thermal desorption aerosol gas chromatography (tag)/ …
TRANSCRIPT
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Thermal Desorption Aerosol Gas Chromatography (TAG)/
Mass Spectrometry Development
Wen Xu, Build Team, John Jayne09/08/2018
AMS User’s meeting
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What is TAG and Why we need TAG
• TAG = Thermal desorption + Gas Chromatography
• AMS only gives total organics with No/Minimal molecular information. TAG complements AMS data by adding molecular information.
• Molecular tracers (specific molecules identified in various sources) identified by TAG could be used for source apportionments.
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What makes ARI TAG different from others
• Online (eliminates sample collection, transportation, storage, and preparation process)
• In-situ derivatization• Liquid injection for internal/external calibration• Optional light weighted portable mini GC oven (ADI)
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GERSTEL TDS 3C / TDS-A2
MarkesTD 100-xr
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TAG theory of operation
MSGC Column
ValvelessManifold
CollectionThermal DesorptionCell
FocusingTrap
Carrier He in
Sample in
Pump out
Step 0
Inner surface of CTD, impactor, and VLM is Inertium® (from AMCX) coated
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TAG theory of operation
MSGC Column
ValvelessManifold
CollectionThermal DesorptionCell
FocusingTrap
Carrier He in Pump out
Vent
Step 1
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TAG theory of operation
MSGC Column
ValvelessManifold
CollectionThermal DesorptionCell
FocusingTrap
Carrier He in Pump out
Back FlushStep 2
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TAG theory of operation
MSGC Column
ValvelessManifold
CollectionThermal DesorptionCell
FocusingTrap
Carrier He in
Sample in
Pump out
Step 3
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TAG theory of operation
MSGC Column
ValvelessManifold
CollectionThermal DesorptionCell
FocusingTrap
Carrier He in Pump out
Vent
Step 1
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Particle humidification, collection, removal, and flow measurement system
Flow measurement element RH/T box
Pump
RHT sensor
RHT sensor
Sample
HEPA HEPA
Auto Valve
3/2 solenoid valve
Humidifier
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Particle humidification, collection, removal, and flow measurement system
Flow measurement element RH/T box
Pump
RHT sensor
RHT sensor
Filter
HEPA HEPA
Auto Valve
3/2 solenoid valve
Humidifier
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Particle humidification, collection, removal, and flow measurement system
Flow measurement element RH/T box
Pump
RHT sensor
RHT sensor
Bypass
HEPA HEPA
Auto Valve
3/2 solenoid valve
Humidifier
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Derivatization (N-Methyl-N-trimethylsilyl-trifluoroacetamide, MSTFA)
Test tube1 Test tube2
MSTFA
Helium flow direction
To the 1/16’’ Swagelok tee
From the 1/16’’ Swagelok union on the ASCO solenoid valve
Test tube cap
Test tube cap
R-COOH R-COO(Si(CH3)3)R-OH R-O(Si(CH3)3)-NH + MSTFA = -N(Si(CH3)3)-SH -S(Si(CH3)3)… …
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Standard liquid injection system7 port/6 position selector valve 6 port/2 position switching valve
Load sample 1 into “sample” loop
Inject sample 1 from “sample” loop into CTD
He
CTD
MXP7970 MXP7900
MXP7970 MXP7900
He
CTDWaste
Waste13
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Helium flow distribution
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Helium flow distribution
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CTD Transfer
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Helium flow distribution
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Back Flush
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Desktop software for sequence creation and data logging
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TAG sequence Builder
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Desktop software for sequence creation and data logging
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TAG Run Builder
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Desktop software for sequence creation and data logging
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TemperatureFlowRHPressureOverview
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Desktop software for sequence creation and data logging
Set and ReadFlowPressureRHAmbient TemperaturesAIODIOGC Ready, …
Configurable names
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Desktop software for sequence creation and data logging
Set and ReadOctal TemperaturesPID Ramp/Soak profiles
Configurable names
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Two different types of instrument
Stand alone TAGand Agilent GC/MS
TAG EI-HTOF
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Systems delivered
• 2 Stand alone TAG• 1 TAG EI-HTOF• 2 TAG-AMS• 3 sets of TAG parts
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Sample data from ambient
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Liquid Internal standard
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Problems list encountered up to date• Liquid water condensation into the system, leading to failure of Focusing trap and/or RHT sensors• Outgas of the HEPA filters, causing problem with filter (gas) channel. Denuder might be better• Clogging of 9-jet impactor. Replacing it requires dissemble the ICTD from the manifold• Transfer line failure (both user fault and mechanical leakage) from GC to MS (specific for the EI-
HTOF)• 24V power supply failure• Might still have cold spots for (CTD-VLM arm and VLM-Trap arm)• Retention time from mini-GC oven Not stable (does not apply to stand alone TAG)• Intermittent loss of Octal temperature controller set temperature command• The DVZ, and standard injection test tube connections are limiting the high end pressure of GC… many moreRecently, ARI auto value leaking
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We are building our own system to work on resolving those issues !
