PM10-Associated Chlorinated Polycyclic Aromatic

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Airborne PM2.5/PM10-associated Chlorinated Polycyclic Aromatic Hydrocarbons and their Parent Compounds in a Suburban Area in Shanghai, China Jing Ma, Zuyi Chen, Minghong Wu, Jialiang Feng, Yuichi Horii, Takeshi Ohura, and Kurunthachalam Kannan Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/es400338h • Publication Date (Web): 14 Jun 2013 Downloaded from http://pubs.acs.org on June 15, 2013

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Environmental Science & Technology

1

Airborne PM2.5/PM10-associated Chlorinated Polycyclic Aromatic Hydrocarbons

2

and their Parent Compounds in a Suburban Area in Shanghai, China

3 4

JING MA†, ZUYI CHEN†, MINGHONG WU†,*, JIALIANG FENG†, YUICHI

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HORII#, TAKESHI OHURA§, KURUNTHACHALAM KANNAN‡,

,*

6 7

†

8

Shanghai, 200444, China

9

‡

School of Environmental and Chemical Engineering, Shanghai University,

Wadsworth Center, New York State Department of Health, and Department of

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Environmental Health Sciences, School of Public Health, State University of New

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York at Albany, Albany, New York 12201-0509, United States

12

#

13

Kitasakitama, Saitama, 347-0115, Japan

14

§

Center for Environmental Science in Saitama, 914 Kamitanadare, Kisai-machi,

Faculty of Agriculture, Meijo University, 1-501 Tempaku, Nagoya, 468-8502, Japan. International Joint Research Center for Persistent Toxic Substances, State Key

15 16

Laboratory of Urban Water Resource and Environment, Harbin Institute of

17

Technology, Harbin 150090, China

18 19 20 21 22

*

Corresponding authors: Minghong Wu Phone: +86-21-66137801 Fax: +86-21-66137787 Email: [email protected]

23

And

24 25 26 27 28

Kurunthachalam Kannan Phone: +518-474-0015 Fax: +518-473-2895 Email: [email protected]

29 30

For submission to: Environmental Science and Technology 1

ACS Paragon Plus Environment


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Abstract

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Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have been reported to be

33

formed during incineration processes.

34

little is known on the occurrence of these chemicals in the environment.

35

study, concentrations of 24-h airborne PM10 and PM2.5-associated ClPAHs and their

36

corresponding parent PAHs were monitored from October 2011 to March 2012 in a

37

suburban area in Shanghai, China.

38

samples were collected for 7 days in April from the same sampling site.

39

twenty ClPAH congeners were found in PM10 and PM2.5 at concentrations ranging

40

from 2.45 to 47.7 pg/m3 with an average value of 12.3 pg/m3 for PM10, and from 1.34

41

to 22.3 pg/m3 with an average value of 9.06 pg/m3 for PM2.5.

42

that ClPAHs are ubiquitous in inhalable fine particles.

43

∑ClPAHs and specific congeners such as 9-ClPhe, 3-ClFlu, 1-ClPyr, 7-ClBaA, and

44

6-ClBaP in particles collected during nighttime were higher than those collected

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during daytime, which suggests not only diffusion of ClPAHs in air by atmospheric

46

mixing but also photochemical degradation during daylight hours.

47

individual ClPAHs determined, 6-ClBaP, 1-ClPyr, and 9-ClPhe were the dominant

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compounds in PM10 and PM2.5.

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7-ClBaA, and 3-ClFlu between PM10 and PM2.5 was similar.

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correlations were found between concentrations of ClPAHs and their corresponding

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parent PAHs, particle mass, and total organic carbon (organic carbon plus elemental

52

carbon), indicating that ClPAHs are sorbed onto carbonaceous matter of PM.

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Concentrations of parent PAHs predicted by multiple linear regression models with

54

PM mass, total organic carbon, temperature, and relative humidity as variables

55

reflected the measured concentrations with a strong coefficient of determination of

Despite dioxin-like toxicities of ClPAHs, In this

In addition, daytime and nighttime particle Twelve of

Our results indicate

The concentrations of

Among the

The percent composition of 6-ClBaP, 1-ClPyr,

2


Significant positive

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0.917 and 0.946 for PM10 and PM2.5, respectively.

However, the models generated

57

to predict ClPAH concentrations in PM did not yield satisfactory results, which

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suggested the differences in physical-chemical properties and formation processes

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between ClPAHs and their corresponding parent PAHs.

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collectively accounted for the preponderance of the total dioxin-like TEQ

61

concentrations of ClPAHs (TEQClPAH) in PM samples.

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compounds such as ClPAHs and PAHs present in PM2.5 can be related to adverse

63

health outcomes in people.

7-ClBaA and 6-ClBaP

Exposure to toxic

64 65

Introduction

66

Airborne particulate matter (PM) has been used as an indicator for evaluating the

67

quality of air in many developed and some developing countries.

68

levels of PM10 (particles below 10 µm size) and PM2.5 (particles below 2.5 µm) have

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become a major research issue worldwide because of their significance and relevance

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to human health, visibility impairment and effects on climate processes 1-4.

