1. Wood burning in PM10, Flanders 1 Assessment of the contribution from wood burning to the PM10 aerosol in Flanders, Belgium Willy Maenhaut 1,2, Reinhilde Vermeylen 2, Magda Claeys 2, Jordy Vercauteren 3, Christina Matheeussen 3 and Edward Roekens 3 1 Ghent University (UGent), Department of Analytical Chemistry, Krijgslaan 281, S12, 9000 Gent, Belgium 2 University of Antwerp (UA), Department of Pharmaceutical Sciences, Universiteitsplein 1, 2610 Antwerpen, Belgium 3 Flemish Environment Agency (VMM), Kronenburgstraat 45, 2000 Antwerpen, Belgium

2. Wood burning in PM10, Flanders 2 Introduction In Flanders (Belgium) we are struggling with too many exceedances of the 50 µg/m 3 daily PM10 mass limit  in the EU : only 35 exceedances per year allowed at any given location  thus, of interest to examine the cause of possible exceedances Wood burning may provide a substantial contribution to the PM10 aerosol mass, as appeared from studies in several European countries (e.g., Switzerland, Austria) Over a decade ago, Simoneit et al., AE [1999] introduced levoglucosan as an indicator for wood burning  levoglucosan (C 6 H 10 O 5 ) arises from the pyrolysis of cellulose, the main building material of wood, at temperatures higher than 300 o C  levoglucosan is accompanied by other minor stereoisomeric monosaccharide anhydrides in atmospheric aerosols, with mannosan and galactosan being the most important ones Flemish Environment Agengy (VMM) wanted to find out what the contribution from wood burning to PM10 was over a full year for 7 sites in Flanders  thereby using levoglucosan as wood burning indicator

3. Wood burning in PM10, Flanders 3 From 7 February 2010 to 6 February 2011 PM10 aerosol samples simultaneously taken every 4th day at 7 monitoring sites in Flanders, Belgium  on 47-mm diam. Pallflex quartz fibre filters Two of the sites (i.e., Gent and Borgerhout) are urban background sites; Mechelen is a suburban background site, and the other 4 sites are rural background sites, whereby Hamme and Lier were expected to be particularly impacted by biomass burning Sampling

4. Wood burning in PM10, Flanders 4 Borgerhout : at 30 m from a busy road (Plantin en Moretuslei) Most polluted of the 2 urban background sites

5. Wood burning in PM10, Flanders 5 Gent : in the Baudelo park in the North-East of the city Least polluted of the 2 urban background sites

6. Wood burning in PM10, Flanders 6 Hamme : in a rural area with individual houses In the neigbourhood of the site are several inhabitants who use wood as fuel

7. Wood burning in PM10, Flanders 7 Houtem : rural background site In the middle of an agricultural area in the polders

8. Wood burning in PM10, Flanders 8 Meteorology Of the 92 sampling days: 60 days with rain

9. Wood burning in PM10, Flanders 9 Meteorology (cont.) Wind direction mostly from South-West and North-North-East

10. Wood burning in PM10, Flanders 10 Analyses PM10 mass determined by weighing of the filters at 20 o C and 50% relative humidity [done by VMM] Organic, elemental, and total carbon [OC, EC, and TC (= OC + EC)] measured with a dual photo-detector (2PD) thermal-optical instrument from Sunset Lab  using NIOSH temperature protocol  transmission (TOT) and reflectance (TOR) simultaneously measured  TOT data retained for further evaluation Levoglucosan, mannosan, and galactosan measured by gas chromatography / mass spectrometry (GC/MS) after trimethylsilylation, using method described in Pashynska et al., J. Mass Spectrom. [2002], but  extraction with methanol  use made of a different recovery standard (RS)  and slightly modified GC temperature program employed

11. Wood burning in PM10, Flanders 11 Schematic diagram of the Sunset Laboratory TOT instrument (V = valve)

12. Wood burning in PM10, Flanders 12 ECOC1PC OC = OC1 + PC (with PC: pyrolytic carbon) : area below the blue line prior to the OC/EC split point (vertical brown line) EC : area below the blue line after the OC/EC split point

