Organics in the Mix during SAPUSS

M. Dall´Ostoand the SAPUSS team

CSIC, Barcelona, Spain

manuel.dallosto@gmail.com

“How can Europe control the composition of its atmosphere

under a changing climate?”

SAPUSS aims to identify sources of particles in the atmosphere and to understand the physical and chemical

transformations occurring in them once emitted.

SAPUSS studies the urban Mediterranean environment

(1)Simultaneous off-line filter measurements at 12 hours resolution, concentrations of 36 neutral and polar organic compounds were obtained by GC-MS, classified by MCR-ALS.

(2)Simultaneous single particle mixing state measurements with Aerosol Time Of Flight Mass Spectrometry (ATOFMS), classified by ART-2a algoritm.

(3)Simultaneous measurements with High Resolution Aerosol Mass Spectrometry (HR-ToF-AMS) were taken; classified by PMF.

To get close to the full picture of the source identification of particles you need to

synergistically deploy a number of aerosol techniques

Part 1: PM1 (12 hours)

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Urban POA

SOA Aged

OOA Urban

BBOA Regional

SOA BIO ISO

SOA BIO PIN

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Part 1. Off line in a nutshell (Marta Alier, Barend Van Drooge, ACP 2013)

Six OA identified at both sites: two primary OA, three of SOA origin (60%), one not clearly defined.

(1) POA from emissions of local anthropogenic activities (43% RS, 18% UB).

(2) Biomass burning (BBOA - 7% RS; 12% UB), regional air mass circulation.

(3) Isoprene oxidation (about 10% both sites), influence of inland air masses.

(4) A SOA biogenic component attributed to α-pinene oxidation (SOA BIO PIN) did not impact the two monitoring site at the same level (about double at UB).

(5) Aged anthropogenic and biogenic SOA, stagnant atmospheric conditions (about 15% both sites).

(6) Component formed by C7-C9 dicarboxylic acids, detected mainly only during daytime (23% RS vs. 10% at UB). Air mass dependent, showing an enhancement under sulphate-rich North African air masses and a reduction under nitrate-rich stagnant regional air masses.

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SOA Isoprene [MRC-ALS score values]

605040302010 % SOA BIO Pinene / Total OA

Anti correlation between SOA ISO and SOA PIN during nucleation days

Growth of urban NPF events linked with biogenic α-pinene oxidation products but inhibited by isoprene organic compounds.

(Marta Alier, Barend Van Drooge, ACP 2013)

Part 2: ATOFMS: UB and RS•Birmingham ATOFMS (RS). Hit 1,042,331 particles; classified 890,873•Cork ATOFMS (UB) Hit 274,974; classified 218,657

MAIN type particle number

%

K-EC 277151 31.1 EC 202227 22.7

EC EC-Nit 102909 11.6 EC-OC-Nit 28656 3.2

OC OC 42680 4.8 OC-Nit 15306 1.7 K-CN 21515 2.4

K K-Sul 52420 5.9 K-Nit_1 13295 1.5 K-Nit_2 9134 1.0

NaCl NaCl_1 75204 8.4 NaCl_2 8926 1.0 Ca 16273 1.8

Metals Fe 7201 0.8 Pb 577 0.1 Amine_58 6698 0.8

Amine Amine_114 3672 0.4 Amine_84 4888 0.5 Amine_59 2141 0.2

main type number % EC EC 76678 35.1

KEC 52074 23.8 Ecnit 9982 4.6

K Ksul 6635 3.0 Knit 15931 7.3 KCN 2778 1.3

nacl Nacl 31853 14.6 Nacl2 8166 3.7

Metals NaEC 2507 1.1 KP 1390 0.6 Pb 382 0.2 Fe 5564 2.5 Ca 2842 1.3 V 1875 0.9

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OC-CHO Lub-Oil OC-NITAro-NIT

Amine-114 Amine-59 Amine-58 ETS K-CN

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2. ATOFMS a nutshell

- Ten different particle types were detected at both locations

- Four were related to amines (primary and secondary origin). Aminium salts were found related to coarse sulphate rich particle types, (heterogeneous reaction mechanisms?).

- Four organic rich particles showed a complex single particle mixing state relationship between organic carbon and nitrate.

The atmosphere in the Mediterranean urban areas has large variability in OA-nitrate mixing state.

Part 3: HR-ToF-AMS

Does it compare well with PM1 filters? Overall, yes.

RS y = 0.30x + 1.4

R2 = 0.68

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However, OA presents lowest correlations…

Both AMSshows same trends at both RS and UB

AMS organic factors:HOA, OOA, SV-OOA, COA

(conservative)

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Time of the day

UB_HOA RS_HOA

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UB_SV-OOA RS_SV-OOA

UB_COA RS_COA

•Trying to push AMS-PMF into more factors to justify more than HOA,SV-OOA,OOA,COA by comparing it with other techniques.

•Receptor modeling applied to all results will simplify the organic aerosol source apportionment during SAPUSS.

QUESTION: “How can Europe control the composition of its atmosphere under a changing climate?”