71

effects of PM exposure on human health have been consistently demonstrated by

72

numerous epidemiological studies

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thought to depend not only on their morphological/physical characteristics, like

74

particle size, but also on the reactive/toxic chemical compounds absorbed onto the

75

particles 1, 4, 5.

76

polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs, polychlorinated

77

dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and quinones, have attracted most

78

attention so far, and these compounds were considered to play a key role in eliciting

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adverse health effects

5-8

.

Atmospheric

Adverse

The effects of PM on human health are

Some organic compounds that are sorbed onto inhalable PM, such as

9-14

.

However, to our knowledge, the focus on chlorinated

3



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PAHs (ClPAHs), which are dioxin-like toxic organics, formed through atmospheric

81

reactions is limited.

82

ClPAHs are a class of anthropogenic compounds with one or more chlorines

83

substituted on the aromatic rings of a PAH molecule 15.

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to be carcinogenic and mutagenic and possess toxic potentials similar to those of

85

PCDD/Fs

86

interest in analysis, occurrence, fate, and behavior of these micropollutants in the

87

environment, with studies documenting the occurrence in tap water, sediments, waste

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incineration processes, automotive exhaust, dust and soil from electronic waste

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(e-waste) recycling operations

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ClPAHs have been carried out by various investigators over the last 20 years 24-29, but

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the earlier studies were focused on total suspended particles (TSP).

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especially PM2.5, can act as a vector for organic contaminants to humans through

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inhalation, thus affecting the health.

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ClPAHs in respirable fine particles and determination of the effects of PM mass,

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organic carbon (OC), and elemental carbon (EC) on the concentrations of ClPAHs are

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important for better understanding the fate of these compounds in air.

16, 17

.

ClPAHs have been reported

Evidences of toxicological significance of ClPAHs have evoked

18-23

.

Pioneering studies on atmospheric levels of

Respirable PM,

Therefore, monitoring of occurrence of

97

The objectives of this study were to determine the concentrations and profiles of

98

ClPAHs and their corresponding parent PAHs in PM10 and PM2.5 in suburban air from

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Shanghai during winter, and to evaluate the role of PM mass, and total organic carbon

100

(TC) content of PM in influencing the concentrations.

An attempt to predict the

101

concentrations of PM10/PM2.5-associated ClPAHs and PAHs was presented by

102

utilizing multiple linear regression models that incorporate the concentrations of PM,

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OC, EC, temperature, and relative humidity as variables.

104

equivalents (TEQs) of ClPAHs in PM10 and PM2.5 were calculated to enable an

4


Dioxinlike toxic

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understanding of potential toxic effects of these emerging environmental

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contaminants.

107 108 109

Materials and Methods Sample Collection and Target Compounds.

Atmospheric samples of PM10

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and PM2.5 were collected at the rooftop (approximately 20 m above ground level) of a

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building on the campus of Shanghai University in Baoshan District, Shanghai

112

(latitude 31°19' N, longitude 121°23' E).

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nearest highway with heavy traffic and is surrounded by small cement and chemical

114

industrial plants, and residential areas.

115

residential area in China.

The sampling site was 1.5 km from the

The sampling location is a typical suburban

116

Samples were collected for 24 h on quartz fiber filters (GM-A, 20.3 cm × 25.4

117

cm, PALL Pallflex Inc., Ann Arbor, MI, USA) with two high-volume air samplers

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(GUV-15HBL1, Thermo Andersen, Smyrna, GA, USA) equipped with a cutting head

119

for 2.5µm and 10µm particle sizes.

120

rate of 1.13 m3/min.

121

and this was done for 6 months (from 26 October 2011 to 28 March 2012, the winter

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season).

123

weather became clear. Thus, a total of 44 24-h samples were collected during the

124

study period.

125

samples were taken from 2 to 8 April, 2012 in the same sampling site.

126

collected from 07:00 to 19:00 (daytime samples) and from 19:00 to 07:00 (nighttime

127

samples), and there was no wet precipitation during the sampling week.

128 129

The samplers were operated at a constant flow

Each sample of 24-h duration was collected for every six days,

During the days of wet precipitation, the air sampling was delayed until the

In addition, a total of 28 12-h daytime-nighttime airborne particle Samples were

All the quartz filters were preheated at 450oC for 6 h before being used, for the removal contaminants that may be present.

After the collection of samples, the

5



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filters were wrapped in pre-cleaned aluminum foil, sealed in plastic bags and stored at

131

-29°C until extraction.

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Twenty individual ClPAHs, representing mono- through tri-chloroPAHs, were

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determined: 9-monochlorofluorene (9-ClFle), 9-monochlorophenanthrene (9-ClPhe),

134

3,9-dichlorophenanthrene

135


136

(3,9,10-Cl3Phe),

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(9-ClAnt),

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(3-ClFlu),

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(5,7-Cl2Flu),

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(3,4-Cl2Flu), 1-monochloropyrene (1-ClPyr), 6-monochlorochrysene (6-ClChr),

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6,12-dichlorochrysene (6,12-Cl2Chr), 7-monochlorobenz[a]anthracene (7-ClBaA),

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7,12-dichlorobenz[a]anthracene (7,12-Cl2BaA), and 6-monochlorobenzo[a]pyrene

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(6-ClBaP).

