Source apportionment of atmospheric pollutants based on the online data by
using PMF and ME2 models at a megacity, China

Baoshuang Liu, Jiamei Yang, Jie Yuan, Jiao Wang, Qili Dai, Tingkun
Li, Xiaohui Bi, Yinchang Feng, Zhimei Xiao, Yufen Zhang, Hong Xu

PII: S0169-8095(16)30523-3
DOI: doi:10.1016/j.atmosres.2016.10.023
Reference: ATMOS 3824

To appear in: Atmospheric Research

Received date: 8 August 2016

Revised date: 16 October 2016
Accepted date: 26 October 2016

Please cite this article as: Liu, Baoshuang, Yang, Jiamei, Yuan, Jie, Wang, Jiao,
Dai, Qili, Li, Tingkun, Bi, Xiaohui, Feng, Yinchang, Xiao, Zhimei, Zhang, Yufen,
Xu, Hong, Source apportionment of atmospheric pollutants based on the online data
by using PMF and ME2 models at a megacity, China, Atmospheric Research (2016),
doi:10.1016/j.atmosres.2016.10.023

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 ACCEPTED MANUSCRIPT

Source apportionment of atmospheric pollutants based on the online

data by using PMF and ME2 models at a megacity, China

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Baoshuang Liua, Jiamei Yanga, Jie Yuanb, Jiao Wanga, Qili Daia, Tingkun Lia, Xiaohui Bia,
Yinchang Fenga*, Zhimei Xiaob, Yufen Zhanga, Hong Xub

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a
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State Environmental Protection Key Laboratory of Urban Ambient Air Particulate Matter
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Pollution Prevention and Control, College of Environmental Science and Engineering, Nankai
University, Tianjin, 300071, China
b
Tianjin Environmental Monitoring Center, Tianjin, 300191, China
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Corresponding authors
Tel.: +86 2223503397; Fax: +86 2223503397
E-mail address: bixh@nankai.edu.cn and fengyc@nankai.edu.cn
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Abstract.
From 1st June to 31st August 2015, the online datasets (the water soluble ions (WSIs), OC

and EC in PM2.5, and SO2, NO2, NO) were measured continuously at Tianjin. Source apportionment

of atmospheric pollutants was carried out by using PMF and ME2 models based on the online

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datasets. During summer in Tianjin, the ammonium sulfate/ammonium hydrogen sulfate might be

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major forms of sulfate in the atmospheric aerosol, while the ammonium nitrate might be major

forms of nitrate. The poor correlation between OC and EC might be caused by the changes of

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emission sources and the production of secondary organic carbon (SOC). Five source-categories

that contributed to atmospheric pollutants were extracted by PMF and ME2 models, respectively.

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The profiles calculated by PMF and ME2 models were consistent, and the source contributions

estimated by the two models were also similar. The correlations (R2 = 0.84-0.94) were better on the
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time series of the contributed concentrations for the same source-category calculated from PMF and

ME2 models. The source-categories were identified as secondary sources (the contribution of
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25.4-26.1 %), vehicle exhaust (23.3-25.4 %), coal combustion (16.5-18.2 %), crustal dust

(13.2-14.0 %) and biomass burning (9.1-10.2 %). For the same source-category identified from
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PMF and ME2 models, the differences of profiles might be attributed to the differences of calculated

methods from the two models and the uncertainties of the online datasets.
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Keywords: Atmospheric pollutants; Rapid source apportionment; Online dataset; PMF; ME2

1. Introduction
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Along with its economic development and urbanization, the heavy hazy episodes always

occurred around China, especially in the Beijing-Tianjin-Hebei, the Pearl River Delta and the

Yangtze River Delta areas (Cheng et al., 2008; Deng et al., 2008; Du et al., 2011; Fu et al., 2008; Hu

et al., 2008; Yang et al., 2011; Zhao et al., 2012). In the hazy episodes, PM2.5 and related gaseous

materials (SO2 and NOx) have been proved to be major atmospheric pollutants. These pollutants

have also adverse effects to human health, atmospheric visibility and climate change (Liu et al.,

2016; Jimnez et al., 2009; Mimura et al., 2014). So far, many studies have been conducted for

obtaining effective information on chemical characteristics of PM2.5 and emission sources, which

could be helpful to pollution control and management (Liu et al., 2016; Tao et al., 2014; Yang et al.,

2011). Studies indicated that PM2.5 could be mainly derived from coal combustion, vehicle exhaust

and biomass combustions, soil dust, construction dust and resuspended dust, etc. (Cheng et al., 2014;
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Elbir and Muezzinoglu, 2004; Liu et al., 2016; Reddy and Venkataraman, 2002; Watson et al., 2001).

However, the gaseous pollutants (SO2 and NOx) along with PM2.5 emission were rarely conducted

source apportionment.

