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10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument description and sample data N.L. Ng, T. Onasch, A. Trimborn, S. Herndon, M. Canagaratna, D. Sueper, D. Worsnop, J. Jayne Aerodyne Research, Inc. AAAR Meeting Oct 27, 2009 Size: 19”D x 21”W x 33”H Aerosol Chemical Speciation Monitor ACSM Weight: 140 lbs (64 kg) Power: 300W Data acquisition via Ethernet connection – basic laptop is sufficient. ACSM-002 SN 140-100

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Page 1: Aerosol Chemical Speciation Monitor ACSM - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg10/ACSM_Users... · 10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument

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1

Aerosol Chemical Speciation MonitorACSM

Instrument description and sample data

N.L. Ng, T. Onasch, A. Trimborn, S. Herndon, M. Canagaratna, D. Sueper, D. Worsnop,

J. Jayne

Aerodyne Research, Inc.

AAAR Meeting Oct 27, 2009

Size: 19”D x 21”W x 33”H

Aerosol Chemical Speciation MonitorACSM

Weight: 140 lbs (64 kg)

Power: 300W

Data acquisition via Ethernet connection – basic laptop is sufficient.

ACSM-002 SN 140-100

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ACSM, aka…

• Ehm-Eye-Ehn-Eye MINI• Mini-AMS• Baby AMS• AMS Light• Cheap AMSp• Ponche• Sammy

Aerosol Chemical Speciation MonitorACSM

• Continuous monitoring of non-refractory aerosol composition by thermal particle vaporization aerosol mass spectrometry.

Sulfate, Nitrate, Chloride, Ammonium, Organics

• Builds on ARI Q and ToF AMS Hardware and analysis concepts.

lower cost, lower sensitivity.

• Designed for monitoring, long term unattended operation.

Performance demonstrations in progress

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Research grade

Particle Beam Generation

Aerodynamic Sizing

Particle Composition

Aerosol Mass Spectrometer

Fast DataResearch gradeTOF mass spectrometer

Thermal Vaporization

Beam Chopper

Particle TOF Region

Fast DataSystemTimersDACs

Vaporization &

Electron Impact

Ionization

Aerodynamic Lens

Particle TOF Region

Pumps (x5)

Particle Beam Generation

Particle Composition

Aerosol Chemical Speciation Monitor

No Sizing

Commercial grade

Thermal Vaporization

&

LaptopComputer

RG

A

gMass Spectrometer

Pfeiffer Prisma

Particle Inlet (1 atm)

Electron Impact

Ionization

Aerodynamic Lens40-1000 nm

Pumps (x3)Slow scan rates, 1 sec/amu. Can’t time resolve SI or SP

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ACSM Designed Around Pfeiffer Prisma RGA

• Prisma electronics supports:• Prisma electronics supports:– 6mm diameter rods, 200 amu range.– 1 mA/mbar sensitivity to Ar (200 amu head)– Ethernet connectivity with OPC1 interface.– A Windows CE computer/OS.

B ilt i di it l d l I/O– Built-in digital and analog I/O.

1OPC is a standard software interface which enables data communication between applications of different manufacturers. OPC stands for Openness, Productivity, Collaboration (formerly OLE for Process Control).

60

40

amps

( x1

0-9 ) Pump 4 installed

Pump 4 removed

Removal of Pump4

20

0

Sig

nal,

a

504540353025201510

AMU

10-9

10-8 Pump 4 installed Pump 4 removed

• Lower Air signal• Slightly larger water signal

10-12

10-11

10-10

Sign

al

14012010080604020

AMU

Slightly larger water signal• Organic background ok

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RG

A

Internal StandardNaphthalene Effusive Source

• m/z marker

I i i• Ion transmission

• Ionization efficiency reference

h h l100

ty EI spectra from NIST for Napthalene

1 µm pin hole

naphthalene molecules

80

60

40

20

0

Rel

ativ

e In

tens

i

14012010080604020

AMU

EI spectra from NIST for Napthalene

1011 s-1

Ion Transmission1.4

1.2

1.0ensi

ty

16 mm (QAMS) 6 (P i )

N2

0.8

0.6

0.4

0.2

0.0

Nor

mai

lzed

Ion

Inte 6 mm (Prisma)

Ne

ArKr

Xe

14012010080604020

m/z

Compares 16mm (QAMS) to 6mm (ACSM)

Page 6: Aerosol Chemical Speciation Monitor ACSM - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg10/ACSM_Users... · 10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument

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1.2

1.0

ion

Noble gas mix ratio of 6mm and 16mm Quad

Naphthalene

Ion Transmission Correction

0.8

0.6

0.4

0 2Rel

ativ

e Io

n Tr

ansm

issi Current estimate

0.2

0.0

R

200150100500

m/z

Naphthalene provides an in-situ measure of IT

30x10-12

25mps

)

34

32 Naphthalene Sig ChamberT

Naphthalene Signal Varies with Chamber Temperature

25

20

15

10

5

Nap

htha

lene

Sig

nal (

am

3/9/2009 3/13/2009 3/17/2009

30

28

26

24

22

Cham

ber Temp., C

-10.8

-10.6

g)