144

USA). 9-ClPhe was obtained from Acros Organics (Geel, Belguim). The remaining

145

ClPAHs standards were synthesized at the University of Shizuoka (Shizuoka, Japan).

146

The purity of the synthesized ClPAH standards were greater than 95% (confirmed by

147

gas chromatograph interfaced with mass spectrometer, GC/MS) 19, 27.

148

U.S. Environmental Protection Agency’s (EPA) priority PAHs were determined.

149

Sixteen PAHs and deuterated PAH standard mixtures, including naphthalene-d8,

150

acenaphthene-d10, phenanthrene-d10, chrysene-d12, and pyrene-d12 were purchased

151

from AccuStandard (New Haven, CT, USA). Silica gel (grade 635, 60–100 mesh)

152

was obtained from Aldrich and was activated at 130 °C for 6 h prior to use.

153 154

(3,9-Cl2Phe),


(9,10-Cl2Phe),

2-monochloroanthracene

9,10-dichloroanthracene

(1,9-Cl2Phe),

3,9,10-trichlorophenanthrene

(2-ClAnt),

9-monochloroanthracene

(9,10-Cl2Ant),

3-monochlorofluoranthene

8-monochlorofluoranthene

(8-ClFlu),

5,7-dichlorofluoranthene


(3,8-Cl2Flu),


2-ClAnt and 9-ClAnt were purchased from Aldrich (St. Louis, MO,

Chemical Analysis.

In addition, 16

The field blanks comprising actual quartz filters that had

been maintained at 40% relative humidity and 20°C for over 48 h were weighed

6


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before and after sampling.

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1.5 cm2 punch taken from each half quartz filter sample used for ClPAHs analysis

157

with a Desert Research Institute (DRI) carbon analyzer using IMPROVE

158

thermal/optical reflectance (TOR)

159

temperatures. The carbon that is evolved at each temperature is oxidized to carbon

160

dioxide (CO2), and then reduced to methane (CH4) for quantification with a flame

161

ionization detector 30. Total organic carbon (TC) is defined as the sum of OC and EC.

162

Instrument blanks were tested every day and one duplicate sample was analyzed for

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every ten samples.

164

C/cm2.

165

OC and EC in PM10 and PM2.5 were determined from a

30

. The quartz filter punch is heated stepwise at

The method detection limits for OC and EC were below 0.2 µg

The method for the analysis of ClPAH and parent PAH congeners were similar to

166

that described previously 18.

167

cm2 punch used for OC and EC analysis has been subtracted when do concentration

168

calculations, was cut into small pieces and then spiked with deuterated PAHs

169

standards, followed by accelerated solvent extraction (ASE-150, Dionex, Sunnyvale,

170

CA, USA) with dichloromethane (DCM) and n-hexane solution (3:1, v/v) at 100°C at

171

10 MPa.

172

column (2 g) chromatography by 20 mL of 20% DCM in n-hexane (denoted as F1)

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after a prewash step, by elution of n-hexane.

174

to 1 mL, and injected into a gas chromatograph-mass spectrometer (GC/MS;

175

Shimadzu QPlus 2010, Shimadzu, Kyoto, Japan) for 16 PAHs analysis.

176

was purified with a disposable polypropylene filtration column for SPE (3 mL, 6.5 cm

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length × 0.9 cm i.d., ANPEL, Shanghai, China) packed with a 0.2 g mixture of

178

activated carbon and silica gel (1:40, w/w; for activated carbon, G-60, 60-100 mesh).

179

The column was pre-cleaned by elution of toluene and n-hexane.

Briefly, half of each quartz filter sample, where the 1.5

The concentrated extracts were fractionated using activated silica gel

Then the fraction, F1, was concentrated

7


Then the F1

After loading the


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fraction F1, the self-packed column was eluted with 50 mL of 20% DCM in n-hexane

181

(F1-1), and then the column was reversed and eluted with 100 mL of toluene (denoted

182

as fraction F1-2).

183

µL, and analyzed by GC/MS.

184

fused silica capillary column (0.25 mm i.d., 0.25 µm film thickness; Restek,

185

Bellefonte, PA, USA).

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280°C for ClPAHs and at 260°C for PAHs.

187

programmed from 80°C (1 min) to 140°C at a rate of 15°C/min, and then raised to

188

300°C at 5°C /min and held at 300°C for 5 min for ClPAH analysis.

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analysis, the oven temperature was ramped from 60 (2 min) to 130°C at a rate of

190

10°C/min, and then to 270°C at 5°C /min, and then finally to 300°C (5 min hold) at

191

10°C/min.

192

monitoring (SIM) mode.

193

The fraction F1-2 that contained ClPAHs was concentrated to 200 GC separation was accomplished by a 30 m Rxi-5MS

Aliquots of 2 µL of extract were injected in splitless mode, at The column oven temperature was

For PAH

The MS was operated in an electron impact (70 eV) selected ion

Quality Assurance/Quality Control.

Field blanks (n=8) were analyzed with

194

every batch of samples, to monitor for contamination or interferences.

Sample

195

concentrations were determined from external calibration curves prepared at

196

concentrations ranging from 0.5 to 1000 ng/mL for ClPAHs and from 1 to 2000

197

ng/mL for PAHs.

