Supplement of Temporal variability and sources of VOCs in urban areas of the eastern Mediterranean

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1 Supplement of Atmos. Chem. Phys., 1, 1 1, 1 doi:1.19/acp supplement Author(s) 1. CC Attribution. License. Supplement of Temporal variability and sources of VOCs in urban areas of the eastern Mediterranean Christos Kaltsonoudis et al. Correspondence to: Spyros N. Pandis (spyros@chemeng.upatras.gr) The copyright of individual parts of the supplement might differ from the CC-BY. licence.

2 1. Measured m/z values by the PTR-MS Table S1. Compounds measured with the PTR-MS m/z Target molecules Calibration Acetonitrile,,,7,,9,1 Acetonitrile Multiple species,,,9 * 7 Formic acid,,9, Ethanol 1,9 * 9 Acetone 1-1, propanal 1,, butanedione 1, methylvinylether Acetone 1 Acetic acid 1,,,,,9,1, Glycolaldehyde,1 * 9 Isoprene 1,,,,,1, Furan,,1, Other species,1 Isoprene 71 MVK&MACR,,,,,9,1, Crotonaldehyde 1, Other species,1 MVK 7 MEK 1,,,9,1, Methyl propanal 1, Other species MEK 7 Hydroxyl acetone,,1, Methyl acetate 1, Butanol 9 * 77 PAN,7, * 79 Benzene 1-1, Ethyl benzene 1 Benzene 1 Monoterpene fragments,,9, Hexanal * Ethyl vinyl ketone,, Other species * 7 Methyl--butene--ol,,9, Other species,1 * 9 Toluene 1,,,,,9,1 Toluene 9 vinyl furan,1, Phenol,,9,1 * 99 Hexanal,,9 * 11 Isoprene hyperoxides, Hexanal 9 * 1 Styrene,, Peroxy isobutyryl nitrate, Other species * 17 Xylenes 1,,,,,9,1, Ethyl benzene,,1, Benzaldehyde, Xylene 11 Various species Chlorobenzene 11 Heptanal,, C7 ketones * 11 C9 aromatics 1,,,,,1 * 19 Octanal,, Naphtalene, * 1 C1 aromatics 1,, * 17 Monoterpenes 1,,,,9, a-pinene 19 Nopinone, * 11 Pinonaldehyde, * 1 C1 aromatics,, Other species * *Concentrations calculated for k=.x1-9 cm s Lindinger et al. (199),. Karl et al. (1),. Karl et al. (),. DeGouw et al. (),. Christian et al. (),. Holzinger et al. (a), 7. Holzinger et al. (b),. DeGouw and Warneke (7), 9. Rinne et al. (),1. Karl et al. (7).

3 . Patras summer campaign WD (degrees) WS (m/s) RH (%) Tair Solar radiation ( C) (W/m ) Global radiation Diffuse radiation 11/ 1/ 1/ 1/ 1/ 1/ 17/ 1/ 19/ / 1/ / / / / / Figure S1. Meteorological conditions during the Patras summer campaign (hourly averages). Date 9 9. Acetone Acetone.. Acetone Acetic acid... Acetic acid Formic acid + ethanol mz9# Formic acid, Ethanol Toluene, Xylenes, Acetonitrile. 1.. Toluene Benzene Xylenes Acetonitrile mz9#1.... Benzene Isoprene.... Isoprene Monoterpenes MVK+MACR MEK mz9#1. 1/1/ 1/ 1/1/17/ 1/19// 1/// / // Monoterpenes, MVK+MACR, MEK Date Figure S. VOC time series for the Patras summer campaign (hourly averages). All values are in ppb.

4 O (ppb) NO x (ppb) SO (ppb) BC (µg m - ) BC SO NO x O 11/ 1/ 1/ 1/ 1/ 1/ 17/ 1/ 19/ / 1/ / / / / / Date Figure S. O, NO x, SO and BC time series for the Patras summer campaign (hourly averages). 1 NOx O BC SO NOx (ppb) : : 9: 1: 1: 1: 1: Time (h) O (ppb). BC (µg/m - ). SO (ppb) Figure S. Diurnal profiles (median values of hourly averages) of nitrogen oxides (NO x ), black carbon (BC), sulfur dioxide (SO ) and ozone (O ) during the Patras summer campaign.

