Supplementary information

Wood burning pollution in southern Chile: PM2.5 source apportionment using CMB and molecular markers

Ana M. Villalobos(1,4), Francisco Barraza(2), Héctor Jorquera(1)* and James J. Schauer(3)

(1) Departamento de Ingeniería Química y Bioprocesos, Pontificia Universidad Católica de Chile, Avda. Vicuña Mackenna 4860, Santiago 7820436, Chile

(2) Instituto de Geografía, Pontificia Universidad Católica de Chile, Avda. Vicuña Mackenna 4860, Santiago 7820436, Chile

(3) Environmental Chemistry and Technology Program, University of Wisconsin-Madison, 660 North Park Street, Madison, WI 53706, USA

(4) Dirección de Investigación Científica y Tecnológica UC (DICTUC), Avda. Vicuña Mackenna 4860, Santiago 7820436, Chile

*Corresponding Author: Phone: (56-2) 354-4421; FAX: (56-2) 354-5803; E-mail: jorquera@ing.puc.cl

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Figures

Figure 1. Map of the urban area of Temuco, showing the three ambient monitoring sites (LE, MF, PLC), the locations of previous monitoring campaigns in Temuco: K (Kavouras et al., 2001), T (Tsapakis et al, 2002), C (Cereceda-Balic et al, 2012) and D (Diaz-Robles et al, 2014) and the location of the present monitoring campaign (P).

Figure 2. Comparison of ambient PM2.5 campaign measurements with data from a continuous air quality monitor (LE). The 1:1 line is included for comparison purposes.

Figure 3. Hourly profiles of wind speed during the 8 weeks analyzed in Temuco.

Figure 4. Daily measurements of a) PM2.5, b) organic carbon and c) elemental carbon for the winter campaign in Temuco (g/m3).

Figure 5. Plot of organic mass PM2.5 (Teflon PM2.5 – EC – ions – dust) against organic carbon (OC) for all daily ambient filter samples.

Figure 6. Box plots of hourly wind speed, ambient PM2.5, temperature and predicted particulate fraction of organic aerosol (XP) during the campaign.

Figure 7. Correlation between "CMB other" and a) diacids b) 2-hydroxy-4-isopropyl adipic acid and c) phthalic acid and its isomers.

Figure 8. HYSPLIT 24-hour back trajectories for each campaign week. The monitoring site is denoted with an ‘o’ symbol.

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Figure 1.

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y = 1.006x - 5.94R² = 0.958

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0 50 100 150 200 250BAM-MMA 24 h PM2.5, g/m3

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Figure 2.

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Wind speed daily profile

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Figure 3.

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Figure 4.

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y = 1.50xR² = 0.94

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Figure 5.

Figure 6.

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R² = 0.6936

R² = 0.7639

R² = 0.6033

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Dicarboxylic acids 2-hydroxy-4-isopropyladipic Acid Phthalic acidsO

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CMB Other, g/m3

Figure 7.

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Figure 8.

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Tables

Table 1. Source profiles used for the CMB model.

Vegetative detritus

µg/µg OC

UNC Wood smoke

µg/µg OC

UNC Diesel emission µg/µg OC

UNC Coal combustion µg/µg OC

UNC

EC 2.90E-02 5.80E-03 1.49E-02 1.49E-03 2.56E+00 2.34E-01 4.19E-02 2.10E-03A27 2.54E-03 5.07E-04 0.00E+00 0.00E+00 1.13E-04 2.26E-05 4.96E-04 9.92E-05A28 7.24E-04 1.45E-04 0.00E+00 0.00E+00 9.52E-05 1.90E-05 1.44E-04 2.88E-05A29 1.84E-02 3.68E-03 0.00E+00 0.00E+00 6.52E-05 1.31E-05 1.49E-04 2.98E-05A30 1.34E-03 2.68E-04 0.00E+00 0.00E+00 0.00E+00 1.00E-08 5.28E-05 1.06E-05A31 2.93E-02 5.86E-03 0.00E+00 0.00E+00 1.52E-04 3.04E-05 1.90E-05 3.80E-06A32 2.34E-03 4.68E-04 0.00E+00 0.00E+00 3.97E-05 7.94E-06 2.13E-05 4.26E-06A33 1.43E-02 2.86E-03 0.00E+00 0.00E+00 8.27E-06 1.66E-06 0.00E+00 1.00E-08A34 2.79E-04 5.57E-05 0.00E+00 0.00E+00 0.00E+00 1.00E-08 0.00E+00 1.00E-08LEVOG 0.00E+00 1.00E-08 7.60E-02 7.60E-03 0.00E+00 1.00E-08 1.30E-02 2.60E-03ABBCHL 0.00E+00 1.00E-08 0.00E+00 0.00E+00 7.43E-06 1.49E-06 0.00E+00 1.00E-08SITO 0.00E+00 1.00E-08 0.00E+00 0.00E+00 6.37E-06 1.27E-06 0.00E+00 1.00E-08TNOHO 0.00E+00 1.00E-08 0.00E+00 0.00E+00 6.28E-06 1.26E-06 1.77E-04 3.54E-05B17NHO 0.00E+00 1.00E-08 0.00E+00 0.00E+00 3.62E-05 7.24E-06 2.66E-04 5.32E-05A17HOP 0.00E+00 1.00E-08 0.00E+00 0.00E+00 1.65E-05 3.30E-06 1.50E-04 3.00E-05PICENE 0.00E+00 1.00E-08 0.00E+00 0.00E+00 0.00E+00 1.00E-08 9.89E-04 1.98E-04BZBFLU 0.00E+00 1.00E-08 1.10E-04 1.10E-05 2.07E-05 4.14E-06 3.78E-03 7.56E-04BZKFLU 0.00E+00 1.00E-08 1.30E-04 1.30E-05 2.90E-05 5.80E-06 4.67E-04 9.34E-05BZEPYR 0.00E+00 1.00E-08 7.90E-05 7.90E-06 3.40E-05 6.79E-06 3.89E-03 7.78E-04INDPYR 0.00E+00 1.00E-08 2.70E-05 2.70E-06 1.15E-07 2.93E-08 1.13E-03 2.26E-04BZGHPL 0.00E+00 1.00E-08 7.20E-05 7.20E-06 6.22E-06 1.25E-06 1.96E-03 3.92E-04