198

every five samples, to monitor for instrument stability and for recovery calculation.

199

Recoveries of deuterated PAHs spiked into individual samples were 43 ± 16% for

200

naphthalene-d8, 78 ± 13% for acenaphthene-d10, 95 ± 20% for phenanthrene-d10, 93 ±

201

19% for chrysene-d12, and 97 ± 21% for pyrene-d12.

202

(0.12 pg/m3 on average), 9-ClPhe (0.26 pg/m3), 2-ClAnt (0.05 pg/m3), 9-ClAnt (0.01

203

pg/m3), and Phe (0.01 ng/m3) were detected in some field blanks.

204

concentrations were not corrected for the recoveries of surrogate standards.

Quality control standards (deuterated PAHs) were analyzed after

Low concentrations of 9-ClFle

8


Reported The

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limit of quantification (LOQ) was set at 3 times the standard deviation of the peak

206

area at the lowest-concentration of calibration standard, which was from 0.11 to 0.26

207

pg/m3 for ClPAHs, and from 0.49 to 1.13 pg/m3 for parent PAHs in air samples.

208

Data Analysis.

For statistical analysis, values below the LOQ, but above

209

method detection limit (MDL, which was set to be 3 times S/N), and non-detects (ND)

210

were set to be zero, whereas concentrations below the LOQ (but above MDL) are

211

presented in the Supporting Information.

212

SPSS version 15.0.

213

correlations between ClPAHs and parent PAHs and the mass of particulate matter.

Statistical analyses were performed using

Non-parametric Spearman’s rho test was used to investigate the

214 215 216

Results and Discussion Mass Concentrations of PM10, PM2.5, OC, and EC.

The concentrations of

217

24-h PM10 and PM2.5 at the monitoring site in Shanghai University Campus are shown

218

in the Supporting Information (Table S1).

219

and PM2.5 were 150 µg/m3 and 90.5µg/m3 during the sampling period, respectively.

220

The PM2.5 concentrations in the suburban air were 2.59 times higher than the new

221

annual standard of 35 µg/m3 set by the China’s National Ambient Air Quality

222

Standards (NAAQS)

223

The concentrations of PM10 and PM2.5 in this suburban area were as high as the

224

concentrations reported for other metropolises like Guangzhou (China) and

225

Zonguldak (Turkey)

226

0.63, which was generally ascribed to high contributions from secondary particles and

227

combustion related sources 33,34.

228 229

31

The average concentrations of 24-h PM10

; the US annual health standard for PM2.5 is 12 µg/m3

8, 30

.

(32)

.

The average ratio of 24-h PM2.5/PM10 concentrations was

OC and EC have important roles and effects on human health due to their physical and chemical characteristics

35

.

The average OC concentrations of PM10

9



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and PM2.5 were 19.3 µg/m3 and 12.8 µg/m3, respectively, and the average EC

231

concentrations of PM10 and PM2.5 were 11.7 µg/m3 and 8.52 µg/m3, respectively.

232

The total organic carbon (TC; OC plus EC) concentrations in PM10 and PM2.5 were

233

30.9 µg/m3 and 21.3 µg/m3, respectively.

234

fuel and biomass burning locally; secondary OC is formed from gas-particle

235

conversion processes in the atmosphere.

236

tracer for the evaluation of origin of carbonaceous matter in the atmosphere

237

there was a constant regional contribution of aged aerosol with high secondary OC,

238

the (OC/EC)min ratios would increase

239

PM10 and 1.08 for PM2.5, with relatively high average EC concentrations in our

240

sampling site, which suggests pollution from fresh local emissions rather than

241

regional and long range transported secondary organic aerosols (SOA). In addition,

242

the low ratios suggest that the origin of organic contaminants in particulate matter was

243

mainly from the local emissions.

EC and primary OC may result from fossil

The ratio of (OC/EC)min has been used as a

35

.

36

.

If

The (OC/EC)min ratios were low, 1.19 for

244 245

PM10/PM2.5-associated ClPAHs and Parent PAHs.

The total concentrations

246

of ClPAHs associated with airborne PM10 and PM2.5 are illustrated in Figure 1 (A and

247

B), and the concentrations for individual compounds are presented in the Supporting

248

Information (Table S2 and Table S3).

249

ClPAH congeners were found at detection rates ranging from 86% to 100% in PM10,

250

and from 82% to 100% in PM2.5, indicating that ClPAHs are ubiquitous in

251

atmospheric particulate matter.

252

of the 12 individual ClPAH congeners that were detected in PM samples.

253

and median concentrations of ∑ClPAHs in PM10 were 12.3 pg/m3 and 10.1 pg/m3,

254

respectively, with a range of 2.45 - 47.7 pg/m3.

During the study period, 12 of the 20 target

∑ClPAHs is referred to as the sum of concentrations The mean

For PM2.5, the mean and median

10


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255

concentrations of ∑ClPAHs were 9.06 pg/m3 and 7.31 pg/m3, respectively, with a

256

range of 1.34 - 22.3 pg/m3.

257

PM2.5-associated ClPAHs were slightly lower than the PM10-associated concentrations.