13. Wood burning in PM10, Flanders 13 Full brown line : laser transmission (T) signal  vertical full brown line : OC/EC split point for T Dashed purple line : laser reflectance (R) signal  vertical dashed purple line : OC/EC split point for R

14. Wood burning in PM10, Flanders 14

15. Wood burning in PM10, Flanders 15 Total ion current (TIC) chromatogram [relative abundance (R.A.) versus time] obtained for the sample that was collected on 23 February 2010 in Hamme. The numbered peaks are for the following compounds: 1: galactosan: 60.6 ng/cm 2 ; 2: mXP: 510 ng/cm 2 (added); 3: mannosan: 145 ng/cm 2 ; 4: levoglucosan: 826 ng/cm 2.

16. Wood burning in PM10, Flanders 16 Comparison of TOT and TOR results TOR provided systematically larger EC data than TOT  thus, TOR provided systematically lower OC data than TOT

17. Wood burning in PM10, Flanders 17 Some tendency for higher ratios at rural sites than at urban sites  exception: Houtem Some tendency for higher ratios in winter than in the other seasons

18. Wood burning in PM10, Flanders 18 TOR/TOT ratio for OC versus TC loading on filter

19. Wood burning in PM10, Flanders 19 Time series for the PM10 mass at the 7 sites Fairly good correlation between the data of the 7 sites At Gent: 3 samples in a row in July with elevated levels  these samples taken during the “Ghent City Festival”

20. Wood burning in PM10, Flanders 20 Retie (RT) Lier (LR) Mechelen (ML) Borgerhout (BO) Hamme (HA) Gent (GE) Houtem (HO)

21. Wood burning in PM10, Flanders 21 Correlation coefficients for the PM10 mass data of the 7 sites 3 "Ghent City Festival" samples excluded

22. Wood burning in PM10, Flanders 22 Time series for EC at the 7 sites EC levels highest at Borgerhout, lowest at Houtem Clearly less correlation between the data from the different sites than was the case for the PM10 mass

23. Wood burning in PM10, Flanders 23 Correlation coefficients for EC data of the 7 sites

24. Wood burning in PM10, Flanders 24 Median EC/TC ratios

25. Wood burning in PM10, Flanders 25 Time series for OC at the 7 sites Fairly good correlation between the data of the 7 sites At Gent: 3 samples in a row in July with elevated levels  these samples taken during the “Ghent City Festival”

26. Wood burning in PM10, Flanders 26 Correlation coefficients for OC data of the 7 sites 3 "Ghent City Festival" samples excluded

27. Wood burning in PM10, Flanders 27 Gent sample of 13 July 2010

28. Wood burning in PM10, Flanders 28 Gent sample of 21 July 2010

29. Wood burning in PM10, Flanders 29 Gent sample of 29 July 2010

30. Wood burning in PM10, Flanders 30 Time series for OC at the 7 sites Fairly good correlation between the data of the 7 sites At Gent: 3 samples in a row in July with elevated levels  these samples taken during the “Ghent City Festival”

31. Wood burning in PM10, Flanders 31 Median TC/PM10_mass ratios

32. Wood burning in PM10, Flanders 32 Time series for levoglucosan at the 7 sites High levels in winter & fall; low levels in spring & summer Time series for Hamme quite peculiar

33. Wood burning in PM10, Flanders 33 Correlation coefficients for levoglucosan data of the 7 sites The levoglucosan data for 5 of the 7 sites (i.e., Retie, Lier, Mechelen, Borgerhout, and Gent) are very highly correlated with each other (all r>0.9, except 0.86 between Retie and Gent)  indicating that the impact from wood burning at these 5 sites was a regional phenomenon

34. Wood burning in PM10, Flanders 34

35. Wood burning in PM10, Flanders 35

36. Wood burning in PM10, Flanders 36 Data for mannosan and galactosan A each site : mannosan and galactosan very highly correlated with each other and with levoglucosan  all r > 0.95 (except at Hamme : 0.93 between levoglucosan and mannosan) Levoglucosan/mannosan (L/M) ratio depends on the type of biomass and wood burnt  Miocene lignite54Fabbri et al., AE [2009]  Peat8.6Kourtchev et al., STE [2011]  Bituminous coal3.1Kourtchev et al., STE [2011]  US woods, fireplacesFine et al., EES [2004] − hardwoods13-24 − softwoods3.9-6.7  Austrian wood stovesSchmidl et al., AE [2008] − hardwoods14-15 − softwoods3.6-3.9

