Supplementary Material

Molecular Marker Characterization and Source

Appointment of Particulate Matter and Its Organic

Aerosols

Jong-Kyu Choia,d, Soo-Jin Banb, Yong-Pyo Kimc, Yong-Hee Kimd, Seung-Muk Yia,

Kyung-Duk Zoha *

a Department of Environmental Health, School of Public Health, Seoul National

University, Seoul 151-742, Korea

bNational Institute of Environmental Research, Ministry of Environment,

Incheon, 404-708, Korea

cDepartment of Environmental Science and Engineering, Ewha Womans University,

Seoul, 120-750, Korea

d Research Institute of Public Health & Environment, Incheon Metropolitan city,

Incheon, 400-036, Korea

Submitted to Chemosphere

Corresponding Author

Kyung-Duk Zoh

Tel: +82-2-880-2737

Fax: +82-2-762-2888

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Email: zohkd@snu.ac.kr

1. Supplementary Tables

The analysis methods for the particle-phase organic compounds and instrument

conditions GC×GC-TOF/MS for analyzing organic species are reported in Table S1.

More detailed descriptions about QA/QC (i.e. MDL, RSD (%), RPD (%), and recovery)

were listed in Table S2. Factor loadings from principal component analysis of organic

aerosol in PM were also listed Table S2. Table S3 shows factor loadings from principal

component analysis of organic aerosol in PM after varimax rotation. Table S4. Pearson

correlation coefficients for individual PAHs between TSP and PM2.5

The analysis methods for the particle-phase organic compounds were well

documented in the following references (Schauer et al. 2002; Sheesley et al. 2004; Choi

et al. 2012). In brief, a quarter of the each quartz filter was extracted with 50 mL of

dichloromethane, two times sonication, followed by 50 mL of hexane extraction. Before

the extraction step, surrogate standard consisting of pyrene-d10, tetracosane-d50, and

hexanoic acid-d6 were added to each sample. Insoluble particles from the extracts are

removed by filtration over a syringe filter and the intermediate filtrates are concentrated

by turbovap to the final volume of 1 mL. After final extraction, each sample was spiked

with a series of deuterated internal standards containing tetracosane-d50 and 6-PAHs

(naphthalene-d8, acenaphthene-d10, phenanthrene-d10, chrysene-d12, perylene-d12),

respectively. Half of the volume of the final extract was methylated using

diazomethane. The other half of the volume of the extract was reacted with silylation

reagent containing the mixtures of BSTFA, and 1% chlorotrimethylsilane to derivatize

COOH and OH groups to the corresponding trimethylsilyl (TMS) esters and ethers,

respectively. Individual organic compounds in PM samples were analyzed by GCGC-

TOF/MS (Hamilton et al., 2004).

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Table S1. GC and MS analysis conditions

Parameter ConfigurationInjection SplitlessInjection volume 2 μLTemperature Injection Port : 250℃

Temperature program

First column ovenRate (℃/min)

Target temp (℃) Duration (min)

Initial 60 55 300 20

Secondary column ovenRate (℃/min)

Target temp (℃) Duration (min)

Initial 70 55 315 20

He gas flow 1.2 mL/min

Column

First column :DB-5MS (cross-linked 5% phenyl methyl silicone 30m,ID;0.25mm, film thickness; 0.25μm)

Secondary column :DB-17MS (cross-linked 5% phenyl methyl silicone 1m,ID;0.18mm, film thickness; 0.18 μm)

Ionization energy EM volt (1800)Temp Transfer line : 300 , Ion source chamber : 230℃ ℃Solvent Delay (min) 3MS Data Collection Mode ScanMS Scan Range (amu) 35-600

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- Quality assurance and control (QA/QC)

Quality assurance and control (QA/QC) procedures were carried out for data

certification. The detailed QA/QC data was described in supplemental materials (Table

S2). For QA in the analysis of the samples, blank filters were simultaneously examined

using the same methods as described above. Background contamination was

periodically monitored (every 20 samples) using field blanks that were simultaneously

processed with the field samples. The background contamination was less than 5% of

the associated samples for all analytes. The relative percent difference (RPD) between

sampled concentrations was also used to evaluate the accuracy of measurement for each

pollutant and was typically within ±10 % of the standard value. The relative standard

deviation (RSD, %) expresses the standard deviation as a percentage of the mean. The