258

Overall, concentrations of ∑ClPAHs and individual ClPAH congeners associated with

259

PM10 and PM2.5 were log-normally distributed, as determined by one sample

260

Kolmogorov-Smirnov test (P > 0.05).

261

been reported for urban air in Japan during 1992 - 2002 (sum of 7 ClPAH

262

concentrations ranged from

323

BaA > Pyr > Phe > Ant > Fle, both in PM10 and PM2.5, which is slightly different

324

from the order found for the corresponding ClPAHs (Figure 3), but similar to that

325

reported for TSP-bound PAHs in urban air from Japan 25.

326

of PAHs were 3 to 4 orders of magnitude higher than those of the corresponding

327

ClPAHs.

328 329

The detection frequencies of individual PAHs in PM ranged The mean and median concentrations of ∑16PAHs in PM10

For PM2.5, the mean and median concentrations were 28600 pg/m3 and These results

Particle size is a major determining factor in

39

.

For seven of the parent

The mean concentrations

The formation of ClPAHs by chlorination of PAHs in the presence of various chlorine sources, UV irradiation, pH, and metallic catalysts has been studied

13


(40-43)

.


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20

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330

Horii et al.

331

parent PAHs in waste incinerators.

332

particulate emissions from a diesel engine fueled with biodiesel, ultra low sulfur

333

diesel, and low sulfur diesel 44; nevertheless, no ClPAH was detected in the particulate

334

samples.

335

automobile exhaust directly, but were potentially formed by secondary reactions in

336

the atmosphere.

337

primary and secondary sources in air is needed to gain better insight on the behavior

338

of these compounds in the environment.

339

suggested that ClPAHs were formed directly from the chlorination of In our previous study, we found PAHs in

These results suggested that some ClPAHs were not released from the

More research on the mechanism of formation of ClPAHs and their

Relationships of Parent PAHs, Particulate Mass and Total Organic Carbon The relationship between the concentrations of ClPAHs and their

340

with ClPAHs.

341

parent PAHs has been investigated in sediment, TSP, fly ash from waste incineration,

342

and dust/soil from an e-waste recycling facility

343

between temperature, TSP mass, incinerator capacity, and urbanization process, with

344

the concentrations of ClPAHs, were also reported

345

investigated the relationship between ClPAH and parent PAH concentrations,

346

particulate mass, and total organic carbon (Table 2).

347

were found between ∑ClPAHs, 9,10-Cl2Phe, 3-ClFlu, 8-ClFlu, 3,4-Cl2Flu, 1-ClPyr,

348

7-ClBaA, and 6-ClBaP, with their corresponding parent PAHs in PM10.

349

correlations were also found for PM2.5 except for 6-ClBaP and 9,10-Cl2Phe.

350

Concentrations of 3-ClFlu, 8-ClFlu, 3,4-Cl2Flu, 1-ClPyr, 7-ClBaA, 6-ClBaP and

351

∑ClPAHs in PM10 and PM2.5 were significantly correlated with TC levels in PM.

352

Airborne carbonaceous materials, EC and OC, are the largest contributors to the

353

particle burden in air

354

and carcinogenic effects have been detected in OC 46, 47.

30, 45

.

18-21, 25

.

In addition, correlations

20, 21, 25

.

In our study, we

Significant positive correlations

A similar

PAHs and other components with possible mutagenic The correlation of OC with

14


Page 15 of 30

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


355

ClPAHs suggests that ClPAHs are sorbed onto organic carbon of PM.

356

we found no correlation between ClPAHs and temperature, or relative humidity.

357

Contrarily, significant correlations were found between particulate mass, total organic

358

carbon, temperature, and humidity, with the concentrations of parent PAHs except for

359

Fle.

360

Nevertheless,

Prediction of Concentrations of PM-associated Total ClPAHs and Parent Multiple linear regression analysis (MLRA) has been used by many

361

PAHs.

362

researchers to predict the ambient concentrations of PAHs

363

MLRA was performed to further investigate the effect of PM, TC, and meteorological

364

conditions, such as temperature and relative humidity on airborne concentrations of

365

ClPAHs and parent PAHs.

366

predict concentrations, PM, TC, temperature, and humidity were selected for MLRA

367

of parent PAHs (p< 0.01).

368

temperature was found in our study, a significant negative correlation was reported

369

between ClPAHs and temperature in an earlier study 25.

370

variables that were selected for the prediction of atmospheric PAH concentrations

371

were included in the regression analysis to predict ClPAH concentrations (p< 0.01).

372

The predicted total concentrations of PM10 and PM2.5 associated ClPAHs and parent

373

PAHs were compared with the measured data (from this study).

374

predicted and measured total concentrations of PM10-PAHs,

PM2.5-PAHs,

375

PM10-ClPAHs, and PM2.5-ClPAHs are shown in Figure 4 (A-D).

The predicted

376

concentrations of parent PAHs agreed well with the measured ones with strong

377

coefficients of determination of 0.918 and 0.950 for PM10 and PM2.5-associated parent

378

PAH concentrations, respectively.

379

results for predicting ClPAH concentrations.

8, 48, 49

.

