Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore

Polyfluorinated alkyl substances (PFASs) are a large group of organic chemicals, many of which are persistent in the environment, bioaccumulative and pose potential adverse effects to human health. The presence of neutral, volatile PFASs in air are of particular concern, as air quality is an importa...

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Main Author: Wu, Yaoxing
Other Authors: Chang Wei-Chung, Victor
Format: Theses and Dissertations
Language:English
Published: 2013
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Online Access:https://hdl.handle.net/10356/51878
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Institution: Nanyang Technological University
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spelling sg-ntu-dr.10356-518782023-03-03T19:20:21Z Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore Wu, Yaoxing Chang Wei-Chung, Victor School of Civil and Environmental Engineering DRNTU::Engineering::Environmental engineering::Environmental pollution Polyfluorinated alkyl substances (PFASs) are a large group of organic chemicals, many of which are persistent in the environment, bioaccumulative and pose potential adverse effects to human health. The presence of neutral, volatile PFASs in air are of particular concern, as air quality is an important determinant in terms of public health. However, little experimental information is available on the physicochemical properties of volatile PFASs. The short-term concentration variations of airborne PFASs also remain unknown due to the lack of a highly sensitive analytical method which can also achieve satisfying temporal resolution. Therefore, the aim of current work is to improve our understanding of the partitioning behavior, occurrence and source strength of neutral, volatile PFASs in Singapore. Firstly, air–water partition coefficient (KH) of 4 fluorotelomer alcohols (FTOHs), a subgroup of volatile PFASs, was measured using inert gas-stripping method (IGS). KH values of FTOHs showed strong propensity to partition into air. However, the expected linear dependence of KH on molecular weight was not observed. The unique molecular geometry of FTOHs, with hydrogen bonding and molecular contortion, was probably responsible for the unusual phenomenon. The results were compared to predictions made by SPARC and EPI suite. The erroneous predications given by modeling software packages appeared to confirm the unusual behavior of the compounds.Secondly, the study attempted to develop a novel method based upon thermal desorption and GC–MS for determination of indoor airborne volatile PFASs, including four FTOHs, two fluorooctane sulfonamides (FOSAs), and two fluorooctane sulfonamidoethanols (FOSEs) through low-volume active air sampling. The optimization of sorbent combination was also conducted. The method recovery exhibited significant improvement compared with other existing methods such as passive air sampling method. The approach also achieved relatively high temporal resolution and low noise level. It has been successfullyapplied to routine quantitation of targeted PFASs in indoor office environment of Singapore, which provided further insights toward the indoor source strength of PFASs and performance of building air handlings. Thirdly, the developed thermal desorption method was further applied for determination of target PFASs in urban atmosphere through low-volume active air sampling (0.108 m3). It displayed greatly improved method recovery but higher detection limits in comparison with the conventional protocol, which employs highvolume sample collection (450 m3) and solvent-based sample extraction. Comparison of their performances in the real samples of urban atmosphere showed a higher portability and temporal resolution of thermal desorption method, which would be very useful in source apportionment analysis and assessment of concentration variations in highly-urbanized regions. In addition, the concentration levels of PFASs detected in the ambient air of Singapore were more in line with the European pattern and might indicate an increasing tendency toward using FTOHs in these regions. Doctor of Philosophy (CEE) 2013-04-15T03:40:26Z 2013-04-15T03:40:26Z 2013 2013 Thesis Wu, Y. (2013). Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/51878 10.32657/10356/51878 en 153 p. application/pdf
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic DRNTU::Engineering::Environmental engineering::Environmental pollution
spellingShingle DRNTU::Engineering::Environmental engineering::Environmental pollution
Wu, Yaoxing
Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore
description Polyfluorinated alkyl substances (PFASs) are a large group of organic chemicals, many of which are persistent in the environment, bioaccumulative and pose potential adverse effects to human health. The presence of neutral, volatile PFASs in air are of particular concern, as air quality is an important determinant in terms of public health. However, little experimental information is available on the physicochemical properties of volatile PFASs. The short-term concentration variations of airborne PFASs also remain unknown due to the lack of a highly sensitive analytical method which can also achieve satisfying temporal resolution. Therefore, the aim of current work is to improve our understanding of the partitioning behavior, occurrence and source strength of neutral, volatile PFASs in Singapore. Firstly, air–water partition coefficient (KH) of 4 fluorotelomer alcohols (FTOHs), a subgroup of volatile PFASs, was measured using inert gas-stripping method (IGS). KH values of FTOHs showed strong propensity to partition into air. However, the expected linear dependence of KH on molecular weight was not observed. The unique molecular geometry of FTOHs, with hydrogen bonding and molecular contortion, was probably responsible for the unusual phenomenon. The results were compared to predictions made by SPARC and EPI suite. The erroneous predications given by modeling software packages appeared to confirm the unusual behavior of the compounds.Secondly, the study attempted to develop a novel method based upon thermal desorption and GC–MS for determination of indoor airborne volatile PFASs, including four FTOHs, two fluorooctane sulfonamides (FOSAs), and two fluorooctane sulfonamidoethanols (FOSEs) through low-volume active air sampling. The optimization of sorbent combination was also conducted. The method recovery exhibited significant improvement compared with other existing methods such as passive air sampling method. The approach also achieved relatively high temporal resolution and low noise level. It has been successfullyapplied to routine quantitation of targeted PFASs in indoor office environment of Singapore, which provided further insights toward the indoor source strength of PFASs and performance of building air handlings. Thirdly, the developed thermal desorption method was further applied for determination of target PFASs in urban atmosphere through low-volume active air sampling (0.108 m3). It displayed greatly improved method recovery but higher detection limits in comparison with the conventional protocol, which employs highvolume sample collection (450 m3) and solvent-based sample extraction. Comparison of their performances in the real samples of urban atmosphere showed a higher portability and temporal resolution of thermal desorption method, which would be very useful in source apportionment analysis and assessment of concentration variations in highly-urbanized regions. In addition, the concentration levels of PFASs detected in the ambient air of Singapore were more in line with the European pattern and might indicate an increasing tendency toward using FTOHs in these regions.
author2 Chang Wei-Chung, Victor
author_facet Chang Wei-Chung, Victor
Wu, Yaoxing
format Theses and Dissertations
author Wu, Yaoxing
author_sort Wu, Yaoxing
title Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore
title_short Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore
title_full Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore
title_fullStr Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore
title_full_unstemmed Partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in Singapore
title_sort partitioning behavior and occurrence of airborne polyfluorinated alkyl substances in singapore
publishDate 2013
url https://hdl.handle.net/10356/51878
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