Additionally, it was very important significance for effective response to the heavy pollution

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process to acquire timely sources information in a short-time hazy episode. Accordingly, comparing

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to the offline sampling method, the online instruments had attracted increasing attentions because

emission sources could be identified rapidly based on the online datasets (Gao et al., 2016). To date,

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the most used online-instruments mainly included Single Particle Mass Spectrometers (SPMS),

Aerosol Mass Spectrometers (AMS), Ambient Ion Monitor (AIM), Particulate Metals Monitor

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(PMM), the Sunset semi-continuous OC/EC analyzer, and the online gaseous pollutants analyzers

(Gao et al., 2016). The online instruments could acquire the mass concentrations of PM2.5 and
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chemical species, as well as related gaseous pollutants, which provided a large dataset with

high-time resolution. Then, the datasets could be applied to investigate the characteristics of
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chemical compositions in PM2.5 and related gaseous pollutants (Gao et al., 2016; Khezri et al., 2013;

Li et al., 2014; Vodika et al., 2015; Zhang et al., 2014). Nevertheless, the studies that conducted
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source apportionment by using high-resolution datasets from online instruments were still limited

around the world (Petit et al., 2014; Sarkhosh et al., 2013; Wang et al., 2014).
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Although the online instruments could obtain the high-resolution datasets so that the

atmospheric pollution-characteristics could be understood timely, and these online datasets had
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larger uncertainties because of rapidly measured methods. In addition, these datasets were measured

by using different online instruments, which were independent of each other in the process of

sampling to analysis. Therefore, the further researches on source apportionment based on the online

datasets were still needed. In order to enhance the rationality of source apportionment results,

multiple receptor models should be applied to carry out source apportionment in terms of the same

online datasets, and then obtained more reasonable results by comparing between different models

(Belis et al., 2015; Cesari et al., 2016). Moreover, the various online-datasets were able to supply

only some pollutants, such as particles number concentrations, VOC species and gaseous materials

(SO2, NO and NO2), so that many studies have tried to combine the marked online and offline

components to conduct source apportionment of the atmospheric particles (Choi et al., 2015; Ke et

al., 2008; Vu et al., 2015; Wang et al., 2016). Nevertheless, these source apportionments cannot
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be conducted timely, especially for a short-time hazy episode.

Tianjin, an economically developed and rapidly growing megacity in China, with a population

of > 14 million and automobiles of > 2.7 million until 2013 (Tianjin Statistical Yearbook, 2014). In

recent years, the heavy hazy episodes always occurred in Tianjin. Therefore, the online instruments

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provided the feasibility for timely identifying sources of atmospheric pollutants, and then suggest

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effective control-measures. The objectives of this study are to: (1) analyze the characteristics of

atmospheric pollutants during summer at Tianjin; (2) conduct source apportionment of atmospheric

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pollutants by using the online datasets; (3) identify sources of atmospheric pollutants by combining

with PMF and ME2 models; and (4) establish rapid source apportionments based on the online

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datasets.

2. Material and method

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2.1 Site description

From 1st June to 31st August 2015, the sampling campaign was carried out at TEPB (Tianjin
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Environmental Protection Bureau), on the rooftop of a five-story building, about 10 meters above

ground level. The sampling site is situated in Nankai district, nearby the center of Tianjin city
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(Fig.1). The sampling site is surrounded by the residential buildings and university buildings, and is

approximately 300 meters distant from a traffic main-road. The meteorological conditions during
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the sampling period were illustrated in Fig. 2. The mean wind speeds (WS) at the sampling site were

1.8 m/s and temperature averaged 27.0 . The mean relative humidity (RH) was up to 54.5 %
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during summer.

Fig. 1. Location of the sampling site at Tianjin.

Fig. 2. The meteorological conditions during summer at Tianjin. Arrowheads represent the direction

of wind blowing toward.

2.2 Sampling method

The URG 9000D ambient ion monitor (AIM) (Chapel Hill, NC) was applied to determine the

ionic fraction in PM2.5 with hourly concentrations, including NO3, Cl, F, SO42, NH4+, Ca2+, Na+,

Mg2+, and K+. The AIM could separate and analyze each ion singly through combining the proven
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analyzing method of Ion Chromatographs (ICs). The AIM composes of a particle collected system

and two ICs for the anion and cation analysis. The atmospheric aerosols are collected at a flow rate

of 3 L/min by using a PM2.5 sharp cut cyclone (Di Gilio et al., 2015; Manigrasso et al., 2010). The

aerosol samples are drawn by a liquid diffusion parallel-plate denuder that separates the gas from

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the aerosol phase. The particle laden air stream enters an aerosol super saturation chamber to

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increase particle growth for accomplishing highly collected efficiencies. The water soluble

compositions of aerosol and the gaseous pollutants, extracted by an H2O2 solution, are collected