In this study,

On the basis of statistical significance and ability to

Although no correlation between ClPAHs and

Thus, the same independent

The comparison of

However, the models did not yield satisfactory As shown in Figure 4C-D, the

15



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 30

380

comparison of predicted and measured total concentrations of PM10 and

381

PM2.5-associated ClPAHs showed weak coefficients of determination.

382

on physical-chemical properties of ClPAHs is scarce and more detailed parameters are

383

necessary for the development of reliable models to predict atmospheric

384

concentrations of these compounds

385

ClPAHs might be different from their corresponding parent PAHs; some ClPAHs are

386

probably formed by secondary reactions with other precursors present in the

387

atmosphere 20.

388

26

.

Information

Furthermore, the formation process of

These factors may affect formation of ClPAHs from parent PAHs.

Toxic Equivalency Quotients of ClPAHs and Parent PAHs.

The

389

AhR-mediated activities of 18 ClPAHs and their corresponding parent PAHs have

390

been reported previously

391

calculated TEQ concentrations of ClPAHs and parent PAHs associated with PM10 and

392

PM2.5 using the following equation:

16

.

On the basis of these relative potency values, we

TEQ = ∑ [C i ]REPBaPi / 60

393 394

where C i is the concentration of individual ClPAH and parent PAH, REPBaPi is

395

the potency of individual ClPAHs and corresponding parent PAHs relative to BaP

396

(based on EC50).

397

(TEQClPAH) were 2.14 pg-TEQ/m3 and 1.24 pg-TEQ/m3 for PM10-ClPAHs and

398

PM2.5-ClPAHs, respectively.

399

PM10 and PM2.5 were 7130 pg-TEQ/m3 and 5620 pg-TEQ/m3 (Table S8).

400

and 6-ClBaP collectively accounted for the preponderance of the total TEQClPAH in

401

PM samples, which is similar to the pattern reported for samples from an e-waste

402

recycling facility in our previous study

403

95% of the total TEQPAH.

The calculated mean dioxin-like TEQ concentrations of ClPAHs

The TEQs of corresponding parent PAHs (TEQPAH) in

18

.

7-ClBaA

BaA and BaP accounted for more than

16


Page 17 of 30

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


In summary, this is the first study to report ClPAH concentrations in airborne

404 405

PM10 and PM2.5 in suburban air.

We found that mono- and di-chloro substituted

406

PAH congeners were ubiquitous and predominant in atmospheric fine particulate

407

matter.

408

those in daytime PM samples.

409

environmental stabilities in air regardless of the particle size.

410

physical-chemical properties of ClPAHs is needed to better understand the behavior,

411

sources and toxic effects of ClPAHs in air.

412

Acknowledgements

413

This work was financially supported by the National Natural Science Foundation of

414

China (Nos. 21007039, 21210102027, 11025526, and 41073073).

415

Supporting Information Available

416

This information is available free of charge via the Internet at http://pubs.acs.org.

The ∑ClPAHs concentrations in nighttime PM samples were higher than 6-ClBaP, 1-ClPyr, 7-ClBaA and 3-ClFlu have strong Further research on the

417 418

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566

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568 569 570

Figure Legends

571

FIGURE 1. Concentrations of (A) total PM10-bound ClPAHs (pg/m3) and PM10 mass

572

(µg/m3), (B) total PM2.5-bound ClPAHs (pg/m3) and PM2.5 mass (µg/m3), (C)

573

PM10-bound 16PAHs (pg/m3) and total organic carbon (TC, µg/m3), and (D)

574

PM2.5-bound 16PAHs (pg/m3) and TC (µg/m3) in suburban air in Shanghai, China,

575

during the sampling period of October 2011-March 2012.

576

FIGURE 2. Concentrations of 12-h daytime-nighttime airborne PM10/PM2.5-bound

577

ClPAHs (pg/m3) during the sampling period of 2-8 April, 2012.

23



578

FIGURE 3. Average abundance (%) of PM10 and PM2.5-associated seven parent

579

PAHs (B) and their corresponding chlorinated PAHs (A) in suburban air in Shanghai,

580

China.

581

FIGURE 4. Comparison of predicted (using multi-linear regression models) and

582

measured concentrations of (A) PM10-PAHs, (B) PM2.5-PAHs, (C) PM10-ClPAHs and

583

(D) PM2.5-ClPAHs for the period of October 2011-March 2012 in a suburban area in

584

Shanghai, China.

585 586 180000

50

ClPAHs PM10

350 300

40 250 30

200 150

20

100

10

PM10-bound ∑16PAHs (pg/m 3)

400

(A)

160000 140000

80

100000 60 80000 60000

40

40000 20 20000 0

30

ClPAHs PM2.5

200 180

140 20

120 100

15

80 10

60 40

5

20

180000

0

(D)

160000

16PAHs TC

60 140000 120000 100000 80000

50 40 30

60000 20 40000 20000 0 10 11 26- 2 11 01- 011 -0 20 11 7- 11 - 2 11 14- 011 - 2 11 20- 011 - 2 12 26- 011 -0 20 12 2- 11 - 2 12 10- 011 - 2 12 15- 011 - 2 12 24- 011 - 2 01 28- 011 -0 2 0 01 4- 11 - 2 01 10- 012 - 2 01 16- 012 - 2 01 24- 012 - 2 02 30- 012 -0 20 02 7- 12 -1 20 03 6- 12 - 2 03 10- 012 - 2 03 17- 012 - 2 03 24- 012 -2 20 8- 12 20 12

