Publication Details

Category Text Publication
Reference Category Journals
DOI 10.1021/acsenvironau.1c00056
Licence creative commons licence
Title (Primary) pH-dependent partitioning of ionizable organic chemicals between the silicone polymer polydimethylsiloxane (PDMS) and water
Author Niu, L.; Henneberger, L.; Huchthausen, J.; Krauss, M. ORCID logo ; Ogefere, A.; Escher, B.I.
Source Titel ACS Environmental Au
Year 2022
Department WANA; ZELLTOX
Volume 2
Issue 3
Page From 253
Page To 262
Language englisch
Topic T9 Healthy Planet
Keywords passive equilibrium sampling; acidity constant; partition constant; speciation; microplastic
Abstract The silicone polymer polydimethysiloxane (PDMS) is a popular passive sampler for in situ and ex situ sampling of hydrophobic organic chemicals. Despite its limited sorptive capacity for polar and ionizable organic chemicals (IOC), IOCs have been found in PDMS when extracting sediment and suspended particulate matter. The pH-dependent partitioning of 190 organics and IOCs covering a range of octanol–water partition constants log Kow from −0.3 to 7.7 was evaluated with a 10-day shaking method using mixtures composed of all chemicals at varying ratios of mass of PDMS to volume of water. This method reproduced the PDMS–water partition constant KPDMS/w of neutral chemicals from the literature and extended the dataset by 93 neutral chemicals. The existing quantitative structure–activity relationship between the log Kow and KPDMS/w could be extended with the measured KPDMS/w linearly to a log Kow of −0.3. Fully charged organics were not taken up into PDMS. Thirty-eight monoprotic organic acids and 42 bases showed negligible uptake of the charged species, and the pH dependence of the apparent DPDMS/w(pH) could be explained by the fraction of neutral species multiplied by the KPDMS/w of the neutral species of these IOCs. Seventeen multiprotic chemicals with up to three acidity constants pKa also showed a pH dependence of DPDMS/w(pH) with the tendency that the neutral and zwitterionic forms showed the highest DPDMS/w(pH). DPDMS/w(pH) of charged species of more hydrophobic multiprotic chemicals such as tetrabromobisphenol A and telmisartan was smaller but not negligible. Since these chemicals show high bioactivity, their contribution to mixture effects has to be considered when testing passive sampling extracts with in vitro bioassays. This work has further implications for understanding the role of microplastic as a vector for organic micropollutants.
Persistent UFZ Identifier
Niu, L., Henneberger, L., Huchthausen, J., Krauss, M., Ogefere, A., Escher, B.I. (2022):
pH-dependent partitioning of ionizable organic chemicals between the silicone polymer polydimethylsiloxane (PDMS) and water
ACS Environ. Au 2 (3), 253 - 262 10.1021/acsenvironau.1c00056