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Slides from Users
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HKPolyU
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Slides from Users
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0
200000
400000
600000
800000
1000000
12000003/
28/1
8 21
:23
3/29
/18
5:31
3/29
/18
13:3
43/
29/1
8 21
:37
3/30
/18
16:0
63/
31/1
8 0:
093/
31/1
8 8:
133/
31/1
8 16
:16
4/1/
18 0
:19
4/1/
18 8
:23
4/1/
18 1
8:03
4/2/
18 0
:30
4/2/
18 8
:33
4/2/
18 1
8:13
4/11
/18
19:0
64/
12/1
8 3:
094/
12/1
8 11
:12
4/12
/18
19:1
64/
13/1
8 3:
194/
14/1
8 8:
494/
14/1
8 16
:57
4/15
/18
2:36
4/15
/18
10:4
04/
15/1
8 18
:43
5/12
/18
8:28
5/12
/18
17:3
85/
13/1
8 1:
425/
13/1
8 9:
465/
22/1
8 14
:58
5/22
/18
23:1
65/
23/1
8 7:
205/
23/1
8 15
:23
Peak
Are
a of
C24
D50
Local time
Test #1 (N=73) Test #2(28) Test #3 (N=59)
HKUST
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Alkanes iso and anteiso alkanes Hopanes and steranes PAHsheptadecane(n-C17) iso-Nonacosane(iso-C29) 22,29,30-Trisnorneophopane (Ts) acenaphthylene152
prstane(i-C19) anteiso-Nonacosane(anteiso-C29) 22,29,30-Trisnorphopane (Tm) acenaphthene154octadecane(n-C18) iso-Triacontane(iso-C30) ab-Norhopane (C29ab-hopane) fluorene166
phytane (i-C20) anteiso-Triacontane(anteiso-C30) 22,29,30-Norhopane (29Ts) phenanthrene178nonadecane(n-C19) iso-Hentriacontane(iso-C31) aa-+baNorhopane (C29aa- +ba-hopane) anthracene178
icosane(n-C20) anteiso-Hentriacontane(anteiso-C31) ab-Hopane (C30ab-hopane) fluoranthene202heneicosane(n-C21) iso-Dotriacontane(iso-C32) aa-Hopane (C30aa-hopane) pyrene202
docosane(n-C22) anteiso-Dotriacontane(anteiso-C32) ba-Hopane (C30ba-hopane) cyclopenta[cd]pyrene226tricosane(n-C23) iso-Tritriacontane(iso-C33) abS-Homohopane (C31abS-hopane) benzo[c]phenanthrene 228
tetracosane(n-C24) anteiso-Tritriacontane(anteiso-C33) abR-Homohopane (C31abR-hopane) benz[a]anthracene 228pentacosane(n-C25) abS-Bishomohopane (C32abS-hopane) chrysene228hexacosane(n-C26) abR-Bishomohopane (C32abR-hopane) triphenylene228
squalane(i-C30) 22S-Trishomohopane (C33) benzo[b+k]fluoranthene252heptacosane(n-C27) 22R-Trishomohopane (C33) benzo[a]fluoranthene252
octacosane(n-C28) 22S-Tretrahomohopane (C34) benzo[e]pyrene252nonacosane(n-C29) 22R-Tretrahomohopane (C34) benzo[a]pyrene252
tracontane(n-C30) 22S-Pentashomohopane (C35) perylene252hentriacontane(n-C31) 22R-Pentashomohopane (C35) indeno[1,2,3-cd]pyrene276
dotriacontane(n-C32) benzo[ghi]perylene276tritractotane(n-C33) aaa 20S+baa 20R-Cholestane 217 dibenzo[a,h]anthracene278
tetratriactoane(n-C34) abb 20R-Cholestane 218 benzo[b]chrysene278pentatriacontane(n-C35) abb 20S-Cholestane 218 dibenzo[a,c]anthracene278hexatriacontane (n-C36) aaa 20R-Cholestane 217 picene278
heptatreacontane(n-C37) aaa 20S 24S-Methylcholestane 217 coronene300octatreacontane(n-C38) abb 20R 24S-Methylcholestane 218 dibenzo[a,e]pyrene302nonatriacontane(n-C39) abb 20S 24S-Methylcholestane 218 302
tetracontane (n-C40) aaa 20R 24R-Methylcholestane 217 1,3,5-triphenylbenzene 306aaa 20S 24R/S-Ethylcholestane 217
abb 20S 24R-+baa 20R 24R-Ethylcholestane 218abb 20S 24R-Ethylcholestane 218aaa 20R 24R-Ethylcholestane 217
Semi-Volatile
Hopanes and low volatility species can’t be detected
in ambient samples!
DetectedNot detected