5 . Athens summer campaign WD (degrees) WS (m/s) RH (%) Tair Solar radiation ( C) (W/m ) /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 /7 Date Figure S. Meteorological conditions during the Athens summer campaign (hourly averages) Acetone Acetone.. Acetone Acetic acid Toluene, Xylenes Isoprene, MVK+MACR, MEK /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date Acetic acid Formic acid + Ethanol Acetonitrile mz9#1 Toluene Benzene Xylenes mz9#1 Isoprene Monoterpenes mz9#1 MVK+MACR MEK Formic acid - Ethanol, Acetonitrile Benzene Monoterpenes Figure S. VOC time series for the Athens summer campaign (hourly averages). All values are in ppb.

6 BC (µg m - ) NO x (ppb) 1 1 BC NO x O (ppb) O /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date Figure S7. O, NO x and BC time series for the Athens summer campaign (hourly averages) NOx O BC. NOx (ppb)... : : 9: 1: 1: 1: 1: Time (h) O (ppb). BC (µg/m - ) Figure S. Diurnal profiles (median values of hourly averages) of nitrogen oxides (NO x ), black carbon (BC) and ozone (O ) during the Athens summer campaign.

7 . Athens winter campaign WD (degrees) WS (m/s) RH (%) Tair ( C) /1 1/1 1/1 1/1 1/1 /1 /1 /1 /1 /1 /1 1/ / / Date Figure S9. Meteorological conditions for the Athens winter campaign (hourly averages). Wind speed m/s Wind Speed (m/s) A B Figure S1. (A) Rose plots during the Athens winter campaign and (B) rose plots only during biomass burning periods ( minute averages). 7

8 Acetonitrile Acetone Acetic acid Toluene, Xylenes Isoprene, MVK+MACR Acetonitrile MEK Acetone Acetic acid Formic acid, Ethanol mz9#1 Toluene Benzene Xylenes mz9#1. Isoprene 9. Monoterpenes.. MVK+MACR mz9#1. 1/1 1/1 1/1 1/1 1/1 /1 /1 /1 /1 /1 /1 1/ / / MEK Acetone Formic acid, Ethanol Benzene Monoterpenes Date Figure S11. VOC time series for the Athens winter campaign (hourly averages). All values are in ppb. NO x (ppb) CO (ppm) SO (ppb) O (ppb) CO (ppm) BC (µg m - ) BC CO O SO CO NOx Date (1) January February Figure S1. NO x, CO, SO, O, CO and BC time series for the Athens winter campaign (hourly averages).

9 CO (ppm) O BC SO CO NOx CO : : 9: 1: 1: 1: 1: Time (h) O, NOx (ppb). BC SO,CO (µg/m - )(ppb,ppm) Figure S1. Diurnal profiles (median values) of nitrogen oxides (NO x ), black carbon (BC), ozone (O ), sulfur dioxide (SO ), carbon monoxide (CO) and carbon dioxide (CO ) during the Athens winter campaign. 9

10 .1 Periods of intense biomass burning In order to select periods where biomass burning dominated the particulate and gas phase composition, daytime measurements were excluded, since contribution from traffic especially during morning rush hours is expected to influence the results. Measurements obtained only during nighttime (1:-: LT) were selected. For these nighttime measurements, background levels for acetonitrile were estimated based on the minimum acetonitrile, CO and CO concentrations. For the above clean periods the average value and standard deviation were estimated. The average acetonitrile value plus six times its standard deviation (=. ppb) was used as a limit. Periods with acetonitrile levels above this limit were characterized as biomass burning periods. Biomass burning periods with duration more than min were used for all the corresponding analyses in this work. Table S. Burning periods that met the criteria set for the Athens winter campaign. Duration Acetonitrile Acetonitrile Start End (hh:mm) average (ppb) sd (ppb) 1/1/1 19: 11/1/1 : : /1/1 1: 1/1/1 : 1:.. 1/1/1 : 1/1/1 : : /1/1 1: 1/1/1 : 11:.. 1/1/1 1: 1/1/1 : :..1 /1/1 : /1/1 : 7:.1. /1/1 :1 /1/1 1: :.9.1 /1/1 : 9/1/1 1: :.7.7 9/1/1 : 9/1/1 : :.. 1//1 1: 1//1 : 1:.7.1 //1 : //1 : 7:..1 //1 : //1 : 7:..1 1

