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Article
Characterization of chromophoric water-soluble organic
matter in urban, forest and marine aerosols by HR-ToF-
AMS analysis and excitation–emission matrix spectroscopy
Qingcai Chen, Yuzo Miyazaki, Kimitaka Kawamura, Kiyoshi Matsumoto, Sean C.
Coburn, Rainer Volkamer, Yoko Iwamoto, Sara Kagami, Yange Deng, Shuhei Ogawa,
Sathiyamurthi Ramasamy, Shungo Kato, Akira Ida, Yoshizumi Kajii, and Michihiro Mochida
Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b01643 • Publication Date (Web): 11 Aug 2016
Downloaded from http://pubs.acs.org on August 12, 2016

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1 Characterization of chromophoric water-soluble organic

2 matter in urban, forest and marine aerosols by HR-ToF-
3 AMS analysis and excitation–emission matrix
4 spectroscopy
5 Qingcai Chen1, Yuzo Miyazaki 2, Kimitaka Kawamura2,3, Kiyoshi Matsumoto4, Sean Coburn5,6,7,
6 Rainer Volkamer5,6, Yoko Iwamoto8,9, Sara Kagami1, Yange Deng1, Shuhei Ogawa1,
7 Sathiyamurthi Ramasamy10, Shungo Kato11, Akira Ida10,12, Yoshizumi Kajii10,13, Michihiro
8 Mochida*1

1
9 Graduate School of Environmental Studies, Nagoya University, Nagoya 464-8601, Japan
2
10 Institute of Low Temperature Science, Hokkaido University, Sapporo 060-0819, Japan
3
11 Now at Chubu Institute for Advanced Studies, Chubu University, Kasugai 487-8501, Japan
4
12 Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi,
13 Kofu 400-8510, Japan
5
14 Department of Chemistry & Biochemistry, University of Colorado, Boulder, CO 80309-0215,
15 USA
6
16 Cooperative Institute for Research in Environmental Sciences (CIRES), University of
17 Colorado, Boulder, CO 80309-0215, USA
7
18 Now at Department of Mechanical Engineering, University of Colorado, Boulder, CO 80309-
19 0215, USA
8
20 Institute for Advanced Research, Nagoya University, Nagoya 464-8601, Japan
9
21 Now at Faculty of Science Division I, Tokyo University of Science, Tokyo 162-8601, Japan
10
22 Graduate School of Global Environmental Studies, Kyoto University, Kyoto 606-8501, Japan
11
23 Department of Applied Chemistry, Tokyo Metropolitan University, Tokyo 192-0397, Japan
12
24 Now at Seraku Co. Ltd., Tokyo 160-0023, Japan
13
25 Center for Regional Environmental Research, National Institute for Environmental Studies,
26 Tsukuba 305-8506, Japan
27 *Corresponding author e-mail: mochida.michihiro@g.mbox.nagoya-u.ac.jp
28 Phone/fax: 052-788-6157
29 Address: Department of Earth and Environmental Sciences, Graduate School of Environmental
30 Studies, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601, Japan

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31 ABSTRACT: Chromophoric water-soluble organic matter in atmospheric aerosols potentially

32 plays an important role in aqueous reactions and light absorption by organics. The fluorescence

33 and chemical-structural characteristics of the chromophoric water-soluble organic matter in

34 submicron aerosols collected in urban, forest and marine environments (Nagoya, Kii Peninsula,

35 and the tropical Eastern Pacific) were investigated using excitation-emission matrices (EEMs)

36 and a high-resolution aerosol mass spectrometer. Three types of water-soluble chromophores,

37 two with fluorescence characteristics similar to those of humic-like substances (HULIS-1 and

38 HULIS-2) and one with fluorescence characteristics similar to those of protein compounds

39 (PLOM), were identified in atmospheric aerosols by parallel factor analysis (PARAFAC) for

40 EEMs. We found that the chromophore components of HULIS-1 and -2 were associated with

41 highly and less-oxygenated structures, respectively, which may provide a clue to understanding

42 the chemical formation or loss of organic chromophores in atmospheric aerosols. Whereas

43 HULIS-1 was ubiquitous in water-soluble chromophores over different environments, HULIS-2

44 was abundant only in terrestrial aerosols and PLOM was abundant in marine aerosols. These

45 findings are useful for further studies regarding the classification and source identification of

46 chromophores in atmospheric aerosols.

47 KEYWORDS: chromophores, organic aerosol, chemical characteristics, aerosol mass

48 spectrometry, excitation-emission matrices

49

50

51

52

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53 INTRODUCTION

54 Water-soluble organic matter (WSOM) constitutes a large fraction of the organics in

55 submicron aerosols in the atmosphere and can affect the role of aerosols in terms of climate

56 processes and human health.1-6 Chromophoric water-soluble organic matter is a component of

57 WSOM that has the ability to absorb sunlight at visible and near-ultraviolet (UV) wavelengths

58 and takes part in photoinitiated reactions. The chromophoric water-soluble organic matter

59 therefore potentially plays important roles in some aqueous reactions of organics in aerosols and

60 thus in the radiative balance of Earth.7-10 Although the origin, composition and chemistry of

61 WSOM in aerosols have attracted great attention over the past decade, the characteristics of the

62 chromophoric fraction of water-soluble organic matter are poorly understood. 1-6

63 Brown carbon in atmospheric aerosols, which contain chromophoric water-soluble organic

64 matter, is primarily emitted from biomass burning and is formed secondarily.11-13 Chromophoric

65 organic matter in aerosol can be formed via a variety of reaction pathways. Nitrophenols are

66 major chromophores in chamber-generated secondary organic aerosols from toluene

67 photooxidation in the presence of NOx.14 The reactions of carbonyl compounds with amines and

68 ammonia can form nitrogen-containing chromophoric organics.15-20 In view of its role in the

69 atmosphere, an important characteristic of chromophoric organic matter is its sensitivity to light.

