Highly Time-Resolved Atmospheric Observations Using a Continuous

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Highly Time-Resolved Atmospheric Observations Using a Continuous PM2.5 and Element Monitor Hitoshi Asano, Tomoki Aoyama, Yusuke Mizuno, and Yukihide Shiraishi, ACS Earth Space Chem., Just Accepted Manuscript • DOI: 10.1021/ acsearthspacechem.7b00090 • Publication Date (Web): 12 Oct 2017 Downloaded from http://pubs.acs.org on October 27, 2017

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ACS Earth and Space Chemistry

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Highly Time-Resolved Atmospheric Observations Using a Continuous

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PM2.5 and Element Monitor

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Hitoshi Asano*,†, Tomoki Aoyama‡, Yusuke Mizuno‡, and Yukihide Shiraishi§

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†Center for Liberal Arts and Sciences, Tokyo University of Science, Yamaguchi, 1-1-1 Daigaku-Dori,

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Sanyo Onoda, Yamaguchi, 756-0884, Japan

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‡Application R&D Center, Horiba, Ltd., 2 Miyanohigashi, Kisshoin, Minami-ku, Kyoto, 601-8510,

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Japan

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§Department of Applied Chemistry, Faculty of Engineering, Tokyo University of Science, Yamaguchi,

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1-1-1 Daigaku-Dori, Sanyo Onoda, Yamaguchi, 756-0884, Japan

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Table of Contents

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PM2.5 S Pb PM2.5 and Elements

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K Si Ca

Fe Mn

HORIBA

Zn

Process & Environmental

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Day of March, 2015

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Key words

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PM2.5, X-ray fluorescence, PM2.5 and element monitor, highly time-resolved analysis, anthropogenic

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elements, mineral elements, transboundary air pollution

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ABSTRACT: We measured the PM2.5 and element (S, Pb, K, Si, Ca, Fe, Mn, and Zn) concentrations in

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March 2015 by using a continuous PM2.5 mass and element concentration monitor at Sanyo Onoda city,

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which is located in the western part of Japan. In addition to the PM2.5 concentration measurements, this

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instrument can continuously and automatically analyze the elements in the PM2.5 without sample

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pretreatment by using X-ray fluorescence at a high time resolution. The PM2.5 concentrations measured

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with our apparatus and the Yamaguchi Prefectural Government’s system had a good correlation, with a

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correlation coefficient of 0.931. The increase in the PM2.5 concentration in the case of the westerly wind

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indicates that the air mass includes a high concentration of particulate matter that is transported from the

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Asian continent. The anthropogenic components (S, Pb, and K) showed a strong correlation with the

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PM2.5. However, there was a moderate correlation between the crustal components (Si, Ca, and Fe) and

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the PM2.5. During a high PM2.5 concentration event, the results of the time lag in the peak between the

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anthropogenic components and the crustal components indicate that the distinct air masses were

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transported from different origins. The Pb/Zn ratio increased with the PM2.5, which might be a useful

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indicator for evaluating the long-range transport.

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1. Introduction

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Particulate matter (PM) exposure has been recognized for causing respiratory hospitalizations1,2 and

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illness3 and lung function and respiratory symptoms4-6 since reports by Pope et al. Moreover,

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epidemiological studies7,8 have shown associations between fine particulate matter (PM2.5), which has

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an aerodynamic equivalent diameter of 2.5 µm or less, and morbidity and mortality. Based on this

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knowledge, the United States Environmental Protection Agency (U.S. EPA) proposed a new national

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ambient air quality standard in 1997 for PM2.5 with concentrations of 15 µg m−3 (annual average) and

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65 µg m−3 (daily average). The daily regulation of 35 µg m−3 was revised in 2006 and the yearly

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regulation of 12 µg m−3 was revised in 2012.

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In Japan, the daily and annual standards for the PM2.5 mass concentration were established in 2009,

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and the regulated values of the environmental quality standards for 24-hour and 1-year average

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concentrations of PM2.5 were 35 µg m−3 (daily average) and 15 µg m−3 (annual average), respectively.

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The provisional PM2.5 mass concentration observed in each city and town in Japan has been updated on

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the Atmospheric Environmental Regional Observation System (AEROS) home page9. Although it is

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important to measure the mass concentration of PM2.5 continuously, it is also necessary to analyze the

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components in the PM2.5 to obtain a substantial amount of information and knowledge about the PM

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emission sources, transport processes, and transformation. Analytical methods for exploring the 4 ACS Paragon Plus Environment

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components in PM include inductively coupled plasma atomic emission spectrometry (ICP-AES)10,

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inductively coupled plasma mass spectrometry (ICP-MS)10-13, atomic absorption spectrometry

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(AAS)13,14, ion chromatography (IC)15-17, electron probe micro analysis (EPMA)18,19, time of flight

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secondary ion mass spectrometry (TOF-SIMS)20, scanning electron microscope energy dispersive X-ray

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spectroscopy (SEM-EDX)21, synchrotron radiation X-ray fluorescence (SR-XRF)22, instrumental

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neutron activation analysis (INAA)23-26, and X-ray fluorescence (XRF)27-31, which have been used to

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analyze the chemical composition and state of PM. Although ICP-AES and ICP-MS are highly sensitive

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analytical methods, pretreatments such as sample dissolution with acid prior to analysis are

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indispensable. To analyze the ion components in PM using IC, a complicated pretreatment such as an

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ultrasonic extraction is often required. EPMA and SEM-EDX can provide information for each type of

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particulate matter, but these analyses take a long time for the sample collection (for example 1 h–24 h).