11 Figure S1. Scatter plots of acetonitrile versus particulate and gas species (BC, CO, levoglucosan (AMS m/z ), benzene, toluene, xylenes, isoprene, MVK&MACR and monoterpenes) for the Athens winter campaign. Blue points indicate the overall measurement period. Black points indicate biomass burning periods. Overall R values show the correlation of the species with acetonitrile for the overall measurement period. BB R values show the correlation of the species with acetonitrile only for the biomass burning periods. 11

12 . Patras summer campaign - PMF Analysis.1. Selection of the Number of factors i a. Σ j e ij b. Σ j e ij c. Σ j e ij /Σ j x ij factor factor d. Σ j e ij /Σ j x ij.9.. e. Σ j (e ij /s ij ) /(Q.exp) 1 1/ 1/ 1/ 1/ / / / / Date 1 ii a. Σ j e ij b. Σ j e ij c. Σ j e ij /Σ j x ij factor factor d. Σ j e ij /Σ j x ij.9.. e. Σ j (e ij /s ij ) /(Q.exp) 1 1/ 1/ 1/ 1/ / / / / Date 1 1

13 iii a. Σ j e ij b. Σ j e ij c. Σ j e ij /Σ j x ij d. Σ j e ij /Σ j x ij e. Σ j (e ij /s ij ) /(Q.exp) / 1/ 1/ 1/ / / / / Date 1 factor factor iv a. Σ j e ij - b. Σ j e ij. c. Σ j e ij /Σ j x ij. -.. d. Σ j e ij /Σ j x ij. 1 e. Σ j (e ij /s ij ) /(Q.exp) 1/ 1/ 1/ 1/ / / / / Date 1 factor factor Figure S1. Selection of the number of factors for the Patras summer campaign. Comparison between model residuals E= X-GF (i) for 1-factor (black lines) and -factors (red lines) PMF solution, (ii) for - factors (red lines) and -factors (green lines) PMF solution, (iii) for -factor (green lines) and -factors (blue lines) PMF solution and (iv) for -factors (blue lines) and -factors (magenta lines) PMF solution. The model residuals were calculated as sums of (a) residuals, (b) the absolute value of residuals, (c) residuals relative to total VOCs, (d) absolute value of residuals relative to total VOCs, and (e) squared, uncertainty-weighted (scaled) residuals, Q(t)=E(t)/S(t), relative to expected values, Qexp(t). The model residuals were estimated using the PMF evaluation tool, PET, by Ulbrich et al. (9). The structure in the residuals were decreased significantly in the p = solution compared to the p =1 solution. Comparing the and factor solutions the residuals had a significant decrease from the p= to the p= solution. A smaller decrease was observed for the p= to p= solution and a minimal decrease from the p= to p= solution. A factor solution was selected. 1

14 . Q/Q expected Current solution 1 Number of factors 7 Figure S1. Q/Q expected versus the number of the factors for the Patras summer campaign.. Evaluation of solutions from the Patras summer campaign PMF in respect to the number of factors..1 factor solution - f peak =. Factor's mixing ratio (ppb) BVOC OVOC BVOC 17 OVOC Factor's fraction of signal 1 1. b-ovoc b-ovoc Time (h) 1 1 mass to charge ratio Figure S17. Diurnal profile and m/z distribution for the Patras summer campaign for the factor solution. 1

15 Factor's mixing ratio (ppb) BVOC OVOC b-ovoc 1/ 1/ 1/ 1/ / / / Date Figure S1. Time series of the factors for the Patras summer campaign... factor solution - f peak =.. (Proposed solution) Factor's mixing ratio (ppb) BVOC BC OVOC b-ovoc 1/ 1/ 1/ 1/ / / / Date BC (µg m - ) Figure S19. Patras summer campaign VOC factor time series. The BC concentration is also shown along with factor. The R between to BC was.. 1