70 Photoinitiated reactions with chromophoric organic matter include both degradation and

71 polymerization.21-23 Substantial photodegradation of chromophoric organic matter in rainwater

72 and laboratory-generated solutions containing brown carbon occurs when the matter is exposed

73 to simulated sunlight.21, 24, 25

Chromophoric organic matter has the potential to be in triplet

74 excited states through the capture of the excitation energy from photons and thus plays a

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75 significant role in aqueous-phase oxidation of organics.8, 10 The triplet state of 1-nitronaphthalene

76 reacts with phenol to form humic-like substances (HULIS).26

77 Excitation-emission matrix (EEM) fluorescence spectroscopy is a commonly used technique

78 to investigate the optical and structural characteristics of chromophores that are responsible for

79 the light absorption and fluorescence by complex organic matter. Although the method has been

80 widely applied to the characterization of chromophoric water-soluble organic matter in terrestrial

81 and oceanic systems,27, 28

it has not been extensively used in atmospheric aerosol research.29-31

82 Chromophore components associated with HULIS and protein-like organic matter (PLOM) have

83 been statistically determined for complex organic matter in terrestrial and oceanic systems as

84 well as atmospheric aerosols by parallel factor analysis (PARAFAC) for EEMs. Although

85 chromophoric water-soluble organic matter in terrestrial and oceanic systems are relatively well

86 characterized by EEMs, the results of the origins and chemical structures of PARAFAC

87 components may not apply to organic matter in the atmosphere because the sources and

88 underlying physicochemical processes are different.30, 32 The organic chromophores in different

89 types of aerosols (e.g., urban, forest and ocean aerosols) may also be different, which must result

90 in differences in the optical properties and the photochemical reactivity of the organic

91 components. Investigating the relationships between the optical properties and structural

92 characteristics of WSOM in different types of aerosols is also important to better understand the

93 structures, sources and chemistry of chromophoric water-soluble organic matter in atmospheric

94 aerosols.

95 Chromophoric water-soluble organic matter in atmospheric aerosols may contain an array of

96 chemical species, as in the case of WSOM.33 For the chemical characterization of such complex

97 matter, high-resolution aerosol mass spectrometers (HR-AMSs) can be used in combination with

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98 the nebulization technique,34, 35

which provides the overall structural characteristics of the

99 complex organic matter, e.g., elemental composition and ion groups of the mass spectra. In this

100 study, EEMs and HR-AMS analyses were performed for WSOM in urban, forest and marine

101 aerosols to characterize the chromophoric water-soluble organic matter therein. Statistical

102 analyses of PARAFAC and non-negative matrix factorization (NMF) were applied to EEMs and

103 HR-AMS spectra to resolve the different components of WSOM that exhibit different chemical-

104 structural and fluorescence characteristics. The chemical structures and possible sources of

105 chromophoric water-soluble organic matter in different types of submicron aerosols are analyzed

106 and discussed based on hierarchical cluster analysis for the WSOM samples, backward air mass

107 trajectory analysis, and correlation analysis using the relative intensity of ion groups from the

108 HR-AMS spectra. Application of the results to future studies is suggested.

109 EXPERIMENTAL SECTION

110 Collection of aerosol samples and WSOM extraction

111 This study used sixty-three PM0.95 samples (50% cutoff: 0.95 µm) collected on 8 × 10 inch

112 quartz fiber filters using high-volume samplers in three different environments. Twenty-seven

113 samples were collected at an urban site in Nagoya, Japan (Nagoya University, 35.15°N,

114 136.97°E) from 11 August to 14 September 2013 (sample ID: 1–17), and from 4 to 24 March

115 2014 (sample ID: 18–27). Sixteen samples were collected at a forest site on the Kii Peninsula,

116 Japan (Wakayama Forest Research Station (WFRS), Kyoto University, 34.06°N, 135.52°E), five

117 from 20 to 30 August 2010 (sample ID: 28–32), and eleven from 28 July to 8 August 2014

118 (sample ID: 33–43). Twenty samples were collected aboard the NOAA RV Ka’imimoana as part

119 of the Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOCs

120 (TORERO) field experiment over the eastern equatorial Pacific ocean during the TORERO/KA-

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121 12-01 cruise in February 2012 (sample ID: 44–63). Blank filters were also collected at different

122 sites and periods. More information on the samples and the environment of the sampling sites are

123 given in Table S1 and section S2 of the Supporting Information (SI), respectively.

124 WSOM for the EEM analysis and HR-AMS analysis was extracted via the ultrasonication of

125 filter punches (diameter: 34 mm) with Milli-Q water for 1 h, followed by filtration through 0.2

126 µm PTFE filters (Millex). Different extraction conditions, i.e., the number of filter punches

127 (diameter: 34 mm) and the mass of Mill-Q water, were applied to different samples, as

128 summarized in Table S1. Quantification of WSOC was performed using a TOC analyzer (Model

129 TOC-VCHS, Shimadzu, Japan), as detailed in the SI (section S3). Analyses of amino acids and

130 biogenic secondary organic aerosol (BSOA) tracers were also performed for urban and forest

131 samples, respectively (see section S3, SI).

