European aerosol phenomenology-5: climatology of black carbon optical properties at 9 regional background sites across Europe

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European aerosol phenomenology-5: climatology of black carbon optical properties at 9 regional background sites across Europe M.Zanatta 1,2, F. Cavalli 3, M. Gysel 2, N. Bukowiecki 2, T. Müller 4, E. Weingartner 2,x, H. Areskoug 5, J. Ström 5, M. Fiebig 6, N. Mihalopoulos 7, G. Kouvarakis 7, D. Beddows 8, R.M. Harrison 8,9, J.P. Putaud 3, G. Spindler 4, A. Wiedensohler 4, A. Alastuey 10, M. Pandolfi 10, K. Sellegri 11, E. Swietlicki 12, U. Baltensperger 2 and P. Laj 1 marco.zanatta@psi.ch 11/11/2015 ACTRIS-2 First WP3 Workshop, Athens, Greece

COMPANION PAPER A European aerosol phenomenology -4: carbonaceous aerosol sampling artifacts, analytical discrepancies, and harmonized concentrations at 10 regional background sites across Europe F. Cavalli 1,, J.P. Putaud 1 1- European Commission, Joint Research Centre (JRC), Institute for Environment and Sustainability (IES), Air and Climate Unit, via E. Fermi 2749, 21027 Ispra VA, Italy 2

MOTIVATION AND GOALS Absorbing optical properties of black carbon: mass absorption cross section (MAC) MMM λ [m 2 /g] = σ aa λ [MM 1 ] m EE [µg/m 3 ] λ σ aa = absorption coefficient m EE = elemental carbon mass concentration MAC is used in Radiative modelling σ ap = BC * MAC Filter based photometers ebc = σ ap / MAC Main concerns MAC is often assumed as location and season constant inaccuracy in RF and ebc Wide range of MAC 637 values in the literature : 4 22 m 2 g -1 Investigate the spatial and seasonal variability of MAC over Europe 3

BC ABSORPTION SENSITIVE TO Size (Bond and Bergstrom,2006) Mixing state (Bond et al., 2006) Also instrumental artifacts play a consistent role in MAC calculation 4

1. Introduction THE OUTLINE 2. Method a. Definitions b. The ACTRIS sites c. Experimental method i. EC determination ii. Abs determination and analysis iii. MAC calculation and errors 3. Results and discussion a. mec and abs variability b. MAC spatial variability c. MAC seasonal cycles d. MAC spatial homogeneity e. MAC enhancement with mixing degree 4. Conclusion 5

THE ACTRIS SITES Selection criterions: Simultaneous mec and σ ap measurements More than 1 year of measurement 9 ACTRIS sites, representative of back ground air masses, data span 2008-2011 6

THE ABSORPTION PHOTOMETER Three filter absorption photometer models 4 MAAP IPR, MEL, MSY, PUY 3 PSAP(custom) APT, BIR, VAV 2 Aethalometer HRL, FKL Instrument correction procedures MAAP (reference) Müller correction: Wavelength shift PSAP Bond correction: Response to absorption and scattering Uncertainty and instrumental errors Aethalometer Weingartner correction: Multiscattering: R(ATN) Shadowing (C=2.14) 7

ABSORPTION COEFFICIENT DATA TREATMENT Inst. correction Adjust to 637 nm Harmonize to MAAP CP: AAE: HF: Correction procedure Absorption Ångström exponent = 1 (PSAP& Aethalometer) Harmonization factor (relative sensitivity PSAP-Aethalometer vs MAAP) Aethalometer = 1.6 (Müller et al., 2011) PSAP = 2 (Personal communication T. Müller & station leaders) 8

ABSORPTION SPATIAL VARIABILITY Latitude gradient: σ ap increases approaching central Europe Max IPR: 10.7 Mm -1 Min BIR: 0.750 Mm -1 Scandinavia C. Europe Med High. Altitude High impact of urban area and industrial activities 9

ABSORPTION SEASONAL VARIABILITY Common seasonal trend: minimum during warm season More intense BC emission and lower PBL height Exceptions: Mediterranean and high altitude sites 10

MAC SPATIAL VARIABILITY Spatial distribution Mean European MAC Span of MAC values: 6.8 17 m 2 g -1 MAC homogeneously distributed: encouraging coefficient of divergence Common European MAC values : 9.5 m 2 g -1 ± 2 11

MAC SEASONAL VARIABILITY Evident seasonal variability at all sites Different sources and atmospheric processing 12

MAC AND MIXING DEGREE Non absorbing matter (NAM)= sum of non-sea salt sulfate, nitrate and organic matter Correlation between optical properties and aerosol composition Not possible to discriminate between effective enhancement and enhancement due to instrumental artifacts Contribution of OM absorption is negligible (<10%) 13

CONCLUSION Homogeneous dataset obtained through a correction and harmonization procedure for σ ap and m BC. Error associated to MAC exceeded in some case the 50% Statistical analysis revealed a discrete homogeneity of considered optical properties, an overall MAC mean of 9.5 m 2 g -1 ± 20% at 637 nm might be representative of BC at European background locations The dominance of seasonal cycle is an indication of a change in morphology or mixing degree of BC with other species. Correlation between optical properties and non absorbing aerosol was found and provides a simple tool to estimate roughly BC optical properties as a function of nonabsorbing aerosol presence. 14

CONSIDERATION ON THE EBAS DATABASE The dataset needs many technical information Here is missing Level Sampling flow Size of the spot Noise or detection limit Info on the data treatment In this case the user must contact the responsible person not only for scientific discussion but also for basic technical information A BIG LOSS OF TIME AND ENERGY FOR BOTH SIDES 15

