Determination of short-chain aliphatic amines in environmental samples

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http://urn.fi/URN:NBN:fi-fe201801151695
Title: Determination of short-chain aliphatic amines in environmental samples
Author: Helin, Aku
Other contributor: Helsingin yliopisto, Matemaattis-luonnontieteellinen tiedekunta, Kemian laitos
University of Helsinki, Faculty of Science, Department of Chemistry
Helsingfors universitet, Matematisk-naturvetenskapliga fakulteten, Kemiska institutionen
Publisher: Helsingin yliopisto
Date: 2018
Language: eng
URI: http://urn.fi/URN:NBN:fi-fe201801151695
http://hdl.handle.net/10138/273503
Thesis level: master's thesis
Discipline: Analytical Chemistry
Analyyttinen kemia
Analytisk kemi
Abstract: Short-chain aliphatic amines (SCAA) are present in multiple different matrices in the environment at low concentration levels. SCAA are considered to be environmentally relevant compounds due to their role as precursors in the formation of carcinogenic N-nitrosoamines in various matrices and new particle formation in the atmosphere. SCAA are characteristically highly volatile, polar, reactive and basic compounds. Consequently, the quantitative determination of SCAA tends to be rather challenging. In the literature part of this thesis, different analytical methods used for the determination of SCAA in environmental samples are reviewed. The typical approach for the analysis of SCAA has been the use of derivatization techniques. Derivatization converts SCAA into less polar and less volatile form, which enables the use of conventional separation techniques, such as gas chromatography (GC) and high-performance liquid chromatography (HPLC). However, the methods involving derivatization can be quite time consuming, require the usage of excess reagents and are mainly applicable for the analysis of primary and secondary SCAA. To reduce the amount of reagent and solvent consumption, microextraction techniques have been implemented as part of the derivatization methods. For the analysis of free SCAA, mainly ion chromatography (IC) and GC have been used. In recent years, also novel online mass spectrometry techniques have been used for the determination of free SCAA in atmospheric air. In the experimental part of this thesis, a novel solid-phase microextraction (SPME) device called SPME Arrow was used for the extraction of free SCAA. Different SPME Arrow sorbent materials were tested, including commercial and custom sorbents, extraction conditions were optimized and the performance of SPME Arrow was compared to conventional SPME fiber. The developed method was applied for the determination of SCAA in wastewater samples and atmospheric air samples. In general, the performance of the custom sorbent coated SPME Arrow was not adequate due to the deterioration of coating, although the preliminary results indicated possible selectivity towards dimethylamine. Considering the commercial sorbent coated SPME devices, the SPME Arrow was better than the SPME fiber in terms of limit of quantification and performance in real sample analysis. When the SPME Arrow was used for wastewater sample analysis, no matrix interferences were observed, opposite to the results obtained with the SPME fiber. In addition, the SPME Arrow could be used for the determination of SCAA in atmospheric air samples following prior preconcentration by using denuder for sampling.


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