132 HR-AMS measurements

133 Each extract was atomized with argon (purity: 99.9999%). The generated aerosol was passed

134 through two diffusion scrubbers to remove water vapors. Then, the aerosol was introduced to the

135 HR-AMS (HR-ToF-AMS, Aerodyne Research Inc., Billerica, MA, USA). The HR-AMS spectra

136 were acquired in V-mode, and the data were analyzed using Squirrel v.1.56A and Pika v1.15A

137 Software (http://cires.colorado.edu/jimenez-group/ToFAMSResources/ToFSoftware/). In the

138 analysis using Pika, all of the CO+ ion signals were considered to have originated from organics

139 because pure argon was used as the carrier gas (Figure S1a). All of the organic ions were

140 classified into CH, CHN, CHO1, CHOgt1, CHO1N, CHOgt1N, CS, Cx, HO, CO, and CO2 groups.

141 Elemental analyses were performed to determine the atomic ratios (O/C, H/C, and N/C), and the

142 mass ratio of organic matter (OM) to organic carbon (OC). N/C was derived according to Aiken

143 et al,36 and O/C, H/C, and OM/OC were derived according to Canagaratna et al.37

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144 UV-visible absorption spectra and EEM fluorescence spectra

145 The extracts were placed in a 1-cm path-length quartz cell and subjected to analysis using a

146 UV-visible spectrophotometer (Model V-570, JASCO, Japan) and a fluorescence

147 spectrophotometer (Model FP-6600, JASCO, Japan). A UV-visible absorption spectrum was

148 recorded in the range of 200 to 800 nm. Before the scans for a series of extracts, Milli-Q water

149 was also analyzed for a baseline correction. The mass absorption efficiency (MAE, m2 g–1 OC)

150 of the organics in the extracts at λ nm (MAEλ) was calculated using the following equation: 38

151 MAEλ = Absλ ln(10)/CWSOC, (1)

152 where Absλ is the light absorption coefficients (m–1) of the extract solutions at λ, and CWSOC is the

153 concentration of water-soluble organic carbon (WSOC, g m-3) in the extracts. Because the MAE

154 of the extracts from the forest and marine samples were low in the visible range (Figure S2), the

155 MAE at 266 nm (MAE266) was used as a measure of absorptivity of the extracts.

156 The EEMs were measured in the range of 200 to 400 nm for excitation and in the range of 250

157 to 650 nm for emission at a scan speed of 1000 nm min–1. The band-passes for excitation and

158 emission were both set as 10 nm.22 The EEMs were calibrated according to the procedures

159 described by Lawaetz and Stedmon, and Murphy. 39, 40 The EEMs were normalized according to

160 the Raman peak of water, so the data are reported in Raman units (RU).39 The fluorescence

161 index, biological index, and humification index, which are the ratios of the fluorescence intensity

162 at excitation/emission wavelengths (Ex/Em) of 370/470 nm to that at 370/520 nm, the intensity

163 at 310/380 nm to that at 310/430 nm, and the intensity at 255/434–480 nm (average of the values

164 on the line between 255/434 and 255/480 nm) to that at 255/300–344 nm (average of the values

165 on the line between 255/300 and 255/344 nm), respectively, were obtained from the EEMs.41, 42

166 To compare the fluorescence efficiency of different water-extract samples, the fluorescence

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167 intensity over excitation wavelengths of 200–400 nm and emission wavelengths of 250–650 nm

168 were normalized by the OC concentration of the extracts (abbreviated to NFV, RU-nm2 [mg L−1

169 OC]–1).

170 Factor analysis for EEMs and HR-AMS spectra

171 PARAFAC analysis with non-negativity constraints of EEMs was performed with the drEEM

172 toolbox version 0.2.0 for MATLAB (http://www.models.life.ku.dk/dreem).27 For the analysis,

173 the EEM data at the excitation wavelengths longer than or equal to those on the line between

174 Ex/Em of 200/570 nm and that of 235/650 nm were omitted. The three-component PARAFAC

175 model was selected from two- to ten-component PARAFAC models because the residual errors

176 decreased noticeably when the number of components increased from two to three (Figure S3).

177 In addition, the three-component model has reasonable spectra of fluorescent components, and it

178 passes the assessment of a split-half analysis with the split style of ‘S4C6T3’ based on the

179 PARAFAC tutorial (Figure S4).27 The seven-component PARAFAC solution, which also

180 exhibits a noticeable decrease in residual errors with the increase in the number of components

181 among four- to ten-component PARAFAC solutions (Figures S3), was used to obtain more

182 detailed information on the chromophores. The seven-component PARAFAC solution passes the

183 split analysis with the split style of ‘S3C3T3’ (Figure S5), indicating that the solution is stable.

184 Non-negative matrix factorization (NMF) analysis was performed for the HR-AMS dataset

185 using the NMF toolbox version 1.4 in MATLAB (https://sites.google.com/site/nmftool/).43 First,

186 a gradient-descent-based multiplicative algorithm was used to find solutions from multiple

187 random starting values, and then a least-squares active-set algorithm was used to find final

188 solutions from the first solutions. To find a final solution, the model was run 100 times with a

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189 different starting point each time. The four-factor NMF model was validated by comparisons of

190 residual errors, split analysis and visualization of spectral loadings (Figures S6, S7 and S8).

191 Hierarchical cluster analysis

192 A hierarchical cluster method was performed to classify aerosol samples based on the relative

193 contributions of PARAFAC components and NMF factors to the respective samples. The

194 Euclidean distance was used to evaluate the distances between samples, and the centroid method

195 was chosen for the hierarchical cluster analysis by comparing the multiple correlation

196 coefficients for nearest neighbor, farthest neighbor, median neighbor and Ward’s method. Six

197 clusters were determined for EEMs and HR-AMS data and were named clusters a-f and clusters

198 A-F, respectively (Figures S9 and S10).

199 RESULTS AND DISCUSSION

200 EEMs and PARAFAC components

201 To identify and quantify the underlying chromophore components in aerosols, the PARAFAC

202 model was applied to separate independently varying fluorescent components. Figure 1 presents

203 the EEMs of the three- (3CM-C1~3) and seven- (7CM-C1~7) component PARAFAC solutions.