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through four syringes (particle and gaseous pollutants, cation and anion) installed into

pre-concentrators, and then injected into the ICs once within an hour. The analyzer (ICS-2000

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Reagent Free, Dionex Corporation) is fitted with a guard column, an analytical column, and a

self-regenerating suppressor. The cation analyzer runs in 27 min isocratic elution with 20 mM
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methane sulphonic at a flow rate of 0.5 mL/min, while the anion analysis is operated in a 27 min

gradient elution program by KOH solution at a flow rate of 1.0 mL/min. The minimum detection
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limits (MDLs) for NO3, Cl, F, SO42, NH4+, Ca2+, Na+, Mg2+ and K+ were 0.2, 0.2, 0.2, 0.3, 1.8,

2.3, 0.6, 0.8 and 0.5 g/m3, respectively. The calibration of the ICs on all of the AIM was carried out
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by the Anion/Cation Calibration Solutions for every three weeks. Generally, the preparation of

calibration solutions will take approximately 1 hour every time, and the process of the calibration
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for the ICs will take approximately 3 hours.

Concentrations of carbonaceous materials (OC and EC) in PM2.5 were determined

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semi-continuously by a model-4 semi-continuous OC/EC Analyzer (Sunset Laboratory Inc., USA)

with 1-hour resolution. This analysis was carried out by using thermal optical transmittance (TOT)

method based on NIOSH protocol (Birch and Cary, 1996). In order to decrease the adsorption

influences of volatile organic compounds (VOCs), the samples were passed through parallel plate

organic denuder to the cleaned quarts-filter. The process that OC and EC were determined mainly

contained two temperature stages: OC was evolved with ultrahigh 100 % Helium while a sample

filter (16.5 mm diameter) was gradually heated in an oxidizing-oven up to 820 . The

oxidizing-oven was then cooled to 550 , and the filter was again stepwise heated to 870 with

98 % Helium and 2 % Oxygen. Evolved carbon is oxidized to CO2 that was measured directly by a

non-dispersive infrared detector (NDIR) during each temperature step. The analyzer determined the

pyrolysis OC though defining the split point between OC and EC as the point when the
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transmittance of the filter was equal to that before analysis. The pyrolysis carbon is quantified as the

carbon evolved after the introduction of oxygen, but before the point where transmittance becomes

equal to its initial value. The OC was determined as the carbon evolved prior to this point, and EC is

measured as the carbon evolved after this point but prior to methane calibration peak. For quality

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control, the analyzer was calibrated every month by using a blank punch of pre-heated quartz fiber

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filter and standard sucrose solutions (3.2 gC/l). The quartz fiber filter was changed for each week

in the analysis process. The MDLs for OC and EC were 0.45 g/cm2 and 0.06 g/cm2, respectively.

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PM2.5 concentrations were measured continuously by the Thermo ScientificTM TEOM 1405-F

Ambient Particulate Monitor, which is composed of a Filter Dynamics Measurement System

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(FDMS) and a Tapered Element Oscillating Microbalance (TEOM) mass sensor installed in an

individual cabinet. The MDL is up to 0.1 g/m. The amount of NOx in the atmosphere is measured
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by using the Thermo Scientific Model 42i analyzer based on chemiluminescence technology. The

analyzer is an individual chamber, individual photomultiplier tube design that cycles between the
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NO and NO2 modes. The analyzer is isolated outputs for NO and NO2, and which can be calibrated

individually. The MDL is up to 0.40 ppb. The Thermo Scientific Model 43i SO2 Analyzer can apply
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pulsed fluorescence technology to measure the amount of SO2 in the atmosphere. The MDL is less

than 0.5 ppb. The Model 48i analyzer is mainly according to the principle that CO can absorb the
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infrared radiation at a 4.6 microns wavelength. The analyzer utilizes an accurate curve of calibration

to exactly linearize the instrument output. The MDL is up to 0.04 ppm. The Thermo Scientific
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Model 49i analyzer is a photometer of dual cell, the concept adopted by the NIST for the national O3

standard. The standard features of Model 49i analyzer are dual and auto range. The analyzer has a

response time of 20 seconds because of both sample and reference flowing at the same time. The

MDL is up to 0.50 ppb.

The meteorological conditions mainly including temperature, relative humidity (RH) and

wind speed (WS) were measured by a VAISALA WST520 automatic weather station with a time

resolution of 5 seconds.

2.3 PMF and ME2 models

2.3.1 PMF model

The PMF model was produced by Paatero and Tapper (1994), which can decompose a matrix

of sample dataset (X) into two matrices: source profile matrix (F) and source contribution matrix (G),
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in terms of observations at the sampling site (Paatero and Tapper, 1994; Paatero, 1997). PMF model

is described by:

(1)

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(2)

P
Where Xij represents the jth species concentration measured in the ith sample, gik represents the

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contribution of the kth source to the ith sample, fkj represents the source profile of jth species from the

kth source, eij represents the residual matrix for the jth species in the ith sample, and p presents the

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total number of independent sources (Paatero, 1997).