37. Wood burning in PM10, Flanders 37 Data for mannosan and galactosan The annual average L/M ratios for our 7 sampling sites ranged from 6.2 to 7.1 and there was little variation with season  suggests that softwood burning was clearly more important than hardwood burning in Flanders in 2010-2011 Schmidl et al., AE [2008] provided the following equation for estimating the %spruce burned from the L/M ratio : %spruce = (14.8 – L/M_ratio) / 0.112  this equation used to estimate the %spruce burned at our 7 sites

38. Wood burning in PM10, Flanders 38 Typically between 70 and 80% from spruce burning  little variation from site to site  little variation with season

39. Wood burning in PM10, Flanders 39 Contribution from wood burning to the OC and the PM10 mass To assess the percentage contribution from wood burning to the OC, we relied on the concentrations of 9.3% levoglucosan and 52% OC in wood smoke as given by Schmidl et al., AE [2008]  meaning that the levoglucosan level is multiplied by a factor of 5.59 (i.e., 52/9.3) to obtain the OC concentration from wood smoke Similarly, we used the conversion factor of 10.7, suggested by Schmidl et al., AE [2008], to convert our levoglucosan concentrations to PM10 mass levels due to wood smoke

40. Wood burning in PM10, Flanders 40 Time series for %OC from wood burning at the 7 sites High values in winter & fall; low levels in spring & summer Time series for Hamme quite peculiar

41. Wood burning in PM10, Flanders 41 In winter (blue) for 6 of the 7 sites : around 40% of OC, on average, from wood burning At Hamme in winter : 60% of OC, on average, from wood burning

42. Wood burning in PM10, Flanders 42 Annual medians of the % OC due to wood burning at the 7 sites

43. Wood burning in PM10, Flanders 43 Time series for %PM from wood burning at the 7 sites High values in winter & fall; low levels in spring & summer Time series for Hamme quite peculiar

44. Wood burning in PM10, Flanders 44 In winter (blue) for 6 of the 7 sites : around 10% of PM10 mass, on average, from wood burning At Hamme in winter : 22% of PM10 mass, on average, from wood burning

45. Wood burning in PM10, Flanders 45 Annual medians of the % PM due to wood burning at the 7 sites

46. Wood burning in PM10, Flanders 46 Annual medians of the % EC in PM10 at the 7 sites

47. Wood burning in PM10, Flanders 47 Wood burning is an important contributor to the OC and PM10 mass in Flanders, especially in winter  on average, 40 % of OC in winter from wood burning (60% at Hamme)  on average, 10% of PM10 mass in winter from wood burning (22% at Hamme) Since most of the exceedances of the 50 µg/m 3 daily PM10 mass limit occur in winter, reducing the wood burning emissions would help in complying with the EU limit of maximum 35 exceedances per year at any given location Wood burning smoke is a regional phenomenon in Flanders  in Hamme: nearby sources very important This study published in Sci. Total Environ.  Maenhaut et al., STE 437 (2012) 226-236 Summary and conclusions

48. Wood burning in PM10, Flanders 48

49. Wood burning in PM10, Flanders 49

50. Wood burning in PM10, Flanders 50 Mechelen : at about 1 km from the inner ring of the city Suburban background site

51. Wood burning in PM10, Flanders 51 Lier : rural site; within a radius of 1 km were two horticulture farms that used wood as fuel, but it appeared in the course of the project that one of the two farms had already stopped its activities at the start of the project

52. Wood burning in PM10, Flanders 52 Retie : rural background site In a meadow, next to a wooded park (Prinsenpark)

53. Wood burning in PM10, Flanders 53 Gent sample of 17 July 2010

54. Wood burning in PM10, Flanders 54 Gent sample of 25 July 2010

55. Wood burning in PM10, Flanders 55 Gent sample of 2 August 2010