Comparison of three sorbents for thin film solid phase microextraction of haloacetic acids from water

Water disinfection inevitably leads to disinfection byproduct formation, such as haloacetic acids. Many disinfection byproducts reportedly have adverse health effects and, in many instances, including four haloacetic acids, are classified as potential carcinogens. As the global awareness of these compounds increases, more regulatory bodies include certain disinfection byproduct groups in their regulations. Rugged, fast, and cheap analytical quantification methods are therefore crucial. In this paper, a thin film extraction method for haloacetic acids is outlined. Thin films were synthesized in-house using a spin coating procedure, which allowed for easy adjustment of the sorbent choice and film geometry. PDMS, Carboxen®, and HLB were of interest and their extraction potential for HAAs from spiked water was tested in three film variations. PDMS films impregnated with HLB or Carboxen® improved the extraction drastically compared to PDMS films. Specifically, HLB impregnated films achieved excellent extraction efficiencies for tri-substituted analytes (51% for BDCAA, 77% for CDBAA, and 92% TBAA), which are often present at extremely low concentrations in water. In addition to the extraction experiment, a computational model was applied to compare PDMS and HLB. Trends observed in the computational data reflected in the experimental results, showing the validity of the model and confirming that physisorption through hydrogen bonding was mainly responsible for successful extraction.