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Comparing with their method, it takes 77 min from the sample collection till the analysis by our method.

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For The SR-XRF and INAA are special types of equipment and are unsuitable for routine analysis.

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It is difficult to obtain information about PM2.5 components that change moment by moment using

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the analytical methods that require pretreatment. However, although the XRF is not sensitive, it can be

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used to perform a highly time-resolved analysis of PM2.5 components, such as an hourly measurement

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of the PM2.5 mass concentration, without sample pretreatment. The continuous PM2.5 mass and 5 ACS Paragon Plus Environment


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element concentration monitor developed by Aoyama et al.32 does not only analyze the PM2.5 mass

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concentration each hour, but it can also be used to identify the elements in PM2.5 at a high temporal

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resolution. Therefore, the detailed changes in the air mass can be revealed by performing analyses of the

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PM2.5 mass and components with the our apparatus. PM2.5 measurements have been performed with an

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automatic monitoring system at 20 sites in the Yamaguchi Prefecture, and the hourly PM2.5 mass

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concentration has been updated33. Unfortunately, the daily average value of PM2.5 in Sanyo Onoda

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exceeded the daily standard value (35 µg m−3), and the annual standard average (15 µg m−3) has not been

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attained since the PM2.5 measurements began in 2012. The Yamaguchi Prefecture is one of the closest

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prefectures to the Asian continent in Japan, and the observation of a high PM2.5 mass concentration

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implies the influence of transboundary air pollution from the Asian continent34-36. We have continuously

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observed the PM and PM2.5 at Sanyo Onoda, Yamaguchi Prefecture, which is located in the western part

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of the primary island of Japan, and we revealed the effects of several factors such as the wind direction,

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wind speed, and weather on the variation in PM components since 201317. Here, we demonstrate the

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analytical results for the PM2.5 mass concentration and components using a continuous PM2.5 mass and

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element concentration monitor with high temporal resolution.

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2. METHODS 6 ACS Paragon Plus Environment

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2.1. Continuous PM2.5 Mass and Element Concentration Monitor

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A continuous PM2.5 mass and element concentration monitor (Horiba Ltd., Kyoto, Japan) was used to

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measure the mass and element concentrations of PM2.5. The dimensions of the instrument are 430

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(W)×560 (D)×285 (H) mm and small-sized (Figure S1). The air mass was aspirated with a pump at a

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flow rate of 16.7 L min−1, and a Very Sharp Cut Cyclone (Model VSCC; BGI, Inc., Waltham, MA, USA)

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was employed to collect the PM2.5. The PM2.5 was collected on a TFH filter37 (TFH-01L, Horiba Ltd.,

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Kyoto, Japan, 40 mm×21 m, tape type) with non-woven fabric backing to reinforce the

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polytetrafluoroethylene filter. The filter has a thickness of approx. 60 m, and the efficiency of

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collection for 0.3 µm dioctyl phthalate particles was more than 99%. The measurement of the PM2.5

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mass concentration was performed using the beta-ray absorbing method, and the measurable ranges are

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0–200 µg m−3, 0–500 µg m−3, and 0–1000 µg m−3. In the present study, the range was selected to be

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0–200 µg m−3. The concentrations of the PM2.5 components were determined using energy dispersive

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X-ray fluorescence spectrometry (EDXRF). To determine the analytical condition of the light elements,

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the voltage and the current of the X-ray tube were 15 kV and 0.2 mA, respectively, and the primary filter

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was not used. To determine the analytical condition of the heavy elements, the voltage and the current of

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the X-ray tube were 50 kV and 0.2 mA, respectively, and the molybdenum thin film was used as a

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primary filter. The measurement time was 1000 s. The X-rays emitted from the sample are detected with 7 ACS Paragon Plus Environment


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a semiconductor detector, and the analysis can be performed under atmospheric pressure. The measured

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elements were S, Pb, K, Si, Ca, Fe, Mn, and Zn. Although it is possible to measure heavier elements than

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Al, Cl was not measured due to the analysis of metal elements mainly. The analytical condition is

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summarized in Table 1.