204 The EEMs of 3CM-C1~3 are similar to those identified from water and alkaline soluble matter in

205 urban aerosols in Granada, Spain and in Aveiro, Portugal.29, 30 Based on a comparison with the

206 EEMs of three fluorescent components defined for terrestrial and oceanic organic matter by Yu

207 et al., 28 the chemical components corresponding to 3CM-C1, -C2 and -C3 are named HULIS-1,

208 HULIS-2 and PLOM, respectively, in this study. Note that the origins and chemical structures of

209 HULIS and PLOM chromophores studied are not necessarily similar to those of the

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210 chromophores with same names in terrestrial and oceanic organic matter. The origins and

211 chemical structures of the chromophores in atmospheric aerosols are discussed below.

212 The seven-component PARAFAC solution provides more detailed information on the

213 chromophores. By comparing the emission wavelengths with the maximum fluorescence of the

214 three-component PARAFAC solution and based on a correlation analysis of the relative

215 abundance of the three and seven components (Table S2), chemical components corresponding

216 to 7CM-C1 and 7CM-C3 are assigned to HULIS-1, whereas 7CM-C2, 7CM-C4 and 7CM-C5 are

217 assigned to HULIS-2, and 7CM-C6 and 7CM-C7 are assigned to PLOM. Among the seven

218 components, 7CM-C1, 7CM-C3 and 7CM-C5 have peaks at emission wavelengths of >400 nm

219 (Figure 1); these emissions probably originate from conjugated systems, e.g., via quinonoid n-π*

220 transitions.44 This claim is supported by the result that the emission wavelength of 7CM-C3

221 (~470 nm) is similar to that of the quinone-like component identified in aerosol WSOM in

222 Granada, Spain.29 Based on the definition of fluorescent components of terrestrial and oceanic

223 organic matter, 7CM-C6 and 7CM-C7 correspond to tryptophan-like and tyrosine-like

224 components, respectively.27, 28

However, non-nitrogen-containing species may account for a

225 major portion of the chromophores of 7CM-C6 and 7CM-C7 in atmospheric aerosols, as

226 discussed below.

227 The relative intensities of different fluorescent components in different types of aerosols were

228 highly variable depending on the sampling site and period, as shown in Figure 2a. This result

229 suggests that the chemical composition of chromophoric water-soluble organic matter differs

230 markedly from sample to sample. HULIS-1was the substance with most intense fluorescence in

231 all samples, and, on average, accounted for 46% of the total fluorescence intensity of all samples.

232 High mass fractions of HULIS were observed in an area similar to that of the marine aerosol

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233 sampling, supporting the particularly intense fluorescence of HULIS-1 in the marine aerosols

234 studied.47 The fluorescence of HULIS-2 was intense in the terrestrial aerosols (urban and forest

235 aerosols) (mean: 47% of the total fluorescence intensity of the extracts), particularly in forest

236 aerosols (mean: 51%). Conversely, the fluorescence of HULIS-2 in marine aerosols was weak

237 (mean: 23%). This result suggests that HULIS-2 primarily has a terrestrial origin. The marine

238 aerosols were enriched in the PLOM (mean: 19%), which can be attributed to marine biological

239 materials.28, 46 The fluorescent components assigned to PLOM were also present in the urban

240 aerosols, among which the fluorescence of tryptophan-like substances (7CM-C6) was the

241 strongest. Accordingly, these aerosols differ from the marine aerosols, in which the relative

242 strengths of the fluorescences of tryptophan-like and tyrosine-like components (7CM-C7) were

243 nearly equal. This result indicates that PLOM in urban and marine aerosols can be attributed to

244 different chemical structures and sources.

245 HR-AMS spectra and the NMF factors

246 The chemical characteristics of WSOM in aerosols were obtained on the basis of the HR-AMS

247 spectra of the extracts in various samples. Four factors were determined from the HR-AMS

248 spectra of the NMF model. The mass spectra and relative abundances of these factors in different

249 types of aerosols are presented in Figures 3 and 2b, respectively. Based on the degree of

250 oxidation (O/C ratio) of organics, the four factors were identified as highly oxygenated organic

251 aerosols (HOOA-1 and HOOA-2) and low oxygenated organic aerosols (LOOA-1 and LOOA-2).

252 Note that each organic aerosol may represent a group of molecules and/or their moieties.

253 The HOOA-1 factor has a high O/C ratio (1.67) and a low H/C ratio (1.1). Approximately half

254 of the total HOOA-1 signal was contributed by CO2+ ions, suggesting a large fraction of

255 carboxylic acids in HOOA-1.37, 47 The mass fraction of HOOA-1 in the marine aerosols (mean:

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256 48%) was obviously higher than those in the urban (mean: 20%) and forest aerosols (mean: 9%),

257 indicating that WSOM in marine aerosols was dominated by more processed oxygenated

258 products.

259 The HOOA-2 factor contains abundant CS ions (16%), primarily CHSO+ (m/z 61), CH2SO+

260 (m/z 62), CH2SO2+ (m/z 78), CH3SO2+ (m/z 79) and CH4SO3+ (m/z 96) ions (Figures 3 and S1).

