Simultaneous quantification of humic acid-water and silanized glass-water partition constants for PCBs, PCDDs and OCDF

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Authors

SCHACHT Veronika Janina MANNING Murray GRANT Sharon C. GAUS Caroline HAWKER Darryl W.

Year of publication 2020
Type Article in Periodical
Magazine / Source Chemosphere
MU Faculty or unit

Faculty of Science

Citation
Web https://doi.org/10.1016/j.chemosphere.2019.125338
Doi http://dx.doi.org/10.1016/j.chemosphere.2019.125338
Keywords Dissolved organic carbon (DOC); Silanization; Polydimethylsiloxane (PDMS); Mass balance; Facilitated transport; Super-hydrophobic organic contaminants (SHOCs)
Description Super-hydrophobic organic contaminants (SHOCs) such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and octachlorodibenzofuran (OCDF) can sorb to dissolved hydrophobic materials including humic acids (HAs), enhancing their apparent aqueous solubility and potentially resulting in increased groundwater contamination and offsite transport. To manage risks associated with transport of and contamination by SHOCs, modelling approaches incorporating partitioning data, i.e. dissolved organic carbon-water partition constants (K-DOC), are necessary. Measurement of K-DOC can however be compromised by SHOC sorption to glassware surfaces leading to an overestimation of experimental values resulting in larger K-DOC. A method for simultaneous derivation of K-DOC and glass-water partition constants (K-GW) is described. It involves a mass balance approach combined with HA as a co-solvent at various concentrations and accounts for SHOC losses to silanized glassware. Measured log K-DOC values ranged from 5.28 to 7.64 for tetra- to decachlorinated PCBs, 6.67 to 7.93 for tetra- to octachlorinated PCDDs and 8.20 for OCDF. These data were linear functions of log K-OW and consistent with relationships reported for more polar compounds. Log K-GW (mm(3) mm(-2)) values (1.62 to 4.06 for PCBs, 2.96 to 3.90 for PCDDs, 3.77 for OCDF) were one order of magnitude greater compared to literature PCB borosilicate glass-water partition constants. Techniques such as those presented in this work present simple, versatile means to provide prediction of the SHOC proportion remaining in aqueous solutions after loss to glassware that was inversely related to container surface area/volume ratio and log K-OW in our study.
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