0

10 11 26- 2 11 01- 011 - 2 11 07- 011 - 2 11 14- 011 - 2 11 20- 011 - 2 12 26- 011 - 2 12 02- 011 - 2 12 10- 011 - 2 12 15- 011 - 2 12 24- 011 - 2 01 28- 011 - 2 01 04- 011 - 2 01 10- 012 - 2 01 16- 012 - 2 01 24- 012 - 2 02 30- 012 - 2 02 07- 012 - 2 03 16- 012 - 2 03 10- 012 - 2 03 17- 012 - 2 03 24- 012 -2 20 8 - 12 20 12

70

FIGURE 1.

589 590 591 592 593 594 595 24


10 0

TC in PM2.5 (µg/m3)

160

25

PM2.5-bound ∑16PAHs (pg/m 3)

(B)

PM2.5 (µg/m3)

PM2.5-bound∑ClPAHs (pg/m3)

100

50

0

588

16PAHs TC

120000

0

587

120

(C)

TC in PM10 (µg/m 3)

PM10-bound ∑ClPAHs (pg/m 3)

60

PM10 (µg/m 3)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 30

Page 25 of 30

596 597 16 14

PM bound ClPAHs (pg/m3)

12

PM2.5-bound daytime samples PM2.5-bound nighttime samples PM10-bound daytime samples PM10-bound nighttime samples

10 8 6 4 2 0

598 599

9Cl F 9- le C 3, lPh e 9C 9, 2l P h 10 -C e l 2P h 2- e C lA nt 9C lA n 3- t C lF l 8- u C l F 3, 4- lu Cl 2F l 1- u C lP 7- yr C lB aA 6C ∑ lBa C P lP AH s

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


FIGURE 2.

600 601 602 603 604 605 606 607 608 609

25



100

100 (A)

(B)

80

80 ClBaP

Abundance %

Abundance %

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ClBaA

60

ClPyr ClFlu ClAnt

40

ClPhe ClFle

20

611

BaP BaA

60

Pyr Flu Ant Phe

40

Fle

20

0

610

Page 26 of 30

0 PM10-ClPAHs

PM2.5-ClPAHs

PM10-PAHs

FIGURE 3.

612 613 614 615 616 617 618 619 620 621 622 623 624 625 626

26


PM2.5-PAHs

Total PM10-bound ClPAHs Concentration (pg/m3)

627

628 60

50

40 Measured ClPAHs Predicted ClPAHs

R2 = 0.918

30

20

10 0

30000 0 10

Measured PAHs

0 10

20

20

30

45

30

40

40

50

20000

10000

0

R2 = 0.356

30

15

0 50

Measured ClPAHs

30

20

10

0 10 -2 11 6-0 20 11 1- 11 - 20 11 07- 11 - 20 11 14- 11 -2 20 11 0- 11 - 20 12 26- 11 - 20 12 02- 11 - 20 12 10- 11 - 20 12 15- 11 -2 20 12 4- 11 -2 20 01 8- 11 - 20 01 04- 11 - 20 01 10- 12 - 20 01 16- 12 - 20 01 24- 12 - 20 02 30- 12 - 20 02 07- 12 -1 20 03 6-2 12 - 0 03 10- 12 -1 20 03 7- 12 -2 20 03 4- 12 -2 20 8- 12 20 12

Total PM2.5-bound parent PAHs Concentration (pg/m3)

40

Measured 7PAHs Predicted 7PAHs

40000

70 60

Measured ClPAHs Predicted ClPAHs

50

40

30

FIGURE 4.

629

630

631

632

633

634

635

636

637

638

639

640

641

642

27


Predicted PAHs

50000

Predicted ClPAHs

40000

50

Total PM2.5-bound ClPAHs Concentration (pg/m3)

60000

10 -2 11 6-2 -0 0 11 1- 11 - 20 11 07- 11 - 20 11 14- 11 -2 20 11 0- 11 - 20 12 26- 11 - 20 12 02- 11 - 20 12 10- 11 - 20 12 15- 11 -2 20 12 4- 11 -2 20 01 8- 11 -0 20 01 4- 11 - 20 01 10- 12 - 20 01 16- 12 - 20 01 24- 12 - 20 02 30- 12 - 20 02 07- 12 -1 20 03 6-2 12 - 0 03 10- 12 - 20 03 17- 12 -2 20 03 4-2 12 -2 0 8- 12 20 12

50000 Predicted PAHs

Measured 7PAHs Predicted 7PAHs

Predicted ClPAHs

10 11 26-0 20 11 1- 11 - 20 11 07- 11 -1 20 11 4- 11 -2 20 11 0- 11 - 20 12 26- 11 - 20 12 02- 11 - 20 12 10- 11 - 20 12 15- 11 - 20 12 24- 11 -2 20 01 8- 11 -0 20 01 4- 11 - 20 01 10- 12 -1 20 01 6- 12 - 20 01 24- 12 - 20 02 30- 12 - 20 02 07- 12 - 20 03 16- 12 - 20 03 10- 12 - 20 03 17- 12 -2 20 03 4-2 12 -2 0 8- 12 20 12