THANKS FOR THE ATTENTION QUESTIONS? 16

Errors Standard propagation error procedure: 2 contributors Absorption: correction parameters, instrumental noise, harmonization factors σ aa = 2 2 2 2 σ aaaaaaa + σ aaaaa + σ aaaaaaa + σ aaaaaa EC concentration: harmonization factor m EE HHHH = 2 + mee m TT mmm EEEEEE 2 Total error MMM = σ aa σ aa 2 + m EE m EE 2 σ ap [%] m EC [%] MAC [%] APT 25 58 63 BIR 26 19 32 FKL 38 32 50 HRL 41 70 81 IPR 4 23 24 MEL 6 50 50 MSY 10 35 36 PUY 17 39 43 VAV 24 25 35 17

HF EC Site HF mec Aspvreten 1.35 Birkenes 1.02 Finokalia 1.19 Harwell 1.45 Ispra 0.93 Melpitz 1.79 Montseny 0.97 Puy de Dome 1.23 Vavihill 0.74 18

Station characteristics Site Coordinates Altitude [m asl] Period m EC Method σ ap Aerosol Fraction Area Aspvreten (SE) 58 48N, 17 23E 30 2010-11 EUSAAR-2 PSAP (522nm) PM10 Scandinavia Birkenes (NO) 58 23N, 8 15E 190 2010-11 EUSAAR-2 PSAP (525nm) PM10 Scandinavia Finokalia (GR) 35 20N, 25 40E 250 2008-10 EUSAAR-2 Aethalometer (880nm) PM10 Mediterranean Harwell (GB) 51 34 N, 1 19 W 60 2010 QUARTZ Aethalometer (880nm) PM10 British Isles Ispra (IT) 45 49N, 8 38E 209 2008-11 EUSAAR-2 MAAP (637nm) PM2.5 Continental Europe Melpitz (DE) 51 32N 12 54E 87 2008-10 VDI MAAP (637nm) PM10 Continental Europe Montseny (ES) 41 46N, 2 21E 720 2008-11 EUSAAR-2 MAAP (637nm) PM10 Mediterranean Puy de Dôme (FR) 45 46N, 2 57E 1465 2008-10 EUSAAR-2 MAAP (637nm) PM10 Continental Europe Vavihill (SE) 56 01N, 13 09E 172 2010-11 EUSAAR-2 PSAP (520nm) PM10 Scandinavia 19

Literature MAC Source-location MAC [m 2 g - 1 ] Remote areas 5 Wavelengt h [nm] MAC 637 nm [m 2 g -1 ] 4.3 Mediterranean 18 15.5 550 Savannah 20 17.3 Urban 12 10.4 Reference Liousse, Cachier & Jennings, 1993 Biomass burning (Brazil) 12.1 550 10.5 Vanderlei Martins et al., 1998 High altitude winter High altitude summer 7.6 7.5 630 11.1 11 Cozic et al., 2008 Traffic 9.1 7.6 530 Biomass burning 13 10.8 Schwarz et al., 2008 High altitude spring 10.2 630 10.1 Liu et al., 2010 Regional background 10.4 635 10.4 Pandolfi et al., 2011 Urban (Barcelona) 9.2 Traffic (Bern) 10.3 Reche et al., 2011 Industrial (Huelva) 9.8 Urban (Paris) 13.6 550 11.7 Laborde et al., 2013 Aspvreten 16.3 14.1 Birkenes 25.9 22.4 Harwell 9.14 550 7.9 Melpitz 4.55 3.9 Vavihill 26.2 22.7 Genberg et al., 2013 High altitude 10.9 Pandolfi et al., 2014 20

Coefficient of divergence (COD) CCC A,B = p 1 p MMM ii MMM ii MMM ii + MMM ii i=1 2 ASP BIR FKL HRL IPR MEL MSY PUY VAV ASP 0.14 0.33 0.36 0.18 0.18 0.14 0.44 0.11 BIR 0.14 0.21 0.24 0.04 0.07 0.03 0.32 0.20 FKL 0.33 0.21 0.00 0.15 0.19 0.19 0.22 0.18 0.37 HRL 0.36 0.24 0.15 0.21 0.21 0.24 0.10 0.41 IPR 0.18 0.04 0.19 0.21 0.07 0.04 0.29 0.25 MEL 0.18 0.07 0.19 0.21 0.07 0.07 0.30 0.25 MSY 0.14 0.03 0.22 0.24 0.04 0.07 0.32 0.21 PUY 0.44 0.32 0.18 0.10 0.29 0.30 0.32 0.48 VAV 0.11 0.20 0.37 0.41 0.25 0.25 0.21 0.48 21

Compostion Mass concentration ± StDev [µg m -3 ] BC OM Sulfate Nitrate BIR 0.10 ± 0.05 1.32 ± 0.60 0.25 ± 0.17 0.17 ± 0.15 HRL 0.41 ± 0.35 2.27 ± 1.26 1.40 ± 1.10 2.02 ± 2.33 IPR 1.43 ± 1.32 6.06 ± 6.10 0.74 ± 0.59 0.76 ± 1.21 MEL 0.96 ± 1.79 6.08 ± 5.89 0.94 ± 1.06 0.95 ± 0.94 MSY 0.24 ± 0.13 1.76 ± 0.68 0.55 ± 0.36 0.26 ± 0.26 22

OM absorption Any absorption enhancement at wavelength longer than 532 nm is to be attributed to a lensing effect driven by internal mixing of BC with organic matter and other non-absorbing species (Lack et al., 2012). OM mass concentration was converted into σ ap-om using a MAC of 0.0297 m 2 g -1 at 532 nm of wavelength (Utry et al., 2013), the latter is representative of humic like substances at European background locations. σ ap-om /σ ap was found to follow a seasonal trend with maximum during summer (<10%). 23