Packed Column Supercritical Fluid Chromatography:
Applications in Environmental Chemistry
av
Nicole Riddell
Akademisk avhandling
Avhandling för filosofie doktorsexamen i Kemi, som kommer att försvaras offentligt
fredag den 12 maj 2017 kl. 10.15, Hörsal B, Örebro universitet Opponent: Dr. John Jake Ryan
Retired from Health Canada, Bureau of Chemical Safety Ottawa, Ontario, Canada
Örebro universitet
Institutionen för naturvetenskap och teknik 701 82 ÖREBRO
Abstract
Nicole Riddell (2017): Packed Column Supercritical Fluid Chromatography: Applications in Environmental Chemistry. Örebro Studies in Chemistry 19. Although gas and liquid chromatography have emerged as dominant separation techniques in environmental analytical chemistry, these methods do not allow for the concurrent analysis of chemically diverse groups of persistent organic pollutants (POPs). There are also a small number of compounds which are not easily amenable to either of these traditional separation techniques. The main objective of this thesis was to address these issues by demonstrating the applicability of packed col-umn supercritical fluid chromatography (pSFC) coupled to mass spec-trometry (MS) in various aspects of environmental chemistry.
First, pSFC/MS analytical methods were developed for legacy POPs (PCDDs, PCDFs, and PCBs) as well as the emerging environmental con-taminant Dechlorane Plus (DP), and issues relating to the ionization of target analytes when pSFC was coupled to MS were explored. Novel APPI and APCI reagents (fluorobenzene and triethylamine) were opti-mized and real samples (water and soil) were analyzed to demonstrate environmental applicability.
The possibility of chiral and preparative scale pSFC separations was then demonstrated through the isolation and characterization of ther-mally labile hexabromocyclododecane (HBCDD) stereoisomers. The analytical pSFC separation of the α-, β-, and γ-HBCDD enantiomers as well as the δ and ε meso forms was shown to be superior to results ob-tained using a published LC method.
Finally, technical mixtures of phosphorus flame retardants (RBDPP, BPA-BDPP, and DOPO; a group of related compounds which are chal-lenging to analyze concurrently) were examined using multiple analytical techniques and pSFC was found to be the only method which facilitated the accurate determination of the components of all 3 mixtures.
This thesis confirms the potential of pSFC/MS as a fast, green, and cost effective means of separating and analyzing environmental contaminants.
Keywords: Supercritical Fluid Chromatography; Mass Spectrometry;
Ionization; POPs; APPI; APCI; chiral; achiral; packed column. Nicole Riddell, School of Science and Technology,