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2.2. Observation sites

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The measurements of PM2.5 and its elemental concentrations were performed from March 11, 2015 to

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March 25, 2015 at Sanyo Onoda. The location of Sanyo Onoda is shown in Figure 1. Sanyo Onoda is

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located in the western part of the primary island of Japan, with a population of ca. 60,000. The ambient

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air was aspirated through the inlet wire hose (hose diameter ca. 12 mm, length ca. 5 m) set on the rooftop

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of the building (ca. 12 m above ground level, AGL) on the campus of the Tokyo University of Science,

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Yamaguchi (TUSY, 33.96° N，131.19° E, Figure 1 (b)), at Sanyo Onoda, Japan. The observation site is

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surrounded by the sea from the west to the south and is located north-northeast of the refinery and west

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of some plants. To the east is a busy road, Japan National route 354. The traffic volume per day was ca.

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10,000–13,000 cars on weekdays38. To estimate the validity of the data for the PM2.5 mass

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concentration as obtained by our monitor, the provisional data9 measured at Sue Park (33.97° N，131.18°

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E, Figure 1 (b)) by the Yamaguchi Prefectural Government was used. The PM2.5 measurement method 8 ACS Paragon Plus Environment

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is the beta attenuation. Sue Park is located 2 km north-north west from TUSY. To the west is prefectural

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route 223, and the 24-hour traffic volume was ca. 7,000–10,000 cars on weekdays. In addition, to discuss

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the transport of air masses from the Asian continent, the hourly PM2.5 data39 measured at Tsushima

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(34.21° N，129.29° E, Figure 1 (a)) were used. Tsushima is located on the isolated Tsushima Island

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between main-land Japan and the Korean Peninsula; it is one of the westernmost cites in Japan and does

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not have any manufacturing plants or local pollutant sources. The island’s area measures 82 km from

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south to north, and 18 km from east to west. Tsushima is located 180 km west of TUSY. We also utilized

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the hourly ambient air concentration of Asian dust from Seoul (37.58° N，127.05° E, Figure 1 (a)), Korea,

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as provided by the Korean meteorological administration40. Seoul, the capital of Korea, is the nation’s

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political, economic, and cultural center and has over 10 million residents. Korea is located 550 km

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northwest of TUSY.

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2.3. Meteorological data and back trajectory analysis

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Meteorological data41 including the wind direction, wind speed, and temperature were continuously

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measured at the Yamaguchi Ube airport station (33.93° N，131.28° E, 5 m AGL, Figure 1 (b)), which is

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maintained by the Japan Meteorological Administration (JMA). Yamaguchi airport is located 8.5 km

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east-south east from the TUSY. Information on the Kosa42, typhoon43, and weather maps44 provided by 9 ACS Paragon Plus Environment


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the JMA was also used.

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To understand the air mass histories, the back trajectories of the air masses were calculated using a

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Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT)45,46, which was developed

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by the National Oceanic and Atmospheric Administration (NOAA). Five back trajectories were traced

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for 48 hours using 6-hour-steps at 500, 1000, and 1500 m AGL.

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3. RESULTS AND DISCUSSION

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3.1. Comparison of our PM2.5 data and the PM2.5 data measured by the Yamaguchi Prefecture

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Figure 2 shows the variation in hourly average concentrations of PM2.5 as measured with a continuous

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mass and element concentration monitor and an auto observation system established by the Yamaguchi

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Prefectural Government. The PM2.5 mass concentrations measured with our apparatus and the

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Yamaguchi Prefectural Government’s system denote the PM2.5_X and PM2.5_Pref., respectively. The

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measurement of the PM2.5 mass concentration was performed with our apparatus for the period from

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16:00 Japan Standard Time (JST) March 11 to 8:00 JST March 25, 2015. Through this observation, 329

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data points were obtained, and no unexpected value was observed with our apparatus. However, 327 data

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points were obtained with the Yamaguchi Prefectural Government’s system, except for two data points at

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14:00 JST and 15:00 JST on March 23, 2015 due to the instrumental trouble. The precipitation was 10 ACS Paragon Plus Environment

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observed on March 14, 18 and 19, 2015, and the mass concentrations of PM2.5 decreased at low levels.

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As shown in Figure 2, the two observed values exhibited a consistent behavior. Both the variation trends

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and the absolute values are consistent between the PM2.5_X and PM2.5_Pref. during this period. A

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significant difference in the air quality between TUSY and Sue Park was not observed, although TUSY

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is located 2 km south-south east from Sue Park (Figure 1 (b)). The average PM2.5_X and PM2.5_Pref.

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are 25.0 µg m−3 and 23.7 µg m−3, respectively, and the two average values nearly coincide (Table 2). The

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hourly PM2.5 mass concentration exceeded 100 µg m−3 on March 22, 2015, and the daily PM2.5_X was

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61.6 µg m−3 (daily PM2.5_Pref.: 58.4 g m−3). On March 22, the Yamaguchi Prefectural Government

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issued an alert due to the possibility that the daily average value of the PM2.5 mass concentration could

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exceed 70 µg m−3. Moreover, the alert was also issued by the neighboring prefectures (Fukuoka,

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Nagasaki, and Saga Prefecture) in Yamaguchi, and Kosa (yellow sand) was observed in western Japan.