Total PM10-bound parent PAHs Concentration (pg/m3)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 10 11 26-0 20 11 1- 11 - 20 11 07- 11 - 20 11 14- 11 - 20 11 20- 11 - 20 12 26- 11 -0 20 12 2- 11 -1 20 12 0- 11 -1 20 12 5- 11 - 20 12 24- 11 -2 20 01 8- 11 - 20 01 04- 11 - 20 01 10- 12 - 20 01 16- 12 - 20 01 24- 12 - 20 02 30- 12 -0 20 02 7- 12 -1 20 03 6- 12 - 20 03 10- 12 -1 20 03 7- 12 - 20 03 24- 12 -2 20 8- 12 20 12

Page 27 of 30 Environmental Science & Technology

60000 60

30000

R2 = 0.950

40

20

0 0

Measured PAHs

20

60

0 5

40

10 15

60

20000

10000

0

45

R2 = 0.434

30

15 0

Measured ClPAHs

20

20

10

0


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

TABLE 1. Concentration Ratios of Selected ClPAHs Normalized to 1-ClPyr and 3-ClFlu Urban air Suburban air (campus) a Road tunnel c Urban street c (campus) b PM10-bound PM2.5-bound TSP-bound TSP-bound TSP-bound 6-ClBaP/1-ClPyr 2.35 2.24 2.83 0.39 0.41 3-ClFlu/1-ClPyr 0.60 0.53 0.68 0.89 0.87 7-ClBaA/1-ClPyr 0.81 0.55 0.60 0.08 0.16 6-ClBaP/3-ClFlu 2.64 2.58 4.84 0.73 0.61 1-ClPyr/3-ClFlu 1.13 1.15 1.68 1.88 1.47 7-ClBaA/3-ClFlu 0.91 0.63 1.00 0.15 0.23 a Mean concentrations were used in this study. b Data calculated from TSP-bound ClPAH compounds (mean concentrations) by Kitazawa, et al. (25). C Data calculated from particulate phase by Nisson and Östman (24).

643 644 645 646 647 648 649 650 651 652 653 654 655 656 657 658 659 660 661 662 663 664

28


Page 28 of 30

Page 29 of 30

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


TABLE 2.

Correlation between ClPAH and Corresponding Parent PAH Concentrations, Particle Mass, and Total Organic Carbon PM10-bound PM2.5-bound Compounds Compounds Parent PAH PM TC Parent PAH PM TC 9-ClFle 0.523* a 0.274 0.116 9-ClFle 0.175 -0.250 -0.294 9-ClPhe 0.189 0.155 0.149 9-ClPhe 0.477* -0.034 -0.049 * 3,9-Cl2Phe 0.344 0.358 0.485 3,9-Cl2Phe 0.102 0.056 0.071 9,10-Cl2Phe 0.694** 0.529* 0.723** 9,10-Cl2Phe -0.049 -0.084 -0.048 2-ClAnt -0.052 0.182 0.111 2-ClAnt 0.254 -0.189 -0.176 9-ClAnt 0.213 0.432* 0.363 9-ClAnt 0.193 -0.064 0.022 3-ClFlu 0.781** 0.660** 0.743** 3-ClFlu 0.770** 0.693** 0.692** 8-ClFlu 0.738** 0.427* 0.663** 8-ClFlu 0.784** 0.549** 0.635** ** * ** ** 3,4-Cl2Flu 0.808 0.486 0.714 3,4-Cl2Flu 0.818 0.458* 0.590** ** * ** ** 1-ClPyr 0.736 0.503 0.670 1-ClPyr 0.889 0.543** 0.631** ** * ** * 7-ClBaA 0.843 0.628 0.807 7-ClBaA 0.862 0.589** 0.694** 6-ClBaP 0.619** 0.532* 0.579** 6-ClBaP 0.340 0.429* 0.448* ** * ** ** * ∑ClPAHs 0.712 0.592 0.700 ∑ClPAHs 0.713 0.432 0.482* * Fle 0.439 0.326 Fle 0.418 0.331 Phe 0.784** 0.827** Phe 0.625** 0.628** Ant 0.632** 0.686** Ant 0.744** 0.829** ** ** Flu 0.787 0.899 Flu 0.670** 0.729** Pyr 0.773** 0.848** Pyr 0.623** 0.684** ** ** BaA 0.633 0.792 BaA 0.638** 0.765** ** ** BaP 0.663 0.796 BaP 0.589** 0.700** ** ** ∑7PAHs 0.782 0.927 ∑7PAHs 0.668** 0.773** a Correlation coefficient: ** p < 0.01 (2-tailed), * p < 0.05 (2-tailed)

665 666 667 668 669 670 671 672 673 674 675 676 677 678 679 680

29



681

TOC Art

Cl

50

PM bound ∑ ClPAHs (pg/m3)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 30

682

40

30

PM2.5

PM10

20

10

0

30


PM10-Associated Chlorinated Polycyclic Aromatic

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