261 Among these ions, the most abundant CS ion in the mass spectrum of HOOA-2 is CH2SO2+,

262 which likely originated from methanesulfonic acid (CH3SO3H, MSA).48, 49 HOOA-2 contributes

263 largely to the WSOM of marine aerosols (mean: 30%) and slightly to the WSOM of the urban

264 (mean: 2%) and forest samples (mean: 5%). The relative abundance of HOOA-2 is particularly

265 high in marine samples collected over the eastern tropical Pacific Ocean in the Southern

266 Hemisphere (mean: 46%), which is consistent with the high mass concentration ratios of MSA to

267 WSOC.50 The above results suggest that HOOA-2 should be representative of the WSOM of

268 marine aerosols. The characteristics of the low abundances of CxHyOz+ (10%) ions and high

269 abundances of CxOy+ (31%) and CxHy+ (31%) ions in HOOA-2 differ from those of the PMF-

270 derived marine organic aerosols in Paris, France (CxHyOz+, CxOy+ and CxHy+ were 41%, 17% and

271 32%, respectively) (URL: http://cires.colorado.edu/jimenez-group/HRAMSsd/).51 This

272 difference may be because marine aerosols are enriched in water-insoluble organic matter

273 (WISOM), which may consist of hydrophobic sugar-like compounds.52 In fact, the WSOC/TC

274 ratio was low (mean: 0.4), thus supporting the high abundance of WISOM in the marine

275 aerosols.50

276 The LOOA-1 factor was dominated by CxHy+ (38%) and CxHyOz+ (24%) ion groups. In

277 contrast, CO2+ was very low in the LOOA-1 spectra, but abundant CO+ (15%) was observed.

278 This result suggests that LOOA-1 is associated with alcohols and ketones or aldehydes, but not

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279 with carboxylic acids and carboxylate esters.37 One of the remarkable characteristics of LOOA-1

280 in comparison with the other factors is the higher mass fraction of the CxHyNq+ ion group (6%),

281 suggesting that nitrogen-containing compounds were abundant. The relative abundances of

282 LOOA-1 in certain urban aerosol samples, particularly in the late winter and early spring

283 samples (mean: 47%), were obviously higher than those in the forest and marine aerosol samples

284 (Figure 2b). Hence, LOOA-1 is probably anthropogenic.

285 The mass spectrum of the LOOA-2 is largely composed of CxHy+ (44%) and CxHyOz+ (31%)

286 ion groups and is characterized by the higher signal of C2H3O+ (11%). The profile of the LOOA-

287 2 factor was similar to that of the factor of semi-volatile oxygenated organic aerosols,

288 determined on the basis of the PMF analysis of the online HR-AMS data at the WFRS forest site,

289 which was interpreted as locally formed BSOA.53 The relative abundance of LOOA-2 was

290 positively correlated with the ratios of total OC concentrations of BSOA tracers (supporting

291 information S3) to WSOC in the forest samples (r = 0.80, p <0.001, n = 16). Furthermore, Figure

292 2b shows that LOOA-2 accounted for a large mass fraction of WSOM in forest aerosols (mean:

293 59%), which is higher than in the fractions of other aerosols. These results suggest that LOOA-2

294 should be representative of the water-soluble part of BSOA. The relative abundance of LOOA-2

295 in the urban aerosols was also high (mean: 39%), particularly in the case of summer aerosols

296 (mean: 46%). Hence, BSOA should have also been abundant in Nagoya.

297 Optical properties and chemical composition of WSOM versus the sample clusters

298 The optical properties and chemical composition of WSOM in aerosols varied from sample to

299 sample. The forest and marine aerosols were unlikely to be rich in water-soluble chromophores.

300 As Figure 2c presents, the values of MAE266 and NFV for the urban aerosols tended to be higher

301 than those for the forest and marine aerosols, and the difference is in particular obvious in the

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302 case of the urban aerosols in late winter and early spring. This result is consistent with the results

303 reported in previous studies; the MAEs of WSOM in aerosols in the cities of Beijing and Los

304 Angeles were obviously higher than the MAEs in Atlanta and Kpuszta, where biogenic aerosols

305 dominated.5, 54-56 The MAE266 and NFV values were positively correlated with C2H4O2+ (Figure

306 4), an ion associated with organics from biomass burning organic aerosol (BBOA).57 This result

307 indicates that the enhancement of the MAEs and NFVs in these urban aerosols is probably linked

308 to biomass-burning sources. This result is consistent with our other work (Chen et al.,

309 submitted), in which the brown carbon in wintertime aerosols over Nagoya was suggested to be

310 derived from biomass burning, and responsible for the increase of the MAEs and NFVs of both

311 the water soluble and insoluble organic matter. E2/E3 (the ratio of absorbance at 250 to that at

312 365 nm) in the UV-visible spectra generally relates to the total aromaticity of organics.58 The

313 E2/E3 values of the WSOM in late winter and early spring were on average 0.8 times that of the

314 summer values, suggesting relatively high aromaticity in late winter and early spring. Nitro-

315 aromatics, which were reported to be detected in biomass-burning-impacted aerosol/cloud

316 samples,59-61 were possible chromophoric compounds in the studied urban aerosols.

317 The influence of aerosols from different origins on the optical properties and chemical

318 composition were further analyzed based on hierarchical cluster analysis of the samples (Figures

319 S9-12) and backward trajectory analysis of the air masses (Figures S13 and S14). The results

320 show that different cluster samples exhibit marked differences in terms of the relative

321 abundances of fluorescent components and HR-AMS factors, as well as the trajectories. Clusters

322 a-f, which were classified on the basis of the relative abundances of the HR-AMS factors, show

323 that most of the urban aerosol samples are classified into clusters a and b. The important

324 difference between these two clusters and the others is that clusters a and b have high mass

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325 fractions of LOOA-1 (mean: 42%). Aerosol samples that belong to cluster b may contain aged

326 BBOA from the Asian continent because they have relatively high MAE and NFV values and the

327 air masses corresponding to cluster b were mainly from the Asian continent (red lines in Figure

328 S14a). Most of the forest aerosol samples are classified into clusters c or d, which are

329 characterized by a high mass fraction of LOOA-2 (mean: 60%). The marine aerosol samples are