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In the vicinity of the PM2.5 peak, the maximum PM2.5_X reached 122.0 µg m−3 at 12:00 JST and then

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120.8 µg m−3 at 13:00 JST. Although a slight difference between the PM2.5_X and the PM2.5_Pref. was

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found, PM2.5_Pref. reached 113 µg m−3 at 12:00 JST and 114 µg m−3 at 13:00 JST. In Seoul, Korea, the

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peak in the Asian dust41 (266 µg m−3) from the event was observed at 19:00 JST on March 21 (Figure

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S2). At Tsushima on the isolated island, the hourly mass concentration of PM2.5 (151 µg m−3) peaked at

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8:00 JST on March 22, which was 13 hours after the Asian dust peak at 19:00 JST on March 21. 11 ACS Paragon Plus Environment


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Therefore, the air mass containing a high concentration of particulate matter was transported from west

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to east. According to meteorological data from Yamaguchi Ube airport, the wind direction changed from

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northerly at 8:00 JST to westerly at 9:00 JST on March 22, and the temperature sharply increased from

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7.1 °C to 10.3 °C (Figure S3). The PM2.5_X increased with the increasing temperature at almost the

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same time. Hence, the results for the meteorological data also indicate that the mass concentration of

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PM2.5 was high due to the transport of another air mass. On March 12 and 14, high PM2.5 was observed.

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The PM2.5_X began to increase at 0:00 JST on March 12 and peaked at 9:00 JST (64.2 µg m−3), and

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thereafter, it decreased to less than 10 µg m−3. The wind direction varied from the southwest to the west

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at 0:00 JST on March 12 (Figure S4). Furthermore, although the temperature was constant at

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approximately 6 °C during the night of March 11, the temperature quickly rose to 8.4 °C at 0:00 JST on

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March 12. Judging from the wind direction and temperature results, different air masses with high

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PM2.5 were flowing. The easterly wind blew from 3:00 JST to 16:00 JST on March 13, and the

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PM2.5_X values were low, with a range from 7.1 µg m−3 to 23.6 µg m−3. However, the wind direction

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varied from easterly to westerly at 17:00 JST, and the PM2.5_X gradually increased and reached ca. 40

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µg m−3 from 1:00 – 4:00 JST on March 14. After 12:00 JST on March 14, a strong wind began to blow at

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over 5 m s−1, and the PM2.5_X decreased to less than 20 µg m−3 due to the disturbance in the air. As

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shown in Figure 3, the correlation between the PM2.5_X and PM2.5_Pref. was high. Because a negative 12 ACS Paragon Plus Environment

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value (−1 µg m−3) was observed in the PM2.5_Pref., the value was not plotted in Figure 3 (n=326). The

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slope and the correlation coefficient were 0.942 and 0.931, respectively. These results validate the

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performance of our monitor as a PM2.5 mass concentration monitor.

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3.2. Effect of the wind direction

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The frequency of the hourly wind direction is shown in Figure 4 (a) from the observation. The most

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frequent wind direction was west, with a frequency of 49 times (15%, n=329). The wind direction with

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almost the same frequency of 44 times (13%, n=329) was to the east. The distribution of the wind

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directions when there was a high PM2.5 concentration is shown in Figure 4 (b). Here, a high

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concentration of PM2.5 is conveniently defined as being over the daily environmental standard value of

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35 µg m−3. As shown in Figure 4 (b), when the wind direction was from the west, the PM2.5

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concentration was mostly high. Consequently, these results indicate the influence of air transport from

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west of the Yamaguchi Prefecture (i.e., Asian Continent). The number of observed high PM2.5

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concentrations is 51 (15.5%) out of 329. The frequency of westerly (from west-southwest to

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north-northwest) and easterly (from north-northeast to east-southeast) winds with high PM2.5

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concentrations were 33 (60%, out of 51) and 15 (30%, out of 51), respectively, and the predominant

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wind direction was westerly with a high PM2.5 concentration. This trend is comparable to the one that 13 ACS Paragon Plus Environment


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we reported previously.17

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3.3. Elemental concentrations

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The limit of detection (LOD) and the limit of quantification (LOQ) are shown in Table 3. The LOD was

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calculated by taking three times the standard deviation (3) of the intensity of a blank filter. The LOQ

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was calculated as ten times the standard deviation of the intensity of a blank filter. As shown in Table 3,

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with an LOD for each element range from 1.8 to 30.6 ng m−3 and an LOQ range from 6.0 to 102.0 ng

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m−3, the present monitor can sensitively analyze the samples. The LOD and the LOQ for our method are

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lower than the previously reported LOD and LOQ values. The standard reference material (from the U.S.