RSDs of ionic species, metallic elements, and individual organic species averaged

approximately 0.8, 1.4, and 1.4%, respectively. The method detection limit (MDL) was

calculated as three times the value of the standard deviation, obtained from seven

consecutive analyses of low level samples. The MDL values of ionic species, metallic

elements, and individual organic species were estimated to be 0.01~0.05 g/m3,

0.0005~0.004 g/m3, and 0.003~0.079 ng/m3, respectively. Recoveries of ionic species

and metallic elements were determined by spiking a standard solution into a blank filter

once every 20 samples and the recovery (%) of organic species was calculated from the

extraction recovery of the surrogate organic standards spiked. The recoveries were

estimated to be 91, 98, 80, 81, and 83% for ionic species, metallic elements, alkanes,

alkanoic acids, and polycyclic aromatic hydrocarbons (PAH), respectively.

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Table S2. Method detection limits, RSD (%), and RPD (%) of target analytes.

AnalyteMDL RSD RPDg/m3 % %

OC 0.255 2.1 1.9WSOC 0.027 0.3 0.6WIOC 0.024 4.6 0.0Na+ 0.055 1.0 2.0NH4

+ 0.021 0.2 0.3K+ 0.048 0.3 0.4Cl- 0.021 0.3 0.3NO3- 0.013 2.1 3.5SO4

2- 0.047 0.4 0.5Mg 0.002 2.1 3.6Al 0.0005 1.0 1.7P 0.003 2.7 3.6Ca 0.004 2.4 4.2Ti 0.001 1.0 1.8V 0.001 1.2 2.0Cr 0.001 1.0 1.8Mn 0.004 0.6 1.0Fe 0.002 1.7 3.0Ni 0.001 0.9 1.6Cu 0.002 1.6 2.8Zn 0.001 1.2 2.1As 0.002 1.4 2.5Se 0.002 1.7 2.9Sr 0.001 1.6 2.7Cd 0.001 1.0 1.8Sn 0.001 1.1 1.9Sb 0.002 1.4 2.4Pb 0.003 0.8 1.3

1. The method detection limit (MDL) was calculated as three times the value of the standard deviation, obtained from seven consecutive analyses of low level samples.

2. The relative standard deviation (RSD, %) expresses the standard deviation as a percentage of the mean.

3. The RPD (relative percent difference, %) was estimated from two time measurement of sample.

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Table S2. (continued)_

Analyte MDL RSD RPDng/m3 % %

Heptadecane 0.003 0.9 0.2Octadecane 0.048 0.6 1.3Nonadecane 0.011 0.7 1.2Eicosane 0.006 0.6 1.0Docosane 0.009 1.3 2.5Tetracosane 0.005 1.3 2.5Hexacosane 0.013 1.9 2.1Heptacosane 0.013 1.9 2.1Nonacosane 0.011 1.9 2.1Dotriacontane 0.009 0.7 1.0Triacontane 0.003 2.5 5.0tetratriacontane 0.004 2.5 5.0Hexanoic acid 0.069 2.7 4.8Heptanoic acid 0.049 3.0 5.2Nonanoic acid 0.050 1.5 2.6Decanoic acid 0.040 0.8 0.1Undecanoic acid 0.070 1.1 1.9Dodecanoic acid 0.058 1.3 0.8Tridecanoic acid 0.033 1.8 3.3Tetradecanoic acid 0.044 0.7 1.3Pentadecanoic acid 0.037 1.1 0.3Hexadecanoic acid 0.030 2.6 4.6Heptadecanoic acid 0.046 1.6 3.2Octadecanoic acid 0.037 0.9 0.3Nonadecanoic acid 0.046 1.3 1.8Eicosanoic acid 0.037 2.4 4.1Heneicosanoic acid 0.052 2.0 4.0Tricosanoic acid 0.058 1.2 2.4Tetracosanoic acid 0.064 2.6 5.2Butanedioic acid 0.044 1.8 3.3Pentanedioic acid 0.037 1.1 0.3Hexanedioic acid 0.030 2.6 4.6Nonanedioic acid 0.046 1.3 1.8Naphthalene 0.015 1.6 1.0Acenaphthene 0.023 0.8 1.0Acenaphthylene 0.021 0.5 0.8Fluorene 0.016 1.1 2.2Phenanthrene 0.016 1.1 2.2Anthracene 0.025 0.3 0.4Fluoranthene 0.019 0.3 0.6