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In this study, the online dataset included WSIs, carbonaceous materials (OC and EC) and SO2,

NO and NO2, were input into EPA PMF 5.0 model (Fig. 4). The input dataset of PMF program
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including the concentration of each sample data and the uncertainties of the dataset, where can be

defined as follows:

(3)
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(4)

where U represents the uncertainty of data; P represents a percentage of the measurement

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uncertainty; c is the sample concentration; The MDLs of SO2, NO2 and NO are estimated by

minimum detection limit of the instruments (Tan et al., 2014). P values were set to 10 % by
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experience (Paatero, 2000; Tan et al., 2014). No samples can acquire the negative

source-contributions because the results have been constrained. Except for F-, and other variables
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are strong in the process of PMF application.

PMF can supply a solution that minimizes the objective function Q, which can be allowed to

review the distribution of each species, which is expressed as:

(5)

Where ij is the uncertainty of jth species in the ith sample, which is applied to weight the

observations that contain detection limits, missing data, sampling errors and outliers (Paatero,

2007).

2.3.2 ME2 model

Multilinear Engine 2 (ME2) is a receptor model produced by Paatero (1999), was used to

identify sources and calculate the corresponding contributions. Compared to PMF model, ME2
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model is able to conduct additional tasks by the programming languages with special objective in a

script file, which can modify a prior information (e.g. linear constraints, mass conservation,

chemical profile and ratios) by auxiliary equations, but no constraints were used in this study. Thus,

ME2 mainly contains a base run (similar to the basic PMF) and a continuation run, resulting in a

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different object function QME2 comparing to the QPMF. The function is viewed as the enhanced

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object function Qenh and can be described by Eq. (6) (Amato and Hopke, 2012).

(6)

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where Qmain is produced by the base run and expressed by Eq. (7) (Paatero and Hopke, 2009).

(7)

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where eij and ij are similar to PMF. Qaux is produced by the continuation run and is generally

described as the pulling equation, as shown in Eq. (8).

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(8)

where is the uncertainty of Qaux, which represents the user confidence. fij represents the factor
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loading element (jth species in ith source) and aij represents the target value. fij can be pulled toward

aij by employing Qaux. Source markers were used as the target values in this study to distinguish
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different emission-sources.

EPA PMF 5.0 and ME2 models were operated based on the online datasets composed of 14
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species (Cl, F, NO3, SO42, NH4+, Ca2+, Mg2+, K+, Na+, OC, EC, SO2, NO and NO2) and 91 (91

days) atmospheric pollutants samples for concentrations. Species with 15% of measured
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concentrations below the MDLs were removed. The missing data were replaced by the mean values

in this study.

3. Results

3.1 Characteristics of atmospheric pollutants

The daily variations of PM2.5 and related gaseous pollutants (e.g. SO2, NO2, NO, CO and O3)

concentrations were shown in Fig. 3. PM2.5 concentrations ranged from 15.7 to 227.0 g/m3, with a

mean value of 82.3 g/m3, which was more approximately 9.7 % than the Chinese Ministry of

Environmental Protection (Grade II standards for 24 h average PM2.5 is 75 g/m3). The gaseous

pollutants (SO2, NO2 and NO) related with PM2.5 were also monitored by the synchronous online

instruments, which were applied to serve as the markers of emission sources (Thimmaiah et al.,
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2009; Liu et al., 2006). The SO2 was mainly emitted from the power plants and other industrials

associated with fuel oil or coal combustion (Chan et al., 2011; Liu et al., 2006; Tan et al., 2014), the

concentrations of which varied from 6.0 to 39.3 g/m3, with a mean value of 17.1 g/m3 during

summer in Tianjin. The NO2, NO and CO in urban areas were mainly derived from the motor

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vehicle (Chan et al., 2011; Liu et al., 2006). The average concentrations of NO2, NO and CO was up

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to 36.6 g/m3, 2.6 g/m3 and 1.3 mg/m3, respectively, during summer in Tianjin. In this study, the

average concentration of O3 was up to 149.8 g/m3 during summer. The Ozone had strong oxidizing

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properties, and so high concentration of O3 could enhance the photochemical reaction of gaseous

precursors (SO2 and NOx) and increase the concentration of secondary ions such as SO42- and NO3-,

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etc. Therefore, the high O3 concentrations might be related to the secondary sources (Liu et al., 2013;

Zhao et al., 2013).

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Fig. 3. The daily concentration-variations of PM2.5 and related gaseous pollutants (SO2, NO2, NO,
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O3 and CO) during summer at Tianjin.