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National Institute of Standards and Technology, air particulate on filter media, NIST SRM 2738) was

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used as a calibration material. Hourly data component concentrations of the PM2.5 were obtained.

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Based on the LOQs of each component in Table 3, the valid data were extracted and analyzed. The

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average, maximum, and minimum concentrations of each component are shown in Table 4. During the

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observation, the average concentration of S was the highest among the analytes at 1340.97 ng m−3. The

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concentration of S ranged widely, from 23.94 ng m−3 to 7108.78 ng m−3. The component with the

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second-highest average concentration (569.50 ng m−3) was Si, which generally originates from soil. The

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K concentration was also high, with an average concentration of 249.81 ng m−3. The concentration of the 14 ACS Paragon Plus Environment

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other components followed the order Fe (152.70 ng m−3), Ca (72.93 ng m−3), Zn (56.57 ng m−3), Pb

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(26.36 ng m−3), and Mn (21.23 ng m−3). Although the number of valid data for Pb and Mn was one-third

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the measured data (329), data over 200 for the other components were obtained.

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The time series for the hourly concentrations of S, Pb, K, Si, Ca, Fe, Mn, and Zn are shown in

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Figure 5. The data that were greater than the LOD of each element were plotted. The variations in the S,

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Pb, and K are consistent with that of the PM2.5. In particular, the peaks of these elements and PM2.5 on

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March 12, 14, and 22 are remarkable. The sources of emissions for S and Pb are the combustion of fossil

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fuel (petroleum, coal and others)47-51, and K originates from burning biomass52,53. These elements are

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emitted by combustion processes and are primarily anthropogenic elements. In particular, it is

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conceivable that S is primarily present as a sulfate species. Moreover, Pb is emitted from waste

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incineration in industrial area54, and the garbage burning was found to contain K55. Although the

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variation is not extremely remarkable, a similar trend in the Si, Ca, Fe, and Mn of PM2.5 is observed.

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During the event when there were high concentrations of S, Pb, and K on March 22, two peaks were

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observed. The first peaks of S, Pb, and K appeared at 12:00 JST on March 22, and they were higher than

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the second peaks of those elements at 19:00 JST on March 22. However, Si, Ca, and Fe peaks appeared

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at 14:00 JST on March 22 at 2 hours after the appearance of the S, Pb, and K peaks (Figure 6 (a), an

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example for S and Si). These components (Si, Ca, and Fe) are crustal elements that help make up the 15 ACS Paragon Plus Environment


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components of soil56-58. The results of the time lag between the components (S, Pb, and K) emitted by

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the combustion processes and crustal components (Si, Ca, and Fe) indicate that the distinct air masses

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were transported from different origins. In addition, the results of the observations when using an optical

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particle counter (RION, KC-52) showed that fine particles (> 1.0 µm in diameter) were transported

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ahead of coarse particles (> 5.0 µm in diameter) (Figure 6 (b)). In general, the anthropogenic and crustal

267

components distribute fine and coarse particles, respectively. According to the temperature, relative

268

humidity, and atmospheric pressure results (Figure 6 (c)), the PM2.5 concentration increased with the

269

increased atmospheric pressure, and the humid air mass containing fine particles was transported with a

270

migratory anticyclone before the dry air with mineral particles arrived. Several similar results relating to

271

the appearance of two different peaks for fine (anthropogenic) and coarse (dust and mineral) particles

272

were reported59-62. Uematsu et al.59 demonstrated that fine sulfur particles appeared first, and after 12

273

hours, the mineral particles arrived. In their work, they revealed that humid air containing high-sulfate

274

aerosols was followed by dry air with high dust. In our study, the transport process of the air mass

275

consistent with these results59-62. Furthermore, to identify the source and transport process of the air mass

276

during the high concentration event on March 22, the back trajectories were calculated by HYSPLIT

277

model (Figure S5). The results of these back trajectory analyses show that the air mass came from the

278

Gobi Desert at 1500 m AGL and the industrial area in central-eastern China at 500 and 1000 m AGL via 16 ACS Paragon Plus Environment

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South Korea. Therefore, the air mass containing the anthropogenic particles was transported from the

280

industrialized region prior to the arrival of the air mass containing dust particles (yellow sand) from

281

desert areas.

282

Table 5 summarizes the correlation between the elements in PM2.5. As shown in Table 5, S, Pb, and

283

K have a strong correlation with the PM2.5, and a strong correlation was also observed between each of

284

these elements. Generally, as described above, components such as S, Pb, and K that are emitted from

285

anthropogenic sources are present in PM2.5 (fine particles). A significant correlation between Si and Fe

286

was observed, and particulate matter that includes these elements originates from crustal sources.

