Thermal Desorption Aerosol Gas

Chromatograph – Aerosol Mass Spectrometer

(TAG – AMS)

A. Bertrand

N. Marchand

AMS User Meeting - Milan 2015

TAG - AMS

• Collaboration between Aerodyne Inc, Aerosol Dynamics and Berkeley

• First Aerodyne prototype sold to LCE (Aix-Marseile U.), and now one at Juelich

Thermal Desorption Aerosol

Gas Chromatograh (TAG)

Aerosol Mass

Spectrometre (AMS)

Introduction to the TAG - AMS

Quad Filter

AMS modified to accomodate a quad filter (for discrimation of lower m/z)

Introduction to the TAG - AMS

Valveless Injection System

Octal Temperature

Controller

Standards Injection

System

CTD Cell

Fast Column

Collection Thermal Desorption (CTD) Cell

Kreisberg, AST, 2011

Fast Column by VICI

• 15 min Run (40 °C to 305 °C)

• ~ 150 runs before it has to be changed

Transfer Line

Heater

Transfer Line

Derivatization System

• Initial TAG modified to incorporate a DVZ system (Isaacman, AMT, 2014)

Derivatization System

Focusing Trap

Valveless

Injection

System

And Internal Standards

D10 Adipic Acid

D4 Phtalic Acid

D31 Palmitic Acid

D42 Eicosane

D50Tetracosane

D6 Cholesterol

Biomass Burning Other

Vehicular Industrial

Biogenic Cooking

Mannosan Acide Palmitique Phenanthene

Galactosan Acide Oleique Anthracene

Levoglucosan Acide Palmitoleique Fluoranthrene

Acide Stéarique Acephenanthrene

Vaniline Acide Linoléique Pyrene

Conyferyl Aldehyde Benzo[a]anthracene

Syringaldehyde Di-ethyl phtalate Chrysene/Triphenylene

Acide Vanilique Di-isobutyle phtalate Benzo[b,k]fluoranthrene

Acetosyringone Di-butyl phatalate Benzo[i]fluoranthrene

Benzyl-butyl phtalate Benzo[a,e]pyrene

Cholesterol Bis(2-ethyl hexyl) phtalate Perylene

Stigmasterol Indeno[1,2,3-cd]pyrene

B-Sistosterol BNT(2,1-d) Indeno[1,2,3-cd]fluoranthrene

BNT(1,2-d) Dibenzoanthracene

Acide DL glycérique BNT(2,3-d) Benzo(ghi)perylene

Acide Abiétique

Acide Pinonique Alcanes C18 à C36 Nor-Hopane (C29)

Hopane (C30)

Homohopane (C31)

HA

PH

op

anes

Su

cres

D

ériv

és S

yr.

Et

Gu

a. S

téro

ls A

utr

es

Aci

des

Aci

des

Gra

s

Ph

tala

tes

HA

P

Sou

ffré

s

Compounds

• Secondary Biogenic Markers, Secondary Anthropogenic Marker … (this list is non-exhaustive !!)

Sequence

300 °C

Desorption

Injection

standards

internes

Sequence

Sequence

Sequence

Typical sequence includes :

• 30 min TAG sampling / AMS run

• 15 min desorption/DVZ

• 15 min Chromatographic un

TAG User Interface

• User Interface developped by T. Hohaus

• Allow to build automatic sequence (control of valves, flow, heaters, AMS menu

switching

Exploration and Integration Toolkit

• Peak Integration via TERN (TAG Exploration, Review, and iNtegration) developped

by D. Sueper and G. Isaacman

1600

1200

800

400

0

TA

G -

AM

S

Sig

na

l R

esp

on

se

900800700600500 Time (s)

4000

3000

2000

1000

0

1

2

3

4

56

7

8

9

10

11

12

13

14

15 16

17

1600

1200

800

400

0

TA

G -

AM

S

Sig

na

l R

esp

on

se

900800700600500

Time (s)

4000

3000

2000

1000

0

1. Galactosan2. Mannosa3. Levoglucosan4. Vanilic Acid5. Phenanthrene6. Anthracene

13. Stearic Acid14. Docosane15. Tetracosane16. Hexacosane17. Octacosane

7. Octadecane8. Nonadecane9. Palmitoleic Acid10. Palmitic Acid11. Eicosane12. Oleic Acid

1

2

3

4

56

7

8

9

10

11

12

13

14

15 16

17

Additional Toolkit

• TICC (TAG Inlab Concentration Calculator) et TACC (TAG Atmospheric

Concentration Calculator) allow for quick access to concentration and time-

series, developed by A. Bertrand

• Need a discussion over calculation of PMF error matrix

TAG influence on AMS

Pump AMS only

Gas Load off

TAG – AMS

He flow 10

psi

TAG - AMS

He flow 20

psi

P2 450 421 421

P3 250 339 359

P4 200 199 222

P5 < 200 275 314

P6 ~ 200 276 277

• Ionization efficiency with TAG and Quad Filter : 2,78E-8

• Original AMS : IE ≈ 2E-7

• Level of m/z of 18, 28, 32, 40 with TAG : 4 to 7 times those when no TAG is

connected

5

4

3

2

1

0

5004003002001000

50

40

30

20

10

0

x10

-3

5004003002001000

• TAG – AMS (Open Spectra)