330 classified into clusters e and f. A notable difference between cluster f and cluster e is that the air

331 masses of the former were mainly from the southwest Pacific and that the relative abundance of

332 HOOA-2 in cluster f is high (mean: 46%).

333 The clusters of samples determined from the hierarchical cluster analysis on the basis of the

334 relative abundances of the seven fluorescent components were similar to those from the HR-

335 AMS factors. All urban aerosol samples were assigned to cluster A or cluster B. The difference

336 between cluster B and cluster A is the relatively low abundance of HULIS-1 (mean: 37%) and

337 high abundance of HULIS-2 (mean: 49%), and the higher MAE and NFV values. The air mass

338 trajectories show that chromophoric water-soluble organic matter in the cluster B samples was

339 likely associated with air masses from the Asian continents (red line in Figure S14c). Marine

340 aerosol samples were assigned to three clusters, i.e., C, D and E. The difference between cluster

341 E and the other clusters is that cluster E has a high abundance of PLOM (mean: 34%).

342 Approximately half of the forest aerosol samples were classified into cluster F, which is

343 characterized by the high abundance of HULIS-2 (mean: 52%).

344 The above results indicate that both the chemical composition and chromophore types are

345 closely related to the origins of organic aerosol components. The correlation analysis between

346 the relative abundances of fluorescent components and HR-AMS factors (Table S3) showed that

347 HULIS-1, HULIS-2 and PLOM were positively correlated to the relative contents of HOOA-1 (r

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348 = 0.66, p <0.001), LOOA-2 (r = 0.62, p <0.001) and HOOA-2 (r = 0.65, p <0.001), respectively.

349 The estimated origins of LOOA-2 and HOOA-2 suggest that HULIS-2 and PLOM were of

350 terrestrial biological origin and marine origin, respectively. HULIS-2 was positively correlated

351 with the signal intensity of C2H4O2+ ions (r = 0.63, p <0.001), suggesting that HULIS-2 partly

352 originated from biomass burning.

353 Chemical structures of chromophores

354 The possible chemical structures of water-soluble chromophores in aerosols were suggested

355 by the HR-AMS spectra of water extracts from various samples. The relationship between HR-

356 AMS ions, EEM components and optical indexes are presented in Figure 4. The MAE266 and

357 NFV values were positively correlated with the relative signal intensity of CxHyO>1+, CxHyNp+

358 and CxHyO>1Np+ ion groups, suggesting that organic compounds with O and N atoms, such as

359 nitro-aromatics, contributed greatly to the total light absorption and fluorescence of water-

360 soluble chromophores in the aerosols. This result is consistent with our other work with aerosols

361 over Nagoya (Chen et al., submitted), in which we found that both the MAE and NFV values

362 were positively correlated with the O- and N-containing ion groups in the case of HULIS, i.e.,

363 the major water-soluble component in aerosols over Nagoya.

364 Figure 4 also shows that the fluorescent components of HULIS-1 and HULIS-2 were

365 correlated positively with highly oxygenated ions (CO+ and CO2+) and less oxygenated ions

366 (CxHy+ and CxHyO1+), respectively, suggesting that the two chromophore components relate to

367 highly oxygenated (HULIS-1) and less-oxygenated (HULIS-2) organic species. Although the

368 PLOM component was usually assigned to biological proteins,28, 46

it was not positively

369 correlated with nitrogen-containing ions (CxHyNp+ and CxHyOzNp+ ions) in the HR-AMS spectra,

370 which is expected to be from nitrogen-containing compounds such as amines and amino acids.

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371 Furthermore, the relative abundance of PLOM was not positively correlated with the ratios of the

372 concentrations of each (r <0.28, p >0.20, n >15) or the sum of amino acids (r = 0.20, p >0.33, n

373 = 27) to WSOC in the urban aerosols. These results suggest that non-nitrogen-containing species

374 with fluorescence similar to the component of PLOM (e.g., naphthalene and phenol compounds)

375 may have also contributed to PLOM.26, 29 Particularly in the case of urban aerosols, naphthalene-

376 like chromophores may have accounted for a major portion of the fluorescence of PLOM, given

377 their presence in diesel exhaust aerosols.29

378 Fluorescence index, biological index and humification index, which are generally used for

379 organic matter in terrestrial and oceanic samples, are possibly associated with the chemical

380 structures of organics in atmospheric aerosols. Both the biological index and fluorescence index

381 were positively correlated with CxHy+ and CxHyO1+, and negatively correlated with CO+ and

382 CO2+, implying their association with the oxidation degree of organics. Although the

383 humification index was not strongly correlated with any AMS ion group, it was correlated with

384 the ratios of fluorescence intensity of the HULIS to PLOM components in the log-log plot

385 (Figure S15). This result shows that the humification index may represent the relative

386 contribution of HULIS to the fluorescence of the atmospheric organic aerosol component.

387 Application of the results to future studies

388 This study shows that the chromophore components of HULIS and PLOM are ubiquitous

389 classes of water-soluble chromophores in different types of aerosols, and their relative contents

390 are highly variable depending on the location and time period. The possible origins and

391 transformations of the HULIS and PLOM components are summarized in Figure 5. This figure

392 also shows comparisons of chromophore types identified in atmospheric particles with

393 components in wet depositions from previous studies. These results should be helpful for the

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394 classification and source identification of water-soluble chromophores in aerosols in future

395 studies using EEM spectroscopy.