287

Although the composition is not clear, the Si also correlated well with the K. As previously reported,63,64

288

K may originate not only from burning biomass but also minerals such as aluminosilicates and felsic. A

289

weak or poor correlation suggests that the particles possess a more complex composition from a variety

290

of sources.

291

Figure 7 shows the variation in the lead to zinc ratio (Pb/Zn) and the concentration of PM2.5. The

292

variation trend in the Pb/Zn ratio almost coincide with that of the PM2.5. The Pb/Zn ratio ranged from 0.04

293

to 1.17 and the average Pb/Zn ratio was 0.33 during the observation period. At low PM2.5 concentrations

294

(PM2.5 ≤ 35 µg m−3), the average Pb/Zn ratio was 0.29. However, the average Pb/Zn ratio of 0.47 at high

295

PM2.5 concentrations (PM2.5 > 35 µg m−3) was almost identical to the ratio (Pb/Zn=0.44, in Fukuoka, 17 ACS Paragon Plus Environment


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Japan in 2010) reported by Kaneyasu et al.65 They reported that the ratio was close to the value measured

297

(0.43) in Beijing from 2008 to 2009. Mukai et al.66,67 reported that the Pb/Zn ratio might be a good

298

indicator for detecting the long-range transport of particulate matter in the Asian region. From 1983 to

299

1991, high Pb/Zn ratios (ca. 0.8) in aerosols collected from Oki Island in the Sea of Japan were reported.

300

In 1986, Japan prohibited the use of leaded gasoline before the rest of the world did, and most Asian

301

countries banned it by 2000 (South Korea in 1993, China in 2000). Owing to this regulation, the Pb/Zn

302

ratio gradually decreased during the 2000s over a range from 0.3 to 0.6 in the Asian region.68-70 In

303

Tokyo71 (2009) and Taipei72 (2002–2003), the Pb/Zn ratio was ca. 0.3 in the case that it contributed to

304

local pollution. Therefore, our results indicate that the Pb/Zn ratio might be useful as an indicator for

305

evaluating the impact of the long-range transport of particulate matter.

306 307

4. CONCLUSION

308

We have demonstrated the PM2.5 observation by using a PM2.5 monitor. This monitor enables

309

simultaneous determination of the PM2.5 and element mass concentrations without sample pretreatment

310

by using XRF at a high time-resolution. The correlation of the PM2.5 data obtained by our apparatus and

311

the Yamaguchi Prefectural Government's system is good, yielding linear fit with r=0.931, and a slope of

312

0.942. We revealed the flow of air masses from the variation of Asian dust in Seoul, Korea, PM2.5 in 18 ACS Paragon Plus Environment

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313

Tsushima, temperature, the wind speed, and the wind direction, and the results indicated the

314

transboundary pollution from the Asian continent. Moreover, we revealed the relationship between the

315

PM2.5 mass concentration and the wind direction, the predominant wind direction was westerly with a

316

high PM2.5 concentration. Two different peaks for anthropogenic and mineral particulate matters were

317

observed during a high PM2.5 concentration event. Our method allowed for the high time-resolved

318

observation such as the identification of the distinct air masses with the consideration of the OPC data,

319

meteorological data (temperature, atmospheric pressure, and relative humidity), and the back trajectory

320

analysis. At high PM2.5 concentrations (PM2.5 > 35 µg m−3), high ratios of Pb/Zn were observed. These

321

results indicate that Pb/Zn ratios can be used to identify transboundary pollution.

322

ASSOCIATED CONTENT

323

Supporting Information

324

The supporting Information is available free of charge on the ACS Publications website at DOI:

325

XXXXX.

326

AUTHOR INFORMATION

327

Corresponding Author

328

*Phone: 81-836-88-4582; e-mail: [email protected]

329

ORCID 19 ACS Paragon Plus Environment


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Hitoshi Asano: 0000-0002-4963-0842

331

Notes

332

The authors declare no competing financial interest.

333

ACKNOWLEDGMENTS

334

This work was supported in part by the Tokyo University of Science Grant for Joint Research. We

335

greatly appreciate the advice from a member of the Atmospheric Science Research Division, Tokyo

336

University of Science, Research Institute for Science & Technology (Director, Prof. Kazuhiko Miura).

337

We also want to thank the Yamaguchi Prefectural Government, Nagasaki Prefectural Government, Korea

338

meteorological administration, and JMA for providing information on the PM, Asian dust, Kosa,

339

typhoon, and meteorological data. The authors gratefully acknowledge the NOAA Air Resources

340

Laboratory (ARL) for the provision of the HYSPLIT transport and dispersion model and/or READY

341

website (http://www.ready.noaa.gov) used in this publication.

342 343

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(65) Kaneyasu, N.; Yamamoto, S.; Sato, K.; Takami, A.; Hayashi, M.; Hara, K.; Kawamoto, K.; Okuda,

515

T.; Hatakeyama, S. Impact of long-range transport of aerosols on the PM 2.5 composition at a major

516

metropolitan area in the northern Kyushu area of Japan. Atmos. Environ. 2014, 97, 416-425.