Table S2. (continued)

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AnalyteMDL RSD RPDng/m3 % %

Pyrene 0.007 2.1 4.1Benzo[a]fluoranthene 0.008 1.4 2.7Benzo[b]fluoranthene 0.004 1.3 2.6Benzo[k]fluoranthene 0.003 1.3 2.6Benzo[a]pyrene 0.003 1.3 2.6Benzo[e]pyrene 0.003 1.3 2.6Benzo[b]triphenylene 0.008 2.9 5.7Benzo[ghi]perylene 0.006 1.0 1.2Chrysene 0.003 1.4 2.4Indeno[1,2,3-cd]pyrene 0.005 1.0 1.017α(H),21β(H)-(22R)-Homohopane 0.029 1.5 0.617α(H),21β(H)-(22S)-Homohopane) 0.035 0.3 0.117α(H),21β(H)-30-Norhopane 0.031 2.4 4.617α(H),21β(H)-Hopane 0.036 1.0 1.417α(H)-22,29,30-Trisnorhopane 0.070 0.8 1.5ααα 20R Cholestane 0.027 0.8 1.5ααα(20R,24R)-24-Ethylcholestane 0.079 1.6 0.1αββ 20R Cholestane 0.072 1.3 1.1αββ(20R,24R)-24-Ethylcholestane 0.054 1.3 0.1αββ(20R,24S)-24-Ethylcholestane 0.025 1.3 2.69,10-Anthracenedione 0.012 2.0 2.69H-Fluorenone 0.025 2.7 3.4Benzofuran 0.006 0.3 <0.111H-Benzo[a]fluorenone 0.005 1.3 2.57H-Benzo[c]fluorenone 0.005 1.3 2.5naphtho[1,2-c]furan 0.005 1.3 2.5Cholestol 0.014 1.2 1.9Levoglucosan 0.005 1.3 2.5Retene 0.005 1.3 2.5Squalene 0.005 1.3 2.5Dibutyl phthalate 0.005 1.3 2.5Benzothiazole 0.005 1.3 2.5Dehydroabetic acid 0.046 1.3 1.8Phenanthrene-2methyl 0.015 1.6 1.0Phenanthrene-3methyl 0.015 1.6 1.0Phenanthrene-1methyl 0.015 1.6 1.0Phenanthrene-1,7dimethyl 0.016 1.6 1.0Pyrene-1methyl 0.007 2.1 4.1Pyrene-4methyl 0.007 2.1 4.1Chrysene-1methyl 0.003 1.4 2.41,2-Benzenecaboxylic acid 0.046 1.3 1.8

Table S3. Factor loadings from principal component analysis of organic aerosol in