16 .. factor solution - f peak =. Factor's mixing ratio (ppb) BVOC-1 BVOC- OVOC b-ovoc Time (h) BVOC mass to charge ratio BVOC-1 17 OVOC b-ovoc Factor's fraction of signal Figure S. Diurnal profile and m/z distribution for the Patras summer campaign for the factor solution. Factor's mixing ratio (ppb) BVOC-1 BVOC- OVOC b-ovoc 1/ 1/ 1/ 1/ / / / Date Figure S1. Time series of the factors for the Patras summer campaign. 1

17 . F peak selection for the Patras summer campaign.. Current solution Q/Q expected f peak Figure S. f peak selection for Patras summer campaign. Q/Q expected for f peaks - to for a factor solution. Values are stable between the f peak -. and.. 17

18 i).. BVOC.1. Factor's fraction of signal OVOC b-ovoc fpeak -1. fpeak. fpeak ii) Figure S. Other solutions for different fpeak values for the Patras summer campaign. (i) m/z contribution to the factors as a fraction of signal for each factor. Solutions for f peak of -1.,. and 1. are presented with green, red and blue color respectively. For the f peak =1. solution all the acetone (m/z 9) is attributed to factor OVOC and all the acetic acid (m/z 1) is attributed to factor b-ovoc. (ii) Diurnal profiles (median values) of the factors for f peak values of., -1. and 1.. Diurnal profiles are similar to the presented factor solutions with the exception of the OVOC factor. This is mainly because of the contribution of acetone (m/z 9) that has been apportioned exclusively to this factor for an f peak of 1. compared to the other solutions. The diurnal profile of the f peak solution of 1. is similar to the acetone (m/z 9) diurnal profile. 1

19 . Wind direction dependence of the PMF factors BVOC ppb ppb OVOC ppb b-ovoc ppb Figure S Rose plots for wind direction, and the PMF factors for values above the 7% percentile. 19

20 . Athens summer campaign - PMF Analysis.1. Selection of the number of factors i 1 factor factor 1 a. Σ j e ij b. Σ j e ij c. Σ j e ij /Σ j x ij d. Σ j e ij /Σ j x ij e. Σ j (e ij /s ij ) /(Q.exp) /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date 1 ii a. Σ j e ij - 9 b. Σ j e ij. c. Σ j e ij /Σ j x ij. -.. d. Σ j e ij /Σ j x ij. e. Σ j (e ij /s ij ) /(Q.exp) 1 factor factor /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date 1 iii a. Σ j e ij - 9 b. Σ j e ij. c. Σ j e ij /Σ j x ij. -.. d. Σ j e ij /Σ j x ij. e. Σ j (e ij /s ij ) /(Q.exp) 1 /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date 1 factor factor

21 iv a. Σ j e ij - b. Σ j e ij. c. Σ j e ij /Σ j x ij. -.. d. Σ j e ij /Σ j x ij. 1 e. Σ j (e ij /s ij ) /(Q.exp) /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date 1 factor factor v a. Σ j e ij - b. Σ j e ij. c. Σ j e ij /Σ j x ij. -.. d. Σ j e ij /Σ j x ij. 1 e. Σ j (e ij /s ij ) /(Q.exp) /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date 1 factor factor Figure S. Selection of the number of factors for the Athens summer campaign. Comparison between model residuals E= X-GF (i) for 1-factor (black lines) and -factors (red lines) PMF solution, (ii) for - factors (red lines) and -factors (green lines) PMF solution, (iii) for -factor (green lines) and -factors (blue lines) PMF solution, (iv) for -factors (blue lines) and -factors (magenta lines) PMF solution and (v) for -factors (magenta lines) and -factors (light green lines) PMF solution. The model residuals were calculated as sums of: (a) residuals, (b) the absolute value of residuals, (c) residuals relative to total VOCs, (d) absolute value of residuals relative to total VOCs, and (e) sum of squared, uncertainty-weighted (scaled) residuals, Q(t)=E(t)/S(t), relative to expected values, Qexp(t). A factor solution was selected. 1

22 Q/Q expected Current solution 1 Number of factors 7 9 Figure S. Q/Q expected versus the number of the factors for the Athens summer campaign.. Evaluation of solutions from the Athens summer campaign PMF in respect to the number of factors...1 factor solution - f peak =.. Factor's mixing ratio (ppb) TERP BVOC OVOC Time (h) mass to charge ratio 11 TERP 17 BVOC 1 17 OVOC Factor's fraction of signal Figure S7. Diurnal profile and m/z distribution for the Athens summer campaign for the factor solution.