517

(66) Mukai, H.; Ambe, Y.; Shiobara, K. Long-term variation of chemical composition of atmospheric

518 519 520 521

aerosol on the Oki Islands in the Sea of Japan. Atmos. Environ. 1990, 24A, 1379-1390.

(67) Mukai, H.; Suzuki, M. Using air trajectories to analyze the seasonal variation of aerosols

transported to the Oki Islands. Atmos. Environ. 1996, 30, 3917-3934.

(68) Pan, Y.; Wang, Y.; Sun, Y.; Tian, S.; Cheng, M. Size-resolved aerosol trace elements at a rural

522

mountainous site in Northern China: Importance of regional transport. Sci. Total Environ. 2013,

523

461-462, 761-771.

524 525

(69) Sun, Y. L.; Zhuang, G. S.; Tang, A. H.; Wang, Y.; An, Z. S. Chemical characteristics of PM2.5 and PM10 in haze-fog episodes in Beijing. Environ. Sci. Technol. 2006, 40, 3148−3155. 31 ACS Paragon Plus Environment


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

526

(70) Okuda, T.; Kato, J.; Mori, J.; Tenmoku, M.; Suda, Y.; Tanaka, S.; He, K.; Ma, Y.; Yang, F.; Yu, X.;

527

Duan, F.; Lei, Y. Daily concentrations of trace metals in aerosols in Beijing, China, determined by

528

using inductively coupled plasma mass spectrometry equipped with laser ablation analysis, and

529

source identification of aerosols. Sci. Total Environ., 2004, 330 145-158.

530

(71) Okuda, T.; Takada, H.; Kumata, H.; Nakajima, F.; Hatakeyama, S.; Uchida, M.; Tanaka, S.; He, K.;

531

Ma, Y. Inorganic Chemical Characterization of Aerosols in Four Asian Mega-Cities. Aerosol Air

532

Qual. Res. 2013, 13, 436-449.

533

(72) Hsu, S.-C.; Liu, S.C.; Jeng, W.-L.; Lin, F.-J.; Huang, Y.-T.; Candice Lung, S.-C.; Liu, T.-H.; Tu, J.-Y.

534

Variations of Cd/Pb and Zn/Pb ratios in Taipei aerosols reflecting long-range transport or local

535

pollution emissions. Sci. Total Environ., 2005, 347 111-121.

536 537 538 539 540 541 542 32 ACS Paragon Plus Environment

Page 32 of 53

Page 33 of 53

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

543


Tables

Table 1. Apparatus and analytical condition

Apparatus

Horiba, Ltd., Continuous Particulate Monitor

with X-ray Fluorescence PX-375

Separator

Cyclone (VSCC)

Flow rate

16.7 L min−1

PM2.5 counter

β-ray absorption method

Filter

TFH filter (PTFE/non-woven fabric membrane

filter)

Target material

Pd

Detector

SDD

X-ray irradiation diameter

7 mm

Exciting voltage

For light elements

15 kV

For heavy elements

50 kV (Mo thin film)

Tube current

200 mA

544 33 ACS Paragon Plus Environment


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 34 of 53

Table 2. Summary of PM2.5 data Average

Maximum

Minimum

(μg m−3)

(μg m−3)

(μg m−3)

PM2.5_X

25.0

122.0

2.5

329

PM2.5_Pref.

23.7

114

−1

327

545 546 547 548 549 550 551 552 553 554 555 556


Number of data

Page 35 of 53

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 3. Limit of detection (LOD) and Limit of quantitation (LOQ)

Element

LODa) (ng m−3)

LOQb) (ng m−3)

Analytical line

S

4.1

13.7

Kα

Pb

3.7

12.3

Lβ

K

30.6

102.0

Kα

Si

19.4

64.7

Kα

Ca

8.7

29.0

Kα

Fe

10.6

35.3

Kα

Mn

3.8

12.7

Kα

Zn

1.8

6.0

Kα

a) The LOD was calculated by taking three times the standard deviation of the blank. Nominal

value. b) LOQ = (10/3)×LOD. 557 558 559 560



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 36 of 53

Table 4. Average concentration, maximum, minimum, and number of samples for each element

Element

Average (ng m−3)

Maximum (ng m−3)

Minimum (ng m−3)

Number of samples

S

1340.97

7108.78

23.94

318

Pb

26.36

93.30

12.49

123

K

249.81

1228.42

103.66

277

Si

569.50

4417.92

65.72

316

Ca

72.93

229.07

29.09

218

Fe

152.70

785.43

36.82

266

Mn

21.23

69.66

12.71

117

Zn

56.57

501.06

6.58

321

561

The number of samples was extracted based on the LOQ. The data below the LOQ were excluded from

562

the analysis.