• AMS (Open Spectra)

Contamination peak

from column bleeding

and Transfer line

Contamination persist for a

while (at much lower level)

even after TAG is

disconnected

TAG influence on AMS

m/z – 110 - 114

m/z 207m/z 281

Thermodesorption : Levoglucosan TGA

levoglucosan

???

• Unknown peak with similar

ts than that of levoglucosan,

at high level (not on filter)

• Possible thermal

decomposition happening

TAG-AMS first deployment

Arve Valley, in the Alps

Passy station

Alt : 583 m

Gaseous Phase

PTR-ToF-MS : Chemical composition and concentration of volatile compounds

NOx, CO, CO2, monitoring

Particle Phase

HR-ToF-AMS : Bulk chemical composition, concentration,and sizing of submicrometer non-refractory aerosol, PM1

TAG-AMS : Hourly Organic Speciation, PM1

MAAP : Measurement of Black Carbon, PM1

SMPS, OPC : Aerosol size distribution and concentrationSMPS (15 - 685 nm)OPC (0,225 – 34 um)

AE 33 : Measurement of Black Carbon

TAG-AMS first deployment

30 sampling period

60 – 80 minutes each

6,7 l/min

1000

800

600

400

200

0

TA

G C

om

po

un

ds (n

g/m

3)

12:00 PM2/25/2014

12:00 AM2/26/2014

12:00 PM 12:00 AM2/27/2014

12:00 PM 12:00 AM2/28/2014

60

50

40

30

20

10

0

Tota

l O

rga

nic

(ug

/m3

)

Vaniline Coriferyl aldehyde

Syringalaldehyde Dérivés Syringuiliques Vanilic Acid

Acetosyringone

Palmitic Acid

Linoleic Acid

Oleic Acid Acides Gras Stearic Acid

Abietic Acid

Pinonic Acid

Diethyl phtalate

Dibutyl phtalate Phtalates Benzylbutyl phtalate

Bis 2 ethyl hexyl phtalate

Phenanthrene

Anthracene HAP Pyrene

Benzo a anthracene

Chyrsene

n-Octadecane

n-Nonadecane

n-Eicosane

n-Docosane Alcanes n-Tetracosane

n-Hexacosane

Galactosan

Manosan Sucres Levoglucosan

Total Organic (AMS)

60

40

20

0

Co

ncen

trati

on

(ug

/m3)

12:00 AM2/25/2014

12:00 AM2/26/2014

12:00 AM2/27/2014

12:00 AM2/28/2014

Organic Ammonium Sulfate Chrlorure Nitrate Black Carbon

SMPS

TAG-AMS first deployment

700

600

500

400

300

200

100

0

TA

G L

evo

glu

co

sa

n (

ng

/m3

)

12:00 PM2/25/2014

12:00 AM2/26/2014

12:00 PM 12:00 AM2/27/2014

12:00 PM 12:00 AM2/28/2014

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0

AM

S C

2H

4O

2+

(ug

/m3

)

TAG Levoglucosan AMS fragment C2H4O2

+

25

3500

3000

2500

2000

1500

1000

500

0

540520500480460

2500

2000

1500

1000

500

0

540520500480460

800

600

400

200

0

TA

G L

evoglu

cosan (

ng/m

3)

8006004002000

AMS C2H4O2 (ng/m3)

R2 = 0.68

slope 0.80

TAG-AMS first deployment

26

TAG-AMS first deployment

60x10-3

40

20

0

Tota

l C

on

trib

utio

n S

ign

al

100806040

0.12

0.08

0.04

0.00

20

15

10

5

0

Con

cen

tratio

n (u

g/m

3)

15/02/2014 27/02/2014

dat

100

80

60

40

20

0

60

40

20

0

0.10

0.08

0.06

0.04

0.02

0.00

OOA - BBOA BBOA HOA (constrained) HOA Ref Spectra [3]

• Some issues, our instrument is the first operational instrument (still a prototype)

• Good sensitivity (500 to 10 000 times more sensitive than offline methods)

• Allows us to look at dynamic happening on very short time span (SOA formation

and ageing of primary emissions)

Thus, possibility to run experiments in smog chamber !

• Need to play on sampling time instead of dilution to avoid saturating the

detector/column

• Questions over the thermostability of some molecules must be investigated more

thoroughly

• Loss of sensitivity for AMS measurements

• Possible contamination

Conclusions

Introduction to the TAG - AMS