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PM after varimax rotation

F1 F2 F3 F4 F5 F6 F7 F8 F9 F10Combustion 1(LMW-PAHs) 0.880

Biomass burning -0.330 0.354Vegetative detritus 0.891

SOA 1 0.780SOA 2 0.322 0.819Combustion 2(HMW-PAHs) 0.859 0.355

Motor vehicle 0.808OC 0.653 0.443 0.300EC -0.364 0.319 0.528SOC 0.362 0.660 0.433POC -0.362 0.322 0.536WSOC 0.425 0.493 0.559WIOC 0.618Na -0.487 0.324 0.415NH4 0.495 0.767K 0.359 0.711Cl 0.517 0.566NO3 0.512 0.710SO4 0.743Mg 0.824Al 0.392 0.333 0.498 -0.326P 0.377 -0.352 0.398Ca 0.823Ti 0.844V 0.711Cr 0.330 0.703Fe 0.856Mn 0.317 0.752Ni -0.369 0.665Cu 0.494Zn 0.497 0.311 0.357As 0.817Pb 0.325 0.433 0.369N-HEXD 0.656N-HEPD 0.501 0.344N-OCTD 0.772 0.457N-NONAD 0.871N-EICO 0.778N-HENEI 0.865N-DOCO 0.721 0.360 0.382N-TRICO 0.625 0.314N-TETRACO 0.613 0.570N-PENTACO 0.619 0.544N-HEXACO 0.896N-HEPTACO 0.632 0.535N-OCTACO 0.858N_NONACO 0.348N_TRICO 0.865N_DOTRICO 0.866

Table S3. (continued)

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F1 F2 F3 F4 F5 F6 F7 F8 F9 F10

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FLU 0.919PYR 0.917B(A)F 0.851 0.369B(B)F 0.842 0.351B(K)F 0.653 0.359BGHIPE 0.807 0.461CHRYSN 0.888 0.331INCDPY 0.835 0.403

BA30NH 0.557 0.381

AB_HOP 0.691

HOPANE 0.678 0.350

CHOLESTANE 0.574N_HEXDA 0.428 0.688

N_HEPDA 0.350 0.569

N_OCTDA 0.301

N_NONDA 0.525N_EICOA 0.381 0.803

N_HENEICOA 0.643

N_TRICOSA 0.791N_TETRACOSA 0.353 0.8159H-FLUORENE 0.878CHOLESTEROL 0.359 0.318LOVOGUCOSAN -0.328 0.358RETENE 0.909SQUALENE 0.560 -0.312 0.323DB PHTHA 0.777

BENZOTHIO 0.408 0.313 0.493

NAPHTHFUR 0.604 0.560

BUTANDIOA 0.819PENTADIOA 0.803NONANDIOAcis-PINOIC ACID 0.358OlLEIC ACID 0.702DEHYDROABIEA 0.774 0.420CO 0.440 0.771SO2 0.442 0.553O3 -0.450 -0.592NO 0.396 0.822NO2 0.792WS -0.315 -0.505 -0.33TEMP -0.746 0.408HUMRAD -0.349 0.364 -0.338

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Table S4. Pearson correlation coefficients for individual PAHs between TSP and PM2.5