23 TERP Factor's mixing ratio (ppb) BVOC OVOC /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date Figure S. Time series of the factors for the Athens summer campaign.... factor solution - f peak =. for Athens summer campaign. Factor's mixing ratio (ppb) /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date TERP BVOC BC OVOC-1 OVOC- Nitrate BC (µg m - ) Nitrate (µg m - ) Figure S9. Athens summer campaign PMF. Factors time-series and correlations with other species. Correlation between factor and BC was. (R ). Factor OVOC- correlates with AMS s NO (R =.).

24 ... factor solution - f peak =. for Athens summer campaign Factor's mixing ratio (ppb) 9 9 IND TERP BVOC OVOC-1 OVOC Time (h) 7 9 IND BVOC TERP 17 OVOC-1 OVOC- 11 mass to charge ratio Factor's fraction of signal Figure S. Diurnal profile and m/z distribution for the Athens summer campaign for the factor solution. Factors mixing ratio (ppb) IND TERP BVOC OVOC-1 OVOC- /7 /7 /7 1/7 1/7 1/7 1/7 1/7 /7 /7 /7 /7 Date Figure S1. Time series of the factors for the Athens summer campaign. The factors proposed by this solution include an additional one (factor IND) that mainly contains toluene and some smaller VOCs. This factor is elevated during the day and could be related to industrial processes and/or traffic.

25 . F peak selection for the Athens summer campaign.. Current solution Q/Q expected F peak Figure S. f peak selection for the Athens summer campaign. Q/Q expected for f peak - to for the factor solution. Values are stable between f peak -. and..

$i). Factor's fraction of signal.....1.1...1.1..........1. TERP BVOC OVOC-1 OVOC- fpeak -. fpeak. fpeak 1. 7 9 1 9 71 7 7 77 79 1 7 9 9 99 11 1 17 11 1111 191 1719 111 ii) Figure S.$

26 i). Factor's fraction of signal TERP BVOC OVOC-1 OVOC- fpeak -. fpeak. fpeak ii) Figure S. Solutions for other f peak values for the Athens summer campaign. (i) M/z contribution to the factors as a fraction of signal for each factor. Solutions for fpeak of -.,. and 1. are presented with green, red and blue color respectively. (ii) Diurnal profiles of the factors for f peak solutions of -.,. and 1.. Diurnal profiles follow the same trend in all cases.

27 . Wind direction dependence of the PMF factors ppb TERP ppb OVOC-1 ppb BVOC ppb OVOC- ppb Figure S. Rose plots for wind direction, and the PMF factors for values above the 7% percentile. 7

28 7. Athens winter campaign - PMF Analysis 7.1 Selection of the Number of factors for the Athens winter campaign i a. Σ j e ij b. Σ j e ij c. Σ j e ij /Σ j x ij d. Σ j e ij /Σ j x ij e. Σ j (e ij /s ij ) /(Q.exp) 1 1/1 1/1 19/1 /1 /1 /1 1/1 / / Date 1 1 factor factor ii a. Σ j e ij b. Σ j e ij c. Σ j e ij /Σ j x ij d. Σ j e ij /Σ j x ij. e. Σ j (e ij /s ij ) /(Q.exp) 1 1/1 1/1 19/1 /1 /1 /1 1/1 / / Date 1 factor factor iii a. Σ j e ij b. Σ j e ij c. Σ j e ij /Σ j x ij d. Σ j e ij /Σ j x ij. 1 e. Σ j (e ij /s ij ) /(Q.exp) 1 factor factor 1/1 1/1 19/1 /1 /1 /1 1/1 / / Date 1

