Passive Sampling of Chemical Warfare Agents in the Marine Environment

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Title: Passive Sampling of Chemical Warfare Agents in the Marine Environment
Author: Pruccoli, Andrea
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
Thesis level: master's thesis
Abstract: Dumping sites of chemical warfare agents related compounds have been created after the two last major wars. The assessment of the risks connected to these sites is a priority as they could threaten the human health directly, through incidents when the dangerous materials come directly into contact with a subject and indirectly, as the poisonous substances can affect the environment and enter the food chain. Many techniques have been involved in the monitoring, for example sediment analysis and mussels bio-monitoring. To overcome the deficiencies of these techniques and to obtain a more complete overview of the situations, new ways of analysis are studied. In this thesis the passive sampler technique was studied as new method to monitor the chemical warfare agents dumping sites. This technique has been often used in the environmental monitoring of air and water samples. In the specific this work focused its attention in the use of silicone sheets as passive samplers, investigating their effectiveness with the substances of interest: sulfur mustard derivatives, arsine related chemical warfare agents derivatives and α-chloroacetophenone. Furthermore, the extraction power of different solvents was tested and a theoretical study of the opposing phenomena that compete in the extraction process was carried out. Finally, the theoretical uptake model was tested on the different substances verifying its validity and showing how the efficacy of the passive sampling technique depends on various factors like the sampler-water partition coefficient, the relative recovery from the sampler and the stability of the compound of interest. The recovery studies have shown how acetone is the best solvent with a wide variety of compounds, but its extraction power can be improved towards less polar compounds using a solution of acetone/ethyl acetate 9:1. The effectiveness of silicone sheets as passive samplers was demonstrated by the kinetic studies. Stable compounds with a high octanol-water partition coefficient (≥ 3) present the best results showing good agreement with the theoretical model. The next step will be testing the silicone sheets near known dumpsites using performance reference compounds as in situ calibration.

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