Date/Time

-11.4

-11.2

-11.0

Log(

Nap

. Si

3.40x10-33.383.363.343.323.30

1/ChamberT (K)

This is a vapor pressure measurement…

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30x10-12

25amps

)

34

32C

Naphthalene Sig Naphthalene T-corrected ChamberT

Temperature Corrected Naphthalene Signal

20

15

10Nap

htha

lene

Sig

nal (

a

30

28

26

24

Cham

ber Temp., C

5

3/9/2009 3/13/2009 3/17/2009

Date/Time

24

22

A measure of SEM gain

Anthracene for AMS systems?Anthracene vapor pressure 1.70E-05naphthalene vapor press 0.078Naph/Anthra vp 4.59E+03

Page 8: Aerosol Chemical Speciation Monitor ACSM - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg10/ACSM_Users... · 10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument

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Automated Valve System for Instrument Zero

3 way Valve

GA

Sample mode

Filter

Filter mode

Filter

3-way Valve

RG

Aerosol mass is determined from difference of ‘Sample – Filter”

Automated ValvesFixed pinhole assemblyFilter

To Cyclone

Achim’s (beer) Shelf

Page 9: Aerosol Chemical Speciation Monitor ACSM - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg10/ACSM_Users... · 10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument

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ACSM Inlet Schematic

Sample Flow~3 LPM from cyclone

100 um pin-hole

~3 LPM from cyclone

iso-kinetic splitNominal flo 10 000cc/minAMS aerodynamic lens

1/2 OD x 0.41” ID tube

Pump

P

pNominal flow 10,000cc/minReynolds No. ~1300

Aerosol mass is determined from difference of ‘Sample – Filter” mass spectra

1008060

e (

x10-1

2 )

Difference Sample Filt

10-11

10-9

10-7

gnal

(am

ps)

4020

0Diff

eren

ce Filter

Naphthalene

Chemical species are determined following Allan et al, 2003Sulfate, Nitrate, Chloride, Ammonium, Organics

10-13

10

Sig

14012010080604020

m/z

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Instrument Stability - Allan Variance

0.2m-3

6:00 PM10/5/2009

12:00 AM10/6/2009

6:00 AMDate/Time

10-4

10-3

10-2

rianc

e (σ

2 )

0.20.0

-0.2µg m

Org

5 min

Va

4 5 6 7 8

1032 3 4 5 6 7 8

1042 3

Integration Time (s)

Measured under (ideal) laboratory conditions

Estimated 3σ Detection Limits

• 1 hr DLs are 100

2

46

1000

-3)

NH4 Org SO4 NO3Chl < 0.2 µg m-3

• 24 hr DLs are < 0.05 µg m-3

12

46

102

46

100

3σ D

L (n

g m

- Chl

Detection limits depend on background signal levels in the spectrum

20151050

Signal Integration Time (hours)

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Ratio of xAMS / ACSM Detection LimitsValues are 30 min 3σ

HTOF-w HTOF-v Ctof QAMSHTOF w HTOF v Ctof QAMSOrg 3.9 63.7 73.8 3.0SO4 2.1 45.3 107.1 1.5NO3 3.3 35.9 86.7 3.3NH4 18.0 70.9 168.4 7.7Chl 1.9 8.2 24.6 3.1

DeCarlo et al, 2006 Anal. Chem, 78, 8281-8289

10-9

10-8

s)

MS Difference in Beam Block mode

13

10-12

10-11

10-10

Sign

al (a

mps

Beam Block Mode (filter on)

10-13

222120191817161514131211

AMU

A consequence of a shorter chamber is a more intense molecular beam

Page 12: Aerosol Chemical Speciation Monitor ACSM - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg10/ACSM_Users... · 10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument

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10-2

3.6

3.4

3.2 sign

al d

ata

12:00 PM10/6/2009

6:00 PM 12:00 AM10/7/2009

6:00 AM

datBeam Block mode, 5 min 1 scan open, 1 scan closed

10-4

10-3

Alla

n V

aria

nce

(σ2 )

4 5 6 7 8 9

1032 3 4 5 6 7 8 9

1042 3

Integration Time (s)

ORG

40x10-3 a

12:00 PM10/6/2009

6:00 PM 12:00 AM10/7/2009

6:00 AM

dat

10-6

10-5

10-4A

llan

Var

ianc

e (σ

2 )

4 5 6 7 8 9

1032 3 4 5 6 7 8 9

1042 3

Integration Time (s)

40x10200

-20-40 si

gnal

dat

a

SO4

Org does not signal average as well in BB mode. Looks like Filter switching is better. But, other species are not as affected?

