Gas Chromatographic Estimation of Vapor Pressures and Octanol–Air Partition Coefficients of Semivolatile Organic Compounds of Emerging Concern

Abstract

The subcooled liquid-phase vapor pressures (p L 298 /Pa) and octanol−air partition coefficients (K OA 298 ) at T/K = 298, enthalpies of vaporization (Δ VAP H/kJ•mol −1 ), and internal energies of phase transfer from octanol to air (Δ OA U/kJ•mol −1 ) were estimated for synthetic musks, novel brominated flame retardants (N-BFR), organophosphate esters, and ultraviolet filters using the capillary gas chromatographic retention time (GC-RT) method. These compounds, which spanned approximately six and three orders of magnitude for p L 298 /Pa and K OA 298 , respectively, were co-chromatographed with one of three reference compounds to give initial estimates of properties at T/K = 298. The initial GC-RT property estimates were subsequently calibrated using 18 compounds that spanned 6 log units for p L 298 /Pa and 13 compounds covering 4 log units for K OA 298 . The calibrated log 10 p L 298 /Pa values estimated here ranged from 0.14 ± 0.19 to −9.19 ± 0.29 for cyclopentadecanone to syndechlorane plus (syn-DDC-CO), respectively, while the range of log 10 K OA 298 values was 6.59 ± 0.26 to 11.40 ± 0.23 for cyclopentadecanone to 2,2′,4,4′,5-pentabromodiphenyl ether (BDE-99), respectively. The calibrated GC-RT-derived values were highly correlated with, and were within an average of 0.70 log units of, the literature data for compounds with well-established p L 298 / Pa and K OA 298 measured or derived using non-GC-RT methods. Nonpolar compounds were used in this study to estimate the target polar compound data, which may introduce systematic errors. However, the comparison of our GC-RT results against the literature non-GC-RT values shows that the GC-RT methods performed similarly well for estimating both polar and nonpolar target compounds studied in this work.

Occurrence and Gas–Particle Partitioning of Organic UV-Filters in Urban Air

“… a Maximum concentrations of drug medicinal ingredients in sunscreens (“Guidance Document Sunscreen Monograph,” Health Canada, 2012). b EPA EPI suite. c Pegoraro et al d Okeme et al e Pegoraro et al f MW = molecular weight, KOA = octanol–air partition coefficient, E = trans isomer, Z = cis isomer. …”

Assessing Human Exposure to SVOCs in Materials, Products, and Articles: A Modular Mechanistic Framework

“…K oa can be determined experimentally, but many K oa values found in the literature have been derived from the air/water partition coefficient K aw , the octanol/water partition coefficient K ow and/or Henry’s law constant H , which introduces additional uncertainty. ,, When K oa is obtained from K aw and K ow , the uncertainty of K oa can be calculated as the combined uncertainty of the parameters used to obtain K oa . For example, if K oa = K ow RT / H is used, the uncertainty of K oa is the combined uncertainty of K ow and H .…”

“…In the absence of reliable measurements and when the set of functional groups of the system components allow its application, the EVAPORATION model by Compernolle et al 191 is the recommended p s estimation method. K oa can be determined experimentally, 192 but many K oa values found in the literature have been derived from the air/ water partition coefficient K aw , the octanol/water partition coefficient K ow and/or Henry's law constant H, which introduces additional uncertainty. 183,193,194 When K oa is obtained from K aw and K ow , the uncertainty of K oa can be calculated as the combined uncertainty of the parameters used to obtain K oa .…”

Novel Bayesian Method to Derive Final Adjusted Values of Physicochemical Properties: Application to 74 Compounds

“…Theoretical Background for more details). FAVs have been used to identify problems or artifacts in established measurement techniques, to calibrate indirect measurements techniques, , to evaluate in silico estimations, and as inputs to multimedia models …”

“…Theoretical Background for more details). FAVs have been used to identify problems or artifacts in established measurement techniques, 30 to calibrate indirect measurements techniques, 31,32 to evaluate in silico estimations, 33 and as inputs to multimedia models. 34 Measured data for several physicochemical properties have traditionally been required to generate FAVs of a property for a compound; this limits the number of compounds for which FAVs may be derived, as many compounds have insufficient published measured data.…”