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The NO3, SO42, NH4+ and Cl are major chemical species in PM2.5 (Kim et al., 2006; Liu et al.,

2016; Viana et al., 2005; Wang et al., 2006). In this study, the concentrations of SO42 and NO3
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were higher in August (13.5 and 11.3 g/m3, respectively), and lower in June (8.3 and 6.6 g/m3,

respectively) (Fig. 4). Higher SO42- concentrations in August were probably attributed to higher
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secondary photochemical activities based on higher RH (the average of 58.2 %) and temperature

(28.7 ), lower WS (1.5 m/s) in August (Fig. 2), as well as higher concentrations of precursors

(SO2, the average of 19.3 g/m3) in August (Fig. 3 and Fig. 4), comparing to June and July (Gao et

al., 2016; Liu et al., 2016). Many reports have indicated that higher temperature was unfavorable to

the conversion of NO3- (Liu et al., 2016; Russell et al., 1983; Tao et al., 2012), therefore, the

conversion ratio of NO3- might be relatively lower in August. However, higher concentrations of

precursors (NO2, the average of 41.6 g/m3) could cause to the increase of NO3- concentrations, so

that high NO3- concentrations occurred in August. The monthly ratios of SO42/NO3 ranged from

1.24 to 1.40, which indicated the change of the emission pattern of stationary and mobile sources

might be less during summer at Tianjin (Arimoto et al., 1996; Liu et al., 2016; Yao et al., 2002).

Table 1 showed the correlations between the WSIs during summer. The correlation between SO42
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and NH4+ was higher (r = 0.96; P<0.01), while that of between SO42 and other WSIs were lower (r

< 0.56), indicating that the ammonium sulfate/ammonium hydrogen sulfate might be major forms of

sulfate in the atmospheric aerosol at Tianjin. In addition, the correlation between NO3- and NH4+

was also higher (r = 0.91, P<0.01) than that of between NO3- and other WSIs (r < 0.82), suggesting

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the ammonium nitrate might be major forms of nitrate in the atmospheric aerosol at Tianjin. Notably,

the correlation between SO42 and NO3 was relatively higher (r = 0.82, P<0.01) (Table 1), probably

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suggested that SO42 and NO3 were mainly originated from the same sources to some extent during

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summer in Tianjin. For instance, the most of SO42 and NO3 could be derived from the secondary

sources or other sources.

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Fig. 4. The concentrations of the water soluble ions (WIs) in PM2.5 and related gaseous pollutants
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(SO2, NO and NO2) during summer at Tianjin.
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Table 1. The correlations between the water soluble inorganic ions during summer at Tianjin.
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The daily variations of OC and EC concentrations, and the ratios of OC/EC during summer

were shown in Fig. 5. The OC concentrations varied from 3.4 to 14.8 g/m3, with a mean value of
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7.3 g/m3. The corresponding EC concentrations ranged from 0.8 to 6.1 g/m3, with a mean value of

2.2 g/m3. During summer, the correlation between OC and EC was relatively lower (R2 = 0.53),
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which might be attributed to the changes of emission sources and the production of SOC (Liu et al.,

2016; Wang et al., 2015). Generally, the ratio of OC/EC greater than 2.0-2.2 was used to identify and

evaluate secondary organic aerosols (SOA) (Chow et al., 1996; Turpin and Huntzicker, 1991). In

this study, the ratios of OC/EC varied from 2.2 to 5.6 during summer, with an average value of 3.4,

indicating the possible presence of SOC. The EC-tracer approach was applied to quantify SOC,

because its parameters could be easily obtained (Castro et al., 1999; Cao et al., 2004; Pio et al., 2011;

Liu et al., 2016), and the concentration of SOC can be expressed as following:

(9)

where OCtot represents the concentration of total OC; (OC/EC)min represents the lowest observed

OC/EC ratio. The monthly concentrations of SOC varied from 1.2 g/m3 (July) to 1.5 g/m3

(August) and the percentage of SOC/OC ranged from 17.1 % (July) to 18.9 % (August) in Tianjin
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(Fig. S5). The mean concentration of SOC was 1.3 ug/m3 and the mean percentage of SOC/OC was

17.8 % during summer. Watson et al. (2001) investigated that the large discrepancies and variability

of OC/EC ratios existed in coal combustion (0.3-7.6), vehicle exhaust (0.7-2.4) and biomass

burning (4.1-14.5). Schauer et al. (2002) have also illustrated OC/EC ratios of 1.0-4.2 for vehicular

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exhaust. Therefore, the vehicle exhaust, coal combustion, secondary aerosols and biomass burning

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might be major sources of atmospheric aerosol during summer at Tianjin.

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Fig. 5. The concentration variations and correlations of OC and EC, and the ratios of OC/EC during

summer at Tianjin.

