Identification of Potential Novel Bioaccumulative and Persistent Chemicals in Sediments from Ontario (Canada) Using Scripting Approaches with GC×GC-TOF MS Analysis

This work describes a single and fast approach using a filtering script as a means of prioritizing sample processing of data acquired by GC×GC-TOF MS for the identification of potentially novel persistent and bioaccumulative halogenated chemicals. The proposed script is based on the recognition of a generic halogenated isotope cluster pattern that allows for the simultaneous detection of chlorinated, brominated, or mixed halogen-substituted compounds in a single classification. Once developed, the script was applied to the identification of organohalogens in stream sediments collected across the southern region of Ontario (Canada). Classified peaks were first compared with available analytical standards and reference libraries to confirm the known chemicals. Unknown potential persistent organic pollutants (POPs) were evaluated for occurrence within the samples and high resolution mass spectrometry was used in order to identify some of the most prevalent compounds in the samples and resulting in the identification of three decachlorinated dechlorane analogs (C<sub>18</sub>H<sub>14</sub>Cl<sub>10</sub>), two undecachlorinated dechlorane species (C<sub>18</sub>H<sub>13</sub>Cl<sub>11</sub>), and a novel mixed chloro/bromo-carbazole (C<sub>12</sub>H<sub>5</sub>NCl<sub>2</sub>Br<sub>2</sub>) in a number of sediments analyzed. Relative peak abundances of these unknown halogenated compounds were in the same order of magnitude or slightly higher than levels observed for conventional POPs detected in the samples.