)/A vs log p_L⁰ plot will tend to intersect at the same (x,y) poitn given by (−m_s, b_s. Exisiting field and laboratory data show this tendency.