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3.2 Source apportionment of atmospheric pollutants
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Results of source apportionment based on environmental datasets were always difficult to be

judged (Gao et al., 2016). In order to reduce the uncertainties of online datasets and enhance the
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rationality of the results, we mainly conducted the following works: (1) eliminated the abnormal

data (far greater/ lower than the average value); (2) conducted source apportionment based on daily
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datasets (calculated from hourly datasets); and (3) multiple receptor models were applied to carry

out source apportionment (Belis et al., 2015; Cesari et al., 2016). In this study, the atmospheric
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pollutants included the WSIs in PM2.5 and related gaseous pollutants (SO2, NO2 and NO) were input

into PMF and ME2 models for calculating, respectively, and eventually five factors were identified
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by the two models at the same time (Fig. 6). Although the principle of PMF and ME2 models were

similar, and the input uncertainties of the online dataset and the calculated methods in the analysis

process of PMF and ME2 models were different. Therefore, the comparison analysis between the

two models was useful to understand the potentialities and limits of the two models. Gao et al.,

(2016) and Xu et al. (2016) had carried out the similar researches by using PMF and ME2 models.

The calculated and measured atmospheric pollutants from PMF and ME2 models performed higher

correlations (R2 = 0.99 for PMF, R2 =0.95 for ME2) (Fig. S1), which suggested a better performance

of the results from PMF and ME2. Additionally, the Q values obtained by PMF (845) and ME2 (832)

models were shown in Table S1 in the supplement material, which were close to the theoretical Q

(819). The results further proved that the results of source apportionment calculated from PMF and

ME2 models were reasonable. As well known that the atmospheric lifetime of CO was longer (1-4
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months) than other gaseous pollutants such as SO2 (about a week), and NOx (1-7 days) (Marmur et

al., 2005; Seinfeld and Pandis, 1998; Wilson et al., 1997), so that CO was easy to be accumulated in

the atmosphere. When CO data was included in the input-data of the receptor models, the source

apportionment by using PMF and ME2 models could be interfered. Therefore, CO was not taken as

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the input-data of PMF and ME2 models.

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The profiles and contributions of sources from PMF model were illustrated in Fig. 6-8. As Fig.

6 shown that, factor 1 was mainly consisted of SO42, NO3, NH4+, and it can be identified as

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secondary sources (Contini et al., 2010; Gao et al., 2016; Liu et al., 2015; Liu et al., 2016;

Srimuruganandam and Nagendra, 2012). The correlation coefficients (r) between the time series of

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secondary sources contributions (factor 1) and the total secondary ions (SO42 plus NO3 plus NH4+)

varied from 0.85 to 0.87 (P0.01) (Fig. S2), illustrating dominate evidence that factor 1 was
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secondary sources. The contribution of factor 1 to atmospheric pollutants was up to 26.1 % in

Tianjin (Fig. 7), which was a major source of atmospheric pollutants during summer in Tianjin, and
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this result further indicated that the intense photochemical-reactions always occurred with higher

ozone concentrations during summer (Fig. 3). Tian et al. (2016) reported that secondary sources (the
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contribution of 26.2 %) was a primary contributor to PM2.5 in Tianjin. Gao et al. (2016) also

indicated that the contribution of secondary sources to PM2.5 was up to 38-39 % in Beijing. PM2.5
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has been found to be a major pollutant in the atmospheric aerosol in many cities (Gao et al., 2016;

Linares and Daz, 2009). Therefore, these results were more consistent with this study.
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Factor 2 had higher loading of NO2, NO, OC, and EC, and these species could indicate vehicle

exhaust (Chan et al., 2011; Kim and Hopke, 2004; Liu et al., 2006; Liu et al., 2016; Tao et al., 2014).

The correlation coefficients (r) between the time series of vehicle exhaust contributions (factor 2)

and CO concentrations was up to 0.71 (P<0.01) (Fig. S3), and hourly tendency of CO

concentrations was conformity with morning and evening traffic peak, which could indicate that CO

in urban area might be mainly derived from vehicle exhaust (Fig. S4), further proved that factor 2

was the vehicle exhaust. In this study, the vehicle exhaust was an important contributor to

atmospheric pollutants in Tianjin, accounting for approximately 25 % (Fig. 7). According to Tianjin

Statistical Yearbook (2014), the number of motor vehicles has been more than 2.7 million until 2013.

Therefore, vehicle exhaust could play an important role on the atmospheric pollution in Tianjin.

Nevertheless, Tian et al. (2016) suggested that the contribution of vehicle exhaust to PM2.5 was
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lower (the contribution of 14.0 %) in Tianjin than other sources. This might indicate that there were

some differences between source apportionments of PM2.5 and the atmospheric pollutants. After all,

PM2.5 was just one of atmospheric pollutants in Tianjin.