396 This study also shows that the HULIS-1 and HULIS-2 chromophores were associated with

397 highly and less oxygenated structures, respectively. This finding provides information on the

398 chemical structures of water-soluble chromophores and may be useful for evaluating the reaction

399 pathways involved in the formation or loss of organic chromophores in atmospheric aerosols. As

400 presented in Figure 5, the fluorescence peak of rainwater samples is similar to band M of

401 HULIS-2, which has been suggested to shift to band A of HULIS-1 through exposure to

402 sunlight.21 This mechanism explains our results. The chromophores may have been degraded by

403 exposure to sunlight and converted into more oxygenated species. Furthermore, the

404 chromophores corresponding to bands C and M, which are attributed to HULIS-1 and HULIS-2

405 components, respectively, can be formed from photodegradation of compounds with the PLOM

406 chromophore component, such as phenol and 4-phenoxyphenol.26, 62 The chromophore group

407 with the strongest fluorescence in WSOM was attributed to HULIS-1 for all samples, which may

408 be due to photochemical reactions of the compounds that have fluorescent properties similar to

409 the chromophore components of HULIS-2 and PLOM. We propose using these results in future

410 studies to understand the chemical transformations, including degradation and polymerization, of

411 chromophores in the atmosphere.

412 ACKNOWLEDGEMENTS

413 We thank the faculty and staff of Wakayama Forest Research Station, Field Science Education

414 and Research Center of Kyoto University, Japan, for the use of the sampling/observation site,

415 and Yuemei Han and Kaori Kawana for their contribution to the field study at this site in 2010.

416 We also thank the Research Center for Materials Science, Nagoya University, for the use of the

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417 UV-visible and fluorescence spectrometer, and Kin-ichi Oyama for the technical support with

418 the instruments. Hiromi Kawakami, Eri Tachibana, Kaori Ono and Mayumi Kuroki are

419 acknowledged for their technical support with the chemical analyses. We acknowledge NOAA's

420 Air Resources Laboratory (ARL) for providing the HYSPLIT model

421 (http://ready.arl.noaa.gov/HYSPLIT.php). The TORERO project was funded by the U.S.

422 National Science Foundation award AGS-1104104 (R.V.); the TORERO team thanks the NOAA

423 TAO Program for the RV Ka’imimoana cruise KA-12-01. S.C. is a recipient of the NASA

424 graduate fellowship. This work was supported in part by JSPS KAKENHI (grant numbers

425 25281002 and 26281007), the Program for Improvement of Research Environment for Young

426 Researchers from Special Coordination Funds for Promoting Science and Technology (SCF)

427 commissioned by the Ministry of Education, Culture, Sports, Science and Technology (MEXT)

428 of Japan, and Environmental Research and Technology Development Fund from Ministry of the

429 Environment of Japan (5-1408, FY2014-2016).

430 SUPPORTING INFORMATION

431 Key acronyms, the environments of the sampling locations, and the procedures for the analysis

432 of WSOC, amino acids and BSOA tracers are explained in the text. The sample information and

433 the results from the correlation analysis for the PARAFAC components and NMF factors are

434 presented in supporting tables. The curve fittings of the HR-AMS spectra with the peaks from N-

435 containing and S-containing ions, average UV-visible absorbance spectra of the extracts, residual

436 analysis and split half analysis for the PARAFAC and NMF models, hierarchical cluster analysis

437 of samples, backward trajectories of air masses, plot of the relative fluorescence intensity of

438 HULIS to PLOM versus the humification index, and EEM spectra of the extracts are presented in

439 supporting figures.

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620 (54) Yang, M.; Howell, S. G.; Zhuang, J.; Huebert, B. J. Attribution of aerosol light
621 absorption to black carbon, brown carbon, and dust in China – interpretations of atmospheric
622 measurements during EAST-AIRE. Atmos. Chem. Phys. 2009, 9, 2035–2050, DOI: 10.5194/acp-
623 9-2035-2009

624 (55) Cheng, Y.; He, K. B.; Zheng, M.; Duan, F. K.; Du, Z. Y.; Ma, Y. L.; Tan, J. H.; Yang, F.
625 M.; Liu, J. M.; Zhang, X. L.; Weber, R. J.; Bergin, M. H.; Russell, A. G. Mass absorption
626 efficiency of elemental carbon and water-soluble organic carbon in Beijing, China. Atmos. Chem.
627 Phys. 2011, 11 (22), 11497–11510, DOI: 10.5194/acp-11-11497-2011

628 (56) Zhang, X.; Lin, Y,-H.; Surratt, J. D.; Zotter, P.; Prévôt, A. H. S.; Weber, R. J. Light-
629 absorbing soluble organic aerosol in Los Angeles and Atlanta: A contrast in secondary organic
630 aerosol Geophys. Res. Lett. 2011, 38, L21810, DOI: 10.1029/2011GL049385

631 (57) Lee, T.; Sullivan, A.P.; Mack, L.; Jimenez, J. L.; Kreidenweis, S.M.; Onasch, T. B.;
632 Worsnop, D. R.; Malm, W.; Wold, C. E.; Hao, W. M.; Collett, J. L. Chemical smoke marker
633 emissions during flaming and smoldering phases of laboratory open burning of wildland fuels.
634 Aerosol. Sci & Tech. 2010, 44 (9), i–v, DOI: 10.1080/02786826.2010.499884

635 (58) Heal, M.R.; Hammonds, M.D. Insights into the composition and sources of rural, urban
636 and roadside carbonaceous PM10. Environ. Sci. Technol. 2014, 48 (16), 8995–9003, DOI:
637 10.1021/es500871k
638 (59) Mohr, C.; Lopez-Hilfiker, F. D.; Zotter, P.; Prevot, A. S. H.; Xu, L.; Ng, N. L.; Herndon,
639 S. C.; Williams, L. R.; Franklin, J. P.; Zahniser, M. S.; Worsnop, D. R.; Knighton, W. B.; Aiken,