Slides from Users
HKUST
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Slides from Users
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Dicarboxylic acid Succinic acidGlutaric acidAdipic acidPimelic acidSuberic acidAzelaic acid
Hydroxyl-carboxylic acid Malic acidCitramalic acidTartaric acidCitric acidGlyceric acid
Aromatic acid 3-hydroxybenzoic acid4-hydroxybenzoic acidVanillic acidIsophthalic acidSyringic acid1,2,3-benzenetricarboxylic acid1,2,4-benzenetricarboxylic acid1,3,5-benzenetricarboxylic acidTerephthalic acid
Fatty acid Palmitic acidStearic acidCholesterolOleic acid
Saccharides GlycerolGalactosanMannitol MannosanLevoglucosanGlucoseSucrose
Isoprene SOA tracers 2-methylglyceric acid *2-methylthreitol *2-methylerythritol *cis-2-methyl-1,3,4-trihydroxy-1-butane *3-methyl-2,3,4-trihydroxy-1-butane *trans-2-methyl-1,3,4-trihydroxy-1-butane
α-pinene SOA tracers Pinonic acidPinic acid *3-hydroxyglutaric acid *3-hydroxy-4,4-dimethylglutaric acid *3-methyl-1,2,3-butanetricarboyxlic acid *3-acetylglutaric acid *3-isopropylglutaric acid *
β-caryophyllene SOA tracer β-caryophyllinic acid *Naphthalene Phthalic acidToluene SOA tracer 2,3-dihydroxy-4-oxopentanoic acid *
Volatility ↑
Polar acids & SOA tracers
DetectedNot detected
HKUST
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Slides from Users
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There is significantly difference on the two groups at 95% confidence level
Trial one Trial two
→ No significantly difference between filtered and total phase sampling !!! ???
HKUST
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Slides from Users
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Cold spots?
HKUST
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Shift of retention in mini GC
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Peak shifts : 13 sDouble the peak width
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Shift of retention in Agilent’s GC
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Peak position on top of each other
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Alternative mini GC oven used for Fast-GC
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http://www.aerodyne.com/sites/default/files/u17/FastGC_Vocus.pdf
Project Leader: Brian LernerEmail: [email protected]
We might be able to modify the design to accommodate higher max temperature for TAG
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Adding extra heater on the arms of Ironman
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Alternative Filter Collection Thermal desorption Cell (F-CTD)
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I-CTDF-CTD
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New rack mount electronics
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c-TAG
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VOC column:Targeted: C5~C16
SVOC column:Targeted: C12~C40Filter CTD
Sorbent tube
6 port chromatography valve
VOC TAG calibration systemAdapted from PTR calibration
EI-HTOF inlet
Ball Valve
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Zoomed in view of the FCTD
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Filter CTD
SVOC Purge Tee
Purge upstream
Purge downstream
Valveless manifold
Ball Valve