P. Schlag1,2, A. Vermeulen3, M. J. Blom3, A. Kiendler-Scharr2 ,A. Khan1, R. Holzinger1

1 Institute for Marine and Atmospheric research Utrecht (IMAU), Utrecht University, The Netherlands2 Institut für Energie- and Klimaforschung: Troposphäre (IEK-8), Forschungszentrum Jülich GmbH, Germany3 Energieonderzoek Centrum Nederland (ECN), The Netherlands

Chemical air speciation at Cabauw, NL

Cabauw Experimental Site for Atmospheric Research (CESAR)

November 2011: AMS, TD-PTR-MSMay-July 2012: AMS, TD-PTR-MS, MARGAJuly 2012 – June 2013: ACSMJan-Feb 2013: PTR-MS, ACSM

Campaigns:

AMS, ACSM: vaporization (600°C), electron ionization

TD-PTR-MS: thermal desorption (50-350°C)Chemical ionization (H3O+)

MARGA: liquid chromatography

Instrument Comparison: AMS, ACMS, MARGA,

TD-PTR-MS

Correlation slopes

HR-ToF-AMS vs. ACSM vs.

MARGA

0.60 (R2=0.92) 0.60 (R2=0.93)0.55 (R2=0.84)0.50 (R2=0.83)

(422 data points)

1.23 (R2=0.96)0.88 (R2=0.93)0.63 (R2=0.86)0.49 (R2=0.26)

(1943 data points)

ACSM

1.03 (R2=0.73)0.85 (R2=0.89) 1.22 (R2=0.71)2.04 (R2=0.76)1.49 (R2=0.31)

(289 data points)

OrganicsNitrate

AmmoniumSulphateChloride

(No. of points)

ACSM: Campaign Overview July 2012 to June 2013

Total average mass loading: 9.6 µg/m3

45

40

35

30

25

20

15

10

5

0

To

tal

Mas

s C

on

cen

trat

ion

/ µ

g/m

³

01.09.2012 01.11.2012 01.01.2013 01.03.2013 01.05.2013

Date and time

12 exceedances of WHO PM2.5 daily mean limit

Total PM1 mass: Daily meansWhole year Org

NO3

SO4

NH3

ChlBC

18

16

14

12

10

8

6

4

2

0

Fac

tor

mas

s co

nce

ntr

atio

n [

µg

/m3 ]

15.01.2013 22.01.2013 29.01.2013 05.02.2013 12.02.2013 19.02.2013 26.02.2013 05.03.2013 12.03.2013 19.03.2013

Date and Time

Hydrocarbon-like Biomass Burning Low volatile Semi volatile

PMF results from ACSM data – Winter 2013

Zeppelin in the Netherlands

Time series of fractional species contribution to PM1 mass (a), excess NH4 (b), and species mass concentration (c)

ToF-AMS: Ground based measurements May-July 2012

16

14

12

10

8

6

4

2

0

Mas

s [

µg

/m3 ]

16.05.2012 21.05.2012 26.05.2012 31.05.2012 05.06.2012 10.06.2012 15.06.2012 20.06.2012 25.06.2012 30.06.2012 05.07.2012 10.07.2012 15.07.2012

Date and Time

1.0

0.8

0.6

0.4

0.2

0.0

Fra

cti

on

of

tota

l ma

ss

0.8

0.6

0.4

0.2

0.0Ex

c N

H4

[µ

g/m

3 ]

Org NO3

SO4

NH4

Chl

Zeppelin flights

a)

b)

c)

excess NH4: 4+ = 4+ − ( 3− + − + 2 𝑛𝑒𝑁𝐻 𝑛𝑁𝐻 𝑛𝑁𝑂 𝑛𝐶𝑙 ∙42− ) 𝑛𝑆𝑂

N/C=15% (AMS 3%)

N/C=6%

N/C=4%

N/C=9% (AMS 2%)

N/C=2% (AMS 0%)

N/C=4% (AMS 1%)

Actris/EMEP winter campaign Jan/Feb 2012Cabauw, PTR-MS, aromatics

young traffic plumes Aged traffic plumes

No biomass burning: acetonitrile always below 0.05 nmol/mol

Actris/EMEP winter campaign Jan/Feb 2012Cabauw, PTR-MS, aromatics 2

young traffic plumes Aged traffic plumes

Actris/EMEP winter campaign Jan/Feb 2012Cabauw, PTR-MS, Oxygenated species

young traffic plumes Aged traffic plumes

Actris/EMEP winter campaign Jan/Feb 2012Cabauw, PTR-MS, isoprene, MVK+MACR, monoterp.

young traffic plumes Aged traffic plumes

Actris/EMEP winter campaign Jan/Feb 2012Cabauw, PTR-MS, others (naphtalene, org. acids)

young traffic plumes Aged traffic plumes

Different air mass origin?

Summary

◘ Intercomparison: AMS, ACSM, MARGA, TD-PTR-MS

◘ 1-year ACSM measurements in Cabauw: 12 exceedances of WHO PM2.5 daily limitNitrate and organics are the most dominant species

◘ TD-PTR-MS factor analysis (PMF) suggests high N/C ratios of OA componentsLink to AMS observations of excess NH4 at Cabauw

◘ Gas phase PTR-MS: full mass spectrum monitoring of organics at levels below 0.01 nmol/molTool for online monitoring of the semivolatile gas phase burden.