TSP PM2.5

FLUORA PYRENE B(A)F B(B)F B(K)F BGHIPE CHRYSN INCDPY FLUORA PYRENE B(A)F B(B)F B(K)F BGHIPE CHRYSN INCDPY

TSP

FLUORA 1.00 1.00** 0.99** 0.99** 0.88** 0.97** 0.99** 0.98** 0.96** 0.96** 0.55 0.84** 0.84** 0.91** 0.78** 0.55

PYRENE 　 1.00 0.99** 0.99** 0.91** 0.98** 1.00** 0.98** 0.96** 0.96** 0.57 0.85** 0.85** 0.92** 0.77** 0.52

B(A)F 　 　 1.00 0.99** 0.87** 0.98** 0.99** 0.99** 0.95** 0.95** 0.55 0.86** 0.86** 0.90** 0.74** 0.57

B(B)F 　 　 　 1.00 0.91** 0.99** 0.99** 0.99** 0.97** 0.98** 0.63* 0.88** 0.88** 0.91** 0.80** 0.60*

B(K)F 　 　 　 　 1.00 0.92** 0.92** 0.89** 0.91** 0.92** 0.72* 0.86** 0.86** 0.90** 0.72** 0.48

BGHIPE 　 　 　 　 　 1.00 0.99** 0.99** 0.94** 0.95** 0.69* 0.90** 0.90** 0.89** 0.71** 0.56

CHRYSN 　 　 　 　 　 　 1.00 0.99** 0.96** 0.96** 0.61* 0.87** 0.87** 0.92** 0.74** 0.53

INCDPY 　 　 　 　 　 　 　 1.00 0.95** 0.95** 0.64* 0.90** 0.90** 0.90** 0.71** 0.55

PM2.5

FLUORA 　 　 　 　 　 　 　 　 1.00 1.00** 0.62* 0.88** 0.88** 0.95** 0.88** 0.67*

PYRENE 　 　 　 　 　 　 　 　 　 1.00 0.67* 0.91** 0.91** 0.94** 0.86** 0.66*

B(A)F 　 　 　 　 　 　 　 　 　 　 1.00 0.79** 0.79** 0.59* 0.40 0.46

B(B)F 　 　 　 　 　 　 　 　 　 　 　 1.00 1.00 0.86** 0.67* 0.53

B(K)F 　 　 　 　 　 　 　 　 　 　 　 　 1.00 0.86** 0.67* 0.53

BGHIPE 　 　 　 　 　 　 　 　 　 　 　 　 1.00 0.79** 0.66*

CHRYSN 　 　 　 　 　 　 　 　 　 　 　 　 　 　 1.00 0.68*

INCDPY 　 　 　 　 　 　 　 　 　 　 　 　 　 　 　 1.00

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2. Supplemental figures

Fig. S1. Location of the study sites in Incheon, Korea

Fig. S2. The diagonistic factor of PMF model using 41 molecular markers only. (a) IM,

IS, and rotational freedom as a function of the factors chosen in PMF, (b) Q-value for

the different factor solutions and the change of “FPEAK” parameter.

Fig. S3. The diagonistic factor of PMF model using traditional 21items couple with 41

molecular markers. (a) IM, IS, and rotational freedom as a function of the factors

chosen in PMF, (b) Q-value for the different factor solutions and the change of

“FPEAK” parameter.

Fig. S4. Source profiles obtained from organic data (prediction ± standard deviation)

using 41organic marker species in Incheon, Korea.

Fig. S5. Timeseries plot for each source contribution to OC mass concentrationscalculated from PMF model using 41 organic marker species.Fig. S6. Source profiles obtained from TSP samples (prediction ± standard deviation)

using 63species in Incheon, Korea.

Fig. S7. Timeseries plot for each source contribution of TSP using 63species in

Incheon, Korea

Fig. S8. The source contributions (%) of identified sources to TSP mass concentrations

calculated from PMF model using 63species.

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Fig.S1. Location of the study sites in Incheon, Korea

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- PMF analysis for Organic Carbon using 41 molecular markers

PMF diagnostics (e.g., model error, Q and rotational ambiguity, rotmat) were based

on those described by Lee et al. (1999). We investigated the Q-value for different

numbers of factors and values of the rotational parameter (FPEAK), as well as

variations in the maximum individual column mean (IM), the maximum individual

column standard deviation (IS), and rotational freedom for the different factors used in

PMF models (see Fig. S2(a) and S2(b)). As the number of factors approached a critical

value, IM and IS clearly decreased. We also investigated the maximum rotmat, which

exhibited a significant increase from seven to ten factors (Figs. S2).

(a)

(b)

Fig.S2. The diagonistic factor of PMF model using 41 molecular markers only. (a) IM, IS, and rotational freedom as a function of the factors chosen in PMF, (b) Q-value for the different factor solutions and the change of “FPEAK” parameter.

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- PMF analysis for TSP using 62 compounds (traditional 21 items + 41

molecular markers)

(a)

(b)

Fig.S3.The diagonistic factor of PMF model using traditional 21items couple with 41 molecular markers. (a) IM, IS, and rotational freedom as a function of the factors chosen in PMF, (b) Q-value for the different factor solutions and the change of “FPEAK” parameter.

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Fig. S4. Source profiles obtained from organic data (prediction ± standard deviation)

using 41organic marker species in Incheon, Korea.

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Fig. S5. Timeseries plot for each source contribution to OC mass concentrations

calculated from PMF model using 41 organic marker species.

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Fig.S6. Source profiles obtained from TSP samples (prediction ± standard deviation) using 63 species in Incheon, Korea.

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Fig.S7. Timeseries plot for each source contribution of TSP using 63 species in

Incheon, Korea.

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Fig.S8. The source contributions (%) of identified sources to TSP mass

concentrations calculated from PMF model using 63 species.

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