29 iv a. Σ j e ij b. Σ j e ij factor factor c. Σ j e ij /Σ j x ij d. Σ j e ij /Σ j x ij e. Σ j (e ij /s ij ) /(Q.exp) /1 1/1 19/1 /1 /1 /1 1/1 / / Date 1 v.. a. Σ j e ij b. Σ j e ij.1 c. Σ j e ij /Σ j x ij d. Σ j e ij /Σ j x ij. e. Σ j (e ij /s ij ) /(Q.exp) 1/1 1/1 19/1 /1 /1 /1 1/1 / / Date 1 factor factor Figure S. Selection of the number of factors for the Athens summer campaign. Comparison between model residuals E= X-GF (i) for 1-factor (black lines) and -factors (red lines) PMF solution, (ii) for - factors (red lines) and -factors (green lines) PMF solution, (iii) for -factor (green lines) and -factors (blue lines) PMF solution, (iv) for -factors (blue lines) and -factors (magenta lines) PMF solution, and (v) for -factors (magenta lines) and -factors (light green lines) PMF solution. The model residuals were calculated as sums of: (a) residuals, (b) the absolute value of residuals, (c) residuals relative to total VOCs, (d) absolute value of residuals relative to total VOCs, and (e) squared, uncertainty-weighted (scaled) residuals, Q(t)=E(t)/S(t), relative to expected values, Qexp(t). A factor solution was selected. 9

Q/Qexpected 1 Current solution 1 7 9 1 Number of factors Figure S. Q/Q expected versus the number of the factors for the Athens winter campaign. 7. Evaluation of solutions from the Athens winter campaign PMF 7.

30 Q/Qexpected 1 Current solution Number of factors Figure S. Q/Q expected versus the number of the factors for the Athens winter campaign. 7. Evaluation of solutions from the Athens winter campaign PMF 7..1 factor solution - f peak =. for Athens winter campaign Figure S7. Diurnal profile and m/z distribution for the Athens winter campaign for the factor solution.

31 Factor's mixing ratio (ppb) 1 BBVOC IND OVOC 1 1/1 1/1 1/1 19/1 /1 /1 /1 1/1 / / Date Figure S. Time series of the factors for the Athens winter campaign factor solution - f peak =. for the Athens winter campaign (selected solution) Factor's mixing ratio (ppb) 1 BBVOC IND OVOC OVOC- 1 1/1 1/1 1/1 19/1 /1 /1 /1 1/1 / / Date Figure S9. Time series of the factors for the Athens winter campaign. 1

32 7... factor solution f peak =. for Athens winter campaign Figure S. Diurnal profile and m/z distribution for the Athens winter campaign for the factor solution. 7.. PMF analysis for the Athens winter campaign including the first day. Air temp. ( o C) Factor concentration (ppb) 1 1 1/1 1/1 1/1 19/1 /1 /1 /1 1/1 / / 1 1/1 1/1 1/1 19/1 /1 /1 /1 1/1 / / Date 1 BBVOC-1 BBVOC- Figure S1. Timeseries of temperature, BBVOC-1, and BBVOC- for the factor solution of the Athens winter campaign (including fist day).

$OVOC- 1 1 mass to charge ratio..1...1.....1...1..... Factor's fraction of signal Figure S.$

33 Factor's mixing ratio (ppb) BBVOC-1 BBVOC- IND OVOC-1 OVOC Time (h) 9 BBVOC BBVOC IND OVOC-1 OVOC- 1 1 mass to charge ratio Factor's fraction of signal Figure S. Diurnal profile and m/z distribution for the Athens winter campaign (including first day) for the factor solution. Figure S. Species percentage (%) attributed to the PMF factors for Athens winter campaign (including first day) for the factor solution.

34 7. F peak selection for Athens winter campaign. 1. Current solution Q/Qexpected f Peak Figure S. f peak selection. Q/Q expected for f peak - to for the factor solution for Athens winter campaign. Values are stable between the f peak -. and..

35 i) Factor's fraction of signal BBVOC IND OVOC-1 fpeak -1. fpeak. fpeak OVOC ii) Factors mixing ratio (ppb) BBVOC IND OVOC-1 OVOC- : : 9: 1: 1: 1: 1: Time (hh:mm) fpeak -1. fpeak. fpeak 1. Figure S. Other f peak solutions for the Athens winter campaign. (i) M/z contribution to the factors as a fraction of signal for each factor. Solutions for f peak of -1.,. and 1. are presented with green, red and blue color respectively. (ii) Diurnal profiles of the factors for the above f peak solutions.