Compound codes:

EC Elemental carbonA27 HeptacosaneA28 OctacosaneA29 NonacosaneA30 TriacontaneA31 HentriacontaneA32 DotriacontaneA33 TritriacontaneA34 TetratriacontaneLEVOG LevoglucosanABBCHL ABB-20R-C27-CholestaneSITO ABB-20R-C29-Sitostane / ABB-20S-C29-Sitostane TNOHO 17A(H)-22,29,30-TrisnorhopaneB17NHO 17B(H)-21A(H)-30-NorhopaneA17HOP 17A(H)-21B(H)-HopanePICENE PiceneBZBFLU Benzo(b)fluorantheneBZKFLU Benzo(k)fluorantheneBZEPYR Benzo(e)pyreneINDPYR Indeno(1,2,3-cd)pyreneBZGHPL Benzo(GHI)perylene

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Table 2. Wilcoxon test results (p values) for paired comparisons among ambient PM2.5 data; i.e., yearly measurements at three sites within the Temuco metropolitan zone.

Year Comparison LE - MF Comparison LE - PLC Comparison MF-PLC2009 0.127 NA NA2010 1.3×10-4 NA NA2011 0.341 NA NA2012 0.990 0.072 2.8×10-6

2013 0.221 0.328 0.6852014 0.612 0.003 3.3×10-4

2015 0.081 0.008 2.4×10-5

2009-2016 0.058 4.1×10-6 2.2×10-9

Table 3. Reduced major axis (RMA) regressions among ambient PM2.5 measured at three sites within the Temuco metropolitan zone. Statistical parameters listed with their central estimate values and 95% confidence intervals (between parentheses).

Variables Intercept (g/m3) Slope R2

LE – MF 0.13 (-1.13, 1.29) 0.917 (0.871, 0.967) 0.729 (0.693, 0.767)LE – PLC 4.12 (2.78, 5.34) 1.054 (1.005, 1.107) 0.811 (0.781, 0.845)MF – PLC 3.83 (2.33, 5.30) 1.114 (1.056, 1.176) 0.741 (0.702, 0.779)

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Table 4. Source contribution to PM2.5 estimated by CMB in Temuco during winter 2014.

Week

Sampling days

(month/day)

Vegetative detritusµg/m3

Wood smokeµg/m3

Coal combustion

µg/m3

Diesel emission

µg/m3

CMB other (SOA) µg/m3

Sulfateµg/m3

Nitrate µg/m3

Ammonium µg/m3

Dust µg/m3

W1

07/15, 07/16, 07/17, 07/18,

07/19 0.30 18.25 1.94 1.63 22.17 1.63 0.91 0.24 1.00

W2

07/22, 07/23, 07/24, 07/25,

07/26 0.43 16.06 4.35 2.35 54.26 1.72 1.14 0.37 1.68

W3

07/29, 07/30, 07/31, 08/01,

08/02 0.19 16.92 1.04 1.05 00.00 0.49 0.28 0.03 0.60

W4

08/05, 08/06, 08/07, 08/08,

08/09 0.31 18.22 2.43 1.71 31.58 1.00 0.74 0.10 1.07

W5

08/19, 08/20, 08/21, 08/22,

08/23 0.52 19.75 2.60 1.46 33.27 2.29 1.57 0.58 1.26

W6

08/26, 08/27, 08/28, 08/29,

08/30 0.34 17.39 2.08 1.72 23.66 1.81 0.96 0.18 1.08

W7

09/02, 09/03, 09/04, 09/05,

09/06 0.22 16.24 1.06 1.18 00.00 0.81 0.43 0.09 0.66

W8

09/09, 09/10, 09/11, 09/12,

09/13 0.34 25.17 1.96 1.85 21.04 0.82 0.73 0.14 1.24

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