Use of Mixed Solvent Systems to Eliminate Sorption of Strongly Hydrophobic Organic Chemicals on Container Walls

Strongly hydrophobic organic chemicals (SHOCs) can be defined as neutral organic chemicals that have soil organic carbon (OC) normalized sorption coefficient (KOC) >10,000. Sorption isotherms of SHOCs are normally measured in aqueous systems to determine KOCSince SHOCs can adsorb on container walls leading to overestimation of KOC, we used mixed solvent systems to characterize this potential error. Sorption coefficient (KM) and percent recovery (%RM) of anthracene, DDT, and dieldrin during sorption on centrifuge tubes made of polytetrafluoroethylene (PTFE), polycarbonate (PC), polypropylene copolymer (PPCO), and glass high pressure liquid chromatography vials (HPLCV) were measured in volume ratio‐varied methanol‐water mixtures until 100% recovery of the sorbate was achieved. The data were evaluated using the Solvophobic theory. The KMvalues of the entire test SHOCs decreased exponentially with increasing fraction of methanol (fc). For sorption on PTFE, 100% recovery of the three chemicals was at fc> 0.45. However, 100% recovery of DDT and anthracene from PC and PPCO was at fc> 0.90. The 100% recovery of dieldrin from HPLC vials was at fc> 0.70. In water the calculated recoveries of DDT, dieldrin, and anthracene from PTFE were 32, 43, and 48%, respectively. However, the recoveries of dieldrin from HPLC vials and DDT and anthracene from PC and PPCO ranged from 2 to 14%. The data demonstrate that sorption on container walls is a source of error that can reduce the integrity of the analyte and might be one of the causes for the large variability in literature KOCvalues for SHOCs.