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640 A. C.; Gorkowski, K. J.; Dubey, M. K.; Allan, J. D.; Thornton, J. A. Contribution of nitrated
641 phenols to wood burning brown carbon light absorption in Detling, United Kingdom during
642 winter time. Environ. Sci. Technol. 2013, 47 (12), 6316–6324, DOI: 10.1021/es400683v

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644 chromatographic method based on ultraviolet-visible and electrospray ionization mass
645 spectrometric detection for the identification of nitrocatechols and related tracers in biomass
646 burning atmospheric organic aerosol Rapid Commun. Mass Spectrom. 2012, 26 (7), 793–804,
647 DOI: 10.1002/Rcm.6170

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663 fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols. Environ.
664 Sci. Technol. 2013, 47 (11), 5763–5770, DOI: 10.1021/es400644c

665

666

667

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668

669 Figure 1. EEM components identified by the three- and seven-component solutions of the

670 PARAFAC model for WSOM. The intensity was normalized to make the maximum to be unity.

671 The chemical components corresponding to the three-component PARAFAC solutions of 3CM-

672 C1, -C2 and -C3 are named as HULIS-1, -2 and PLOM, respectively. The arrows represent

673 combinations of three- and seven-component solutions with high positive correlations (r>0.5,

674 p<0.01). The emission wavelength (Em.) at the maximum fluorescence intensity for each

675 component is also given.

676

677

678

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679

680 Figure 2. (a and b) Relative abundances of (a) the PARAFAC derived components (7CM-C1

681 and -C3 are associated with HULIS-1; 7CM-C2, -C4 and -C5 are associated with HULIS-2;

682 7CM-C6 and -C7 are associated with PLOM) and (b) NMF derived fractions (HOOA-1: F1;

683 HOOA-2: F4; LOOA-1: F3; LOOA-2: F2) of WSOM of different samples, as well as different

684 clusters (label on the horizontal axis: A–F and a–f) classified by hierarchical cluster analysis. (c)

685 The normalized fluorescence volume (NFV, normalized to a WSOC concentration of 1 mg L−1)

686 and the mass absorption efficiency at 266 nm (MAE266) for different samples. The sample IDs

687 correspond to different types of aerosols as follows: ID 1-17: the urban aerosols in August and

688 September; ID 18-27: the urban aerosols in March; ID 28-43: the forest aerosols; ID 44-63: the

689 marine aerosols. Sample 43 and samples 5 and 56 were screened out in the course of the

690 PARAFAC and NMF analyses, respectively.

691

692

693

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694

695 Figure 3. The mass spectra, elemental compositions, and relative intensities of ion groups of the

696 four components from the NMF analysis (HOOA-1, HOOA-2, LOOA-1 and LOOA-2) of the

697 WSOM fractions.

698

699

700

701

702

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703

704 Figure 4. Pearson’s correlation coefficients and significance levels (p, two-sided t-test)

705 calculated through the correlation analysis of the relative intensities of ion groups in the HR-

706 AMS spectra and relative contents of the (a) 3-component solution of PARAFAC (3CM-C1:

707 HULIS-1; 3CM-C2: HULIS-2; 3CM-C3: PLOM) and (b) 7-component solution of PARAFAC

708 (7CM-C1 and -C3 are associated with HULIS-1; 7CM-C2, -C4 and -C5 are associated with

709 HULIS-2; 7CM-C6 and -C7 are associated with PLOM), and (c) MAE266, NFV, and EEM-

710 derived indices (fluorescence index (FI), biological index (BIX), and humification index (HIX)).

711

712

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713

714 Figure 5. Diagram of the association of the EEM profiles with the possible chemical structures,

715 sources, and atmospheric chemical processes of chromophoric water-soluble organics in

716 atmospheric aerosols. The blue, green, and red boxes represent the fluorescence ranges of PLOM,

717 HULIS-2, and HULIS-1, respectively. The colors of circles represent the relative fluorescence

718 intensities around the peaks of EEM components. The designated peaks of A, C and M represent

719 the UVC-excited, UVA-excited and marine humics that were defined for terrestrial and oceanic

720 systems in previous studies.41 The markers labeled a–i represent, from left to right: aQuinone-like,

721 terrestrial-HULIS, and naphthalene-like components in WSOM of PM10 in Granada, Spain;29

b
722 HULIS, anthropogenic aromatics, fulvic acid, and anthropogenic low molecular weight

723 substance in alkaline soluble matter of road dust in Ulsan, Korea;31 ctwo HULIS components and

724 protein-like components both in water and alkaline soluble matter of PM2.5 in Aveiro, Portugal;30

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d
725 HULIS and ocean protein-like substances in High Arctic TSP;46 eHULIS, marine-HULIS, and

726 protein-like substances in rainwater in Rameswaram, India;63 fHULIS, marine-HULIS, and

727 protein-like substances in rainwater in Aveiro, Portugal;64 gHULIS, marine-HULIS, and protein-

728 like substances in fogwater in Prairieville, Louisiana;42 hchamber-generated water-soluble

729 secondary organic aerosols from naphthalene and those from α-pinene;57, 65 i
brown carbon

730 formed from glycol and ammonium sulfate in solution and that formed from methylglyoxal and

731 ammonium sulfate in solution.20 The arrows labeled j–l represent the shifts of peak positions in

732 the cases of: jdimerization of phenol in the presence of triplet state 1-nitronaphthalene;26
k
733 photobleaching of chromophoric organics by the exposure of rainwater collected in Wilmington,

734 USA, to sunlight;21 lphotolysis of chamber-generated water-soluble secondary organic aerosols

735 from limonene.57, 65

736

737

738

739

740

741

742

743

744

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745 TOC/Abstract Art

746

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