Atomizer

Setup for Mass Based IE Determination

By-passDrier

Must consider lens transmission and multiply charged diameters from DMA

ACSMDMA

CPC

AerosolDiluter

filter

Mixing Tube

Input Mass = ρ x Volume(size) x Number Reported Mass

Plot Measured Mass vs Input Mass

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700

600

00s x1

0-12 ) 5.6

5.4

s x1

0-9 )

NH4NO3 Ionization Efficiency Calibration

NO3 NH4500

400

300

200

100

0NO

3 io

n si

gnal

s (a

mps

76543210

Slope=8.62e-11

5.2

5.0

4.8

4.6

NH

4 io

n si

gnal

s (a

mps

2.52.01.51.00.50.0

Slope=4.05e-10

4

NO3 mass (ug/m3) NH4 mass (ug/m3)

Calibration based on calculated mass delivered from atomizer/DMA/CPC system

NO3 = NO+ + NO2+ NH4 = NH+ + NH2

+ + NH3+

2.5

2.0

0-10

Correlation of AN-IE with naphthalene Signal

1.5

1.0

0.5

0 0

IE (a

mp/

mas

s)x1

0.0140120100806040200

Naphthalene Sig (Temp corrceted)x10-12

Want to demonstrate that naphthalene signal is an effective measure of IE

Page 14: Aerosol Chemical Speciation Monitor ACSM - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg10/ACSM_Users... · 10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument

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• Spain, March 2009 – 3 weeks• Houston May 2009 – 6 weeks

Recent Field Deployments of the ACSM

Houston, May 2009 6 weeks• Queens, NY June 2009 – 8 weeks

NYSDEC

http://www.dec.ny.gov/chemical/54360.html

ACSM Data Sample Queens, NY 2009

10

8

6

4gs (u

g/m

3)

NH4 Org SO4 NO3 Chl

4

2

0

Load

ing

7/16

/200

9

7/21

/200

9

7/26

/200

9

7/31

/200

9

8/5/

2009

8/10

/200

9

8/15

/200

9

8/20

/200

9

8/25

/200

9

8/30

/200

9

9/4/

2009

9/9/

2009

UTC Time• 8 weeks unattended 29.0% 6.7% 8 weeks unattended continuous measurements • Data upload to a FTP site 0.2%

12.4%

51.7% cp5

15.9 µg m-3

average

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ACSM vs HTOF-AMS Time TrendsQueens, NY 2009

Org4

25201510

50

HTOF AMS

NO3

NH4

Chl

12

µg m

-3

43210

43210 0.20

0.150.100.050.00

Qi Zhang, Yele Sun SUNY Albany

SO4

12840

7/15/2009 7/19/2009 7/23/2009 7/27/2009 7/31/2009

Local Time

0

cep8

0.20

0.15

Results from PMF AnalysisOOA and HOA Factors

OOA – Oxidized Organic

0.12

0.08Rel

ativ

e Io

n In

tens

ity 0.10

0.05

0.00

Aerosol“Photochemically Aged Aerosol”

HOA – Hydrocarbon-like Organic Aerosol

0.04

0.0014012010080604020

AMU

like Organic Aerosol“Primary Particles”

Queens Data, 2009

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OOA and HOA Time seriesACSM and AMS Comparison

12 ACSM OOA ACSM HOA AMSOOA 8

4

010

8

6

µg m

-3

AMS

HOA

OOA

7/16/2009 7/20/2009 7/24/2009 7/28/2009 8/1/2009

Date/Time (EST)

4

2

0

Qi Zhang, Yele Sun SUNY Albany

0.0 0.0

ACSM AMS

PMF Mass fractions

0.6

0.4

0.2HOA = 27%

OOA = 71%

0.6

0.4

0.2HOA = 26%

OOA = 73%

Fract_Mass1.0

0.8 Residual 2%

Fract_Mass1.0

0.8 Residual 1%

Page 17: Aerosol Chemical Speciation Monitor ACSM - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg10/ACSM_Users... · 10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument

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Future Work for ACSM

• Vaporization cage to capture and sample “bounced” particles.

• PM2.5 lens.

• Particle sizing module.• Integrated aerosol drier for RH treatment.

• Continued sw development.p

• Continue field demonstrations.

• Magnets

1200

1000Small Covered Ionizer

with magnets no magnets

Magnets on the Ionizer Average Single Particle Signal

800

600

400

200

NO

2+

03002001000-100-200

time (x10-6 sec)

Increases effective IE 2-3x

Page 18: Aerosol Chemical Speciation Monitor ACSM - CIREScires.colorado.edu/jimenez-group/UsrMtgs/UsersMtg10/ACSM_Users... · 10/31/2009 1 Aerosol Chemical Speciation Monitor ACSM Instrument

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Flow Control ModuleBlower with active flow

regulation.3-20 LPM 25mBar

Cyc

lone

Iso-kinetic split ACSM

3 20 LPM, 25mBar50W, 24VDC14” x 4” x 6”~5 lbs

MFMFilterBlower

Flow Control Elec.

Portable Met Monitor Portamon• RH 10-90%

• Temp• Barometric Pressure, 30-100 kPa,

resolution of 1.5Pa, ~12 cm air.• Wind Speed, spinning cup ~0.2

m/s/pulse• Wind Direction, 10 bit=360degree• Solar • RTC• GPS• Data logging to USB thumb drive or

RS232• Data rates: 1, 2, 5, 10, 15, 30, 60 secs, , , , , ,