36 7. Wind direction dependence of the PMF factors OVOC-1 ppb IND ppb BBVOC ppb ppb OVOC- ppb Figure S. Rose plots for wind direction, and the PMF factors for values above the 7% percentile

37 . PMF overview Estimated (PMF) total VOC concentration (ppb) 1 a Patras summer campaign 1 Observed total VOC concentration (ppb) Estimated (PMF) total VOC concentration (ppb) 1 b Athens summer campaign 1 Observed total VOC concentration (ppb) Estimated (PMF) total VOC concentration (ppb) 1 1 c Athens winter campaign 1 1 Observed total VOC concentration (ppb) Figure S7. Predicted (PMF) vs observed total VOC concentrations for the three campaigns. References Christian, T.J., Kleiss, B., Yokelson, R.J. and Holzinger, R.: Comprehensive laboratory measurements of biomass-burning emissions:. First intercomparison of open-path FTIR, PTR-MS, and GC- MS/FID/ECD. Journal of Geophysical Research, 19, D11, doi: 1.19/JD7,. DeGouw, J. A., Goldan, P. D., Warneke, C., Kuster, W. C., Roberts, J. M., Marchewka, M., Bertman, S. B., Pszenny, A. A. P., and Keene, W. C.: Validation of proton transfer reaction-mass spectrometry (PTR-MS) measurements of gas-phase organic compounds in the atmosphere during the New England Air Quality Study (NEAQS) in. Journal of Geophysical Research, 1,, doi: 1.19/JD,. DeGouw, J. and Warneke, C.: Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry. Mass Spectrometry Reviews,, 7, 7. Holzinger, A., Lee, A., Paw, K.T., and Goldstein, A.H.: Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds. Atmos. Chem. Phys.,, 7 7, a. Holzinger, R., Williams, J., Salisbury, G. Klupfel, dereus, T., Traub, M., Crutzen, P. and Lelieveld, J.: Oxygenated compounds in aged biomass burning plumes over the Eastern Mediterranean: evidence for strong secondary production of methanol and acetone. Atmos. Chem. Phys.,, 9, b. 7

38 Karl, T., Crutzen, P.J., Mandl, M., Staudinger, M., Guenther, A., Jordan,A., Fall, R. and Lindinger, W.: Variability-lifetime relationship of VOCs observed at the Sonnblick Observatory estimation of HO-densities. Atmospheric Environment, 7, 1. Karl, T., Jobson, T., Kuster, W.C.,Williams, E., Stutz, J., Shetter, R., Hall, S.R., Goldan, P., Fehsenfeld, F. and Lindinger, W.: Use of proton-transfer-reaction mass spectrometry to characterize volatile organic compound sources at the La Porte super site during the Texas Air Quality Study. J Geophysical Res. 1,, doi:1.19/jd,. Karl, T., Christian, T., Yokelson, R., Artaxo, P., Hao W. and Guenther, A.: The Tropical Forest and Fire Emissions Experiment: method evaluation of volatile organic compound emissions measured by PTR-MS, FTIR, and GC from tropical biomass burning. Atmos. Chem. Phys., 7, 97, 7. Lindinger, W., Hansel, A. and Jordan, A.: On-line monitoring of volatile organic compounds at pptv levels by means of Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) Medical applications, food control and environmental research. International Journal of Mass Spectrometry and Ion Processes. 17, 191-1, 199. Rinne, J., Ruuskanen, T.M., Reissell, A., Taipale, R., Hakola, H. and Kulmala, M.: On-line PTR-MS measurements of atmospheric concentrations of volatile organic compounds in a European boreal forest ecosystem. Boreal Environment Research. 1, -,. Ulbrich, I. M., Canagaratna, M. R., Zhang, Q., Worsnop, D. R., and Jimenez, J. L.: Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data, Atmos. Chem. Phys., 9, 91 91, 9.

Supplement for Understanding primary and secondary sources of. ambient carbonyl compounds in Beijing using the PMF model

1 2 3 4 5 6 7 8 9 Supplement for Understanding primary and secondary sources of ambient carbonyl compounds in Beijing using the PMF model W. T. Chen 1, M. Shao 1, S. H. Lu 1, M. Wang 1, L. M. Zeng 1, B.