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Functionalized glass fiber filters for the
simultaneous sampling of vapour and
particle phase PCDD/Fs and dl-PCBs
Valerio Paolini1,2, Ettore Guerriero1, Paolo Benedetti1,
Silvia Mosca1, Marina Cerasa1, Mauro Rotatori1, Alessandro Bacaloni2
1 National Research Council of Italy , Institue of Atmospheric Pollution Research (CNR IIA)
2 Sapiernza University of Rome, Chemistry Department
36th International Symposium on Halogenated Persistent Organic Pollutants
Florence, August 28th - September 2nd 2016
PCDD/Fs and dl-PCBs air sampling
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Filters do not retain the total amount of analytes:
•Vapour/particle partitioning
•Desorption (and ab/adsorption) phenomena
Filter/adsorbent sampling:
•PUF (polyurethane foam), XAD (microporous styrene/divinylbenzene) etc
•Does the adsorbent/filter ratio gives the atmospheric vapour/particle partitioning?
PCDD/Fs and dl-PCBs air sampling
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Other adsorbent problems:
•Reuse or not: higher sampling costs or higher sampling blanks?
•Size problems with personal/automated samplers
•Accelerated (pressurised) solvent extraction vs Soxhlet
Simultaneous filtering and adsorbing device
Simultaneous filtering and adsorbing devices
ENVITM (Sigma Aldrich/Supelco) adsorbent microspheres
deposited on a fiber filter (loss of microspheres with sampled
analyte); medium impedance
EMPORETM (3M) adsorbent microspheres incorporated on a
teflon filters with inglobed; high impedance
In order to reduce the impedance, we developed a FILTER
MADE OF FUNCTIONALIZED FIBERS, without adsorbent
microspheres (very low impedance)
ATLANTICTM (Horizon) adsorbent microspheres beetween two
fiber filters (sandwich); very high impedance
We looked for a simultaneous filtering and adsorbent device, trying to use in
air devices commonly used for water samples, but all these devices could not
be used in air because of their high impedance:
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Functionalisation of filters
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Whatman GF/D glass microfiber filtre (47 mm and
100 mm diametre)
•Pretreatments
•Dehydration (anhydrous acetone and toluene)
•Functionalisation (PTES in toluene)
Pretreatment
Increase in weight
No
pretreatment (0.7 ± 0.1) %
HCl
0.5 M for 24 hours (1.2 ± 0.1) %
NaOH
0.5 M for 24 hours (6.2 ± 0.1) %
NaOH
0.5 M for 24 hours,
then
HCl
0.5 M for 24 hours (2.8 ± 0.1) %
NaOH
0.1 M for 24 hours (5.1 ± 0.1) %
NaOH
0.2 M for 24 hours (6.2 ± 0.1) %
NaOH
0.5 M for 24 hours (6.3 ± 0.1) %
NaOH
1 M for 24 hours (6.3 ± 0.1) %
NaOH
0.2 M for 12 hours (5.9 ± 0.1) %
NaOH
0.2 M for 48 hours (6.4 ± 0.1) %
Reaction
time Reaction
temperature Increase in
weight
12 h 25 °C (2.9 ± 0.1) %
24 h 25 °C (4.1± 0.1) %
48 h 25 °C (4.2± 0.1) %
12 h 80 °C (5.8 ± 0.1) %
24 h 80 °C (6.2 ± 0.1) %
48 h 80 °C (6.3 ± 0.1) %
Characterisation of filters
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•DSC/TGA (air, 5 °C/min)
•Oxidation of phenyls
•Hygroscopicity
Functionalised fiber filters: air sampling
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PAH sampling efficiency
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Paolini et al., Aerosol and Air Quality Research, 16: 175–183, 2016
PAH sampling efficiency
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Paolini et al., Aerosol and Air Quality Research, 16: 175–183, 2016
PAH extraction and purification recovery
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Comparison with other SPE disks not possible
PCDD/Fs and dl-PCB sampling
•Tecora EcoPUF samplers
•Filters 110 mm diameter
•Filters followed by a PUF cartridge
•PUF: density 0,022 g cm-1, 5 cm diameter per 5 cm length; Tisch Environmental.
•200 L min-1 flow rate
•48 h sampling time
•Parallel sampling using normal and functionalized filters was performed.
•Filters and PUF separately extracted and analysed
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PCDD/Fs sampling efficiency
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PCBs sampling efficiency
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Remarks and open questions
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•Normal filter/PUF efficiency: 15-95%
•Functionalised filter sampling >80% (including all carcinogenic PAHs)
•Is filter/PUF partitioning a useful information?
•Industrial emission samplig:
•improved efficiency… but not enough!
•oxidation is the predominant phenomenon for PAHs
•Water samples?
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Thank you for your kind attention
v.paolini@iia.cnr.it
www.iia.cnr.it