Factor 3 was relevant with biomass burning, which was identified by higher loading of K+, OC

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and EC (Fig. 6) (Andreae, 1983; Almeida et al., 2015; Hleis et al., 2013; Liu et al., 2016; Watson et

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al., 2001). The contribution of this factor to atmospheric pollutants was as much as 10.2 % (Fig. 7),

which implied that biomass burning had relatively low impact on atmospheric pollutants in urban

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areas of Tianjin. As mentioned above section 3.1, the OC/EC ratios ranged from 2.2 to 5.6 during

summer, with a mean value of 3.4, and Watson et al. (2001) and Cachier et al. (1989) reported that

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the OC/EC ratios for biomass burning were up to 4.1-14.5. Therefore, the relatively lower

contribution of biomass burning during summer was reasonable.

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Factor 4 had the high loading of Ca2+ and Mg2+, and which were closely related to the crustal

dust (Almeida et al., 2013; Bi et al., 2007; Liu et al., 2016). The contribution of this factor to the
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atmospheric pollutants in Tianjin accounted for 13.2 % (Fig. 7). Moreover, the contribution of this

factor to the atmospheric pollutants was lower than any sources, like due to the frequent rainfall
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during summer, which couldnt cause crustal dust to be suspended easily into the atmosphere (Liu et

al., 2016). Therefore, this result was rational and conformed to the characteristics of summer.
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Factor 5 was mainly represented by SO2, Cl, OC and EC, and these species were closely

associated with coal combustion (Bhangare et al., 2011; Cao et al., 2011; Chan et al., 2011; Liu et al.,
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2006; Liu et al., 2016). Watson et al. (2001) reported that the ratios of OC/EC for coal combustion

was 0.3-7.6, and as mentioned above, the average OC/EC ratio in this study was 3.4. Moreover, the

contribution of this factor to atmospheric pollutants was up to 16.5 % (Fig. 7). Therefore, coal

combustion also played a vital role on decreasing in air quality at Tianjin. Coal combustion was an

important emission source of atmospheric pollutants in China, especially in the northern regions

(Liu et al., 2016; Yao et al., 2009). Generally, coal combustion was always used in the power plants,

the industries and heating for the cold winter (Gao et al., 2016; Liu et al., 2016). However,

comparing to secondary sources and vehicle exhaust, the contribution of coal combustion was

relatively lower (Fig. 7), which was likely attributed to that there was no domestic heating during

summer (Gao et al., 2016). However, some unknown sources (the contributions of 8.6 %) were not

apportioned by PMF model. That was because sources of atmospheric pollutants were extremely
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complicated and diverse, especially for the unorganized emission sources (Liu et al., 2016). Of

course, actually the lack of element analysis for metals could limit the ability of receptor models to

identify all the sources present in a site. Moreover, the regional transportation of atmospheric

pollutants might also make an important contribution at Tianjin during summer.

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Fig. 6. The source profiles calculated by PMF and ME2 models.

Fig. 7. The contribution of each source calculated by PMF and ME2 models.

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Fig. 8. The time series of sources contributions, calculated by PMF and ME2 models.

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ME2 model also extracted five factors, and the result was similar to PMF model (Fig. 6). The

specific markers of each source were the same to the results of PMF, and factor 1 to 5 was identify as
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secondary sources, vehicle exhaust, biomass burning, crustal dust and coal combustion, respectively.

The source contributions calculated from ME2 model were showed in Fig.7. Secondary sources
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made the highest contribution (25.4 %), and followed by vehicle exhaust (23.3 %), coal combustion

(18.2 %), crustal dust (14.0 %) and biomass burning (9.1 %). The other sources contributed 10.0 %
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to the atmospheric pollutants during summer in Tianjin.

3.3 Comparison of source appointment by PMF and ME2

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As shown in Fig. 6, five factors were extracted by PMF and ME2 models, respectively, and

the profiles of the same source-category from PMF and ME2 models were more consistent. The
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contributions of markers from each source were almost same, and this result was similar to Gao et al

(2016). Nevertheless, there were some differences, for instance, the profile of secondary sources

from PMF model had lower loading of SO42- and NH4+, compared to ME2 model. Additionally, all

the species loadings of vehicle exhaust from PMF model were higher than from ME2 model. For

coal combustion, the loading of SO42- from PMF model was higher than that from ME2 model.

Notably that Ca2+ and K+ are absent in secondary sources from PMF results unlike ME2 model. For

biomass burning, the percentage of Ca2+ from PMF model was up to 18.4 %, whereas it should have

been enriched in crustal dust. EC was falling in secondary sources, and these might be related with

the differences of calculated methods from the two models and the uncertainties of the online

datasets (Gao et al., 2016). To evaluate the ability of PMF and ME2 models for calculating the daily

source contributions of atmospheric pollutants, the correlation analysis was carried out between the
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contributions obtained by the two models (Fig. 8). The correlations (R2 = 0.84-0.94) were better on

the time series of the contributed concentrations for the same source-category calculated from PMF

and ME2 models. Nevertheless, the lower R2 value (0.84) was acquired for crustal dust, and the

lower slope ( = 0.85) values obtained for biomass burning. This was likely due to the inconsistent

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source profiles produced by PMF and ME2 models, and different source contributions acquired by

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the two models in terms of the fact that inconsistent source profiles calculated by two models.

However, for five sources, similar tendencies and values of contributions obtained by the two

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models were observed in Fig. 8, which indicated that the similar results acquired by PMF and ME2

models. Fig. 7 suggested that the calculated contribution of each source to atmospheric pollutants by

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using PMF and ME2 models was comparable. Overall, secondary sources made the most

significantly contribution (25.4-26.1 %) to the atmospheric pollutants in Tianjin, followed by

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vehicle exhaust (23.3-25.4 %), coal combustion (16.5-18.2 %), crustal dust (13.2-14.0 %) and

biomass burning (9.1-10.2 %).

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4 Conclusion

In this paper, the online datasets (the water soluble ions (WSIs), OC and EC in PM2.5, and SO2,
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NO2, NO) were monitored continuously from 1st June to 31st August at Tianjin, which were used to

conduct source apportionment of atmospheric pollutants by using PMF and ME2 models,
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respectively. SO2 and NOx could be taken as markers of the fuel oil/coal combustion source and the

vehicle exhaust, respectively. During summer at Tianjin, the ammonium sulfate/ammonium

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hydrogen sulfate might be major forms of sulfate in the atmospheric aerosol, while ammonium

nitrate might be major forms of nitrate. The changes of emission sources and production of SOC

caused the poor correlation between OC and EC during summer.

Five source-categories that contributed to atmospheric pollutants were extracted by PMF and

ME2 models, respectively. The profiles calculated by PMF and ME2 models were consistent, and

the source contributions estimated by the two models were also similar. The correlations (R2 =

0.84-0.94) were better on the time series of the contributed concentrations for the same

source-category calculated from PMF and ME2 models. The source-categories mainly included

secondary sources (the contribution of 25.4-26.1 %), vehicle exhaust (23.3-25.4 %), coal

combustion (16.5-18.2 %), crustal dust (13.2-14.0 %) and biomass burning (9.1-10.2 %). While the

differences of the same source profiles from PMF and ME2 models, might be attributed to the
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differences of calculated methods from the two models and the uncertainties of the online datasets.

Acknowledgments

This work is supported by the National Key Research and Development Program of China

(2016YFC0208500) and Tianjin Science and Technology Foundation (16YFZCSF00260). The

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authors also gratefully acknowledge Tianjin Environmental Monitoring Center for supporting in the

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monitoring campaign.

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Phys. 14, 12237 12249.

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Zhao, B., Wang, P., Ma, J.Z., Zhu, S., Pozzer, A., Li, W., 2012. A high-resolution emission inventory of primary

pollutants for the Huabei region, China. Atmos. Chem. Phys. 12, 481 501.
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Zhao, X.J., Zhao, P.S., Xu, J., Meng, W., Pu, W.W., Dong, F., He, D., Shi, Q.F., 2013. Analysis of a winter regional

haze event and its formation mechanism in the North China Plain. Atmos. Chem. Phys. 13, 5685 5696.
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Fig. 1. Location of the sampling site at Tianjin.

Fig. 2. The meteorological conditions during summer at Tianjin. Arrowheads represent the direction

of wind blowing toward.

Fig. 3. The daily concentration-variations of PM2.5 and related gaseous pollutants (SO2, NO2, NO,

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O3 and CO) during summer at Tianjin.

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Fig. 4. The concentrations of the water soluble ions (WIs) in PM2.5 and related gaseous pollutants

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(SO2, NO and NO2) during summer at Tianjin.
Fig. 5. The concentration variations and correlations of OC and EC, and the ratios of OC/EC during

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summer at Tianjin.

Fig. 6. The source profiles calculated by PMF and ME2 models.

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Fig. 7. The contribution of each source calculated by PMF and ME2 models.

Fig. 8. The time series of sources contributions calculated by PMF and ME2 models.
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Fig. 1.
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Fig. 2.

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Fig. 3.
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Fig. 4.
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Fig. 5.
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Fig. 6.
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Fig. 7.
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Fig. 8.
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Graphical Abstract.

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Table 1.
The correlations between the water soluble inorganic ions during summer at Tianjin.

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Cl- SO42- NH4+ Ca2+ Mg2+ K+ Na+

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Cl-

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Mg2+

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K+

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r represents the correlation coefficient calculated by SPSS analysis, P<0.01 represents extremely significant correlation, P<0.05 represents significant correlation.

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Highlights

1. Source apportionment of atmospheric pollutants was conducted by using the online datasets.

2. Source contributions and profiles obtained from PMF and ME2 models were consistent.

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3. Secondary sources, vehicle exhaust, coal combustion were major sources during summer.

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