563 564 565 566 567 36 ACS Paragon Plus Environment

Page 37 of 53

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 5. Correlation coefficients between each element

S

569

Pb

K

Si

Ca

Fe

Mn

Zn

S

1

Pb

0.662

1

K

0.743

0.897

1

Si

0.533

0.625

0.809

1

Ca

0.539

0.439

0.492

0.561

1

Fe

0.476

0.551

0.683

0.780

0.541

1

Mn

0.306

0.662

0.617

0.594

0.400

0.643

1

Zn

0.379

0.477

0.344

0.296

0.168

0.360

0.605

1

PM2.5

0.841

0.837

0.864

0.680

0.497

0.632

0.563

0.300

The bold figures denote the meaningful correlations. (above 0.6)

570


PM2.5

1


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

(a)

Page 38 of 53

(b) Sanyo Onoda

Ube

Beijing

Tsushima Seoul

Tokyo

Sanyo Onoda

10 km

200 km

571 572

Figure 1. Location of the observation sites. (a) East Asia map. The PM2.5 observation sites used as

573

references are Seoul, Korea and Tsushima, Japan. (b) Local map. The PM2.5 observation performed with

574

our apparatus was at the Tokyo University of Science, Yamaguchi, in Sanyo Onoda, Japan (red closed

575

circle). The PM2.5 observation used as a reference here is Sue Park in Sanyo Onoda, Japan (yellow

576

closed circle). The meteorological data were observed at Yamaguchi Ube airport in Ube, Japan (open

577

circle).

578 579 580 581


Page 39 of 53

140 PM2.5_X 120

PM2.5 (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


PM2.5_Pref.

100

80 60 40 20

0 11 582 583

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

Day of March, 2015 Figure 2. Comparison of hourly average PM2.5 concentrations between the continuous PM2.5 levels by

584

an Element Monitor (our apparatus) and an auto-observation system established by the Yamaguchi

585

Prefecture. The PM2.5 mass concentrations measured with our apparatus and the Yamaguchi Prefectural

586

Government’s system are denoted as PM2.5_X (red closed circles) and PM2.5_Pref. (blue open circles),

587

respectively. Blue bands represent the precipitation.

588 589 590 591 592 39 ACS Paragon Plus Environment


150

PM2.5_PX-375 (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 40 of 53

y = 0.942x + 2.74 R = 0.931

100

50

0 0

50

100

150

PM2.5_Pref. (µg m−3) 593 594

Figure 3. The relationship between the PM2.5 mass concentrations measured with a continuous PM2.5

595

mass and element concentration monitor (our apparatus) and the Yamaguchi Prefectural Government’s

596

system. The PM2.5 mass concentrations measured with our apparatus and the Yamaguchi Prefectural

597

Government’s system are denoted as PM2.5_X and PM2.5_Pref., respectively.

598


Page 41 of 53

N NNW

(a)

50

NW

20

NNE

40

(b)

NE

30

WNW

ENE

20 10

W

E

0

WSW

ESE

SW

SE SSW

Number of high PM2.5

15

Easterly

Westerly

10

5

SSE S

599

N

NNW

NW

W

WNW

SW

WSW

S

SSW

SE

SSE

ESE

E

ENE

0 NE

The distribution of the wind directions during the observation The distribution of the wind directions with high concentrations of PM2.5 High PM2.5 >35 µg m −3

NNE

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


Wind direction

600 601

Figure 4. Wind directions frequency (a) and distribution of wind directions with high concentrations of

602

PM2.5 (b). A high concentration is greater than 35 μg m−3. The easterly wind directions denote a range

603

from NNE to SSE. The westerly wind directions denote a range from SW to NNW.

604 605 606 607 608 609



100

8000

Pb

S 80

Pb (ng m−3)

S (ng m−3)

6000

4000

2000

60

40

20

0

0

11

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

5000

1400

Si

K 1200 4000

Si (ng m −3)

K (ng m−3)

1000 800 600

3000

2000

400 1000 200 0

0 11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

26

300

1000

Ca

Fe

250

800

Fe (ng m−3)

Ca (ng m−3)

200

150

600

400

100

200

50

0

0 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

80 70

600

Zn

Mn 500

60 400

50

Zn (ng m−3)

Mn (ng 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 42 of 53

40

30

300

200 20 100

10 0

0 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

610

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

Day of March, 2015

611

Figure 5. Temporal variations in the element concentrations (S, Pb, K, Si, Ca, Fe, Mn, and Zn) for

612

PM2.5. Observation dates: March 11–25 2015. 42 ACS Paragon Plus Environment

Page 43 of 53

8000

S Si

6000

Crustal element (Si)

4000

Anthoropogenic element (S) 2000

6:00

12:00

18:00

0:00 500

(b)

>5 um

20000

400

←Fine 15000

300

Coarse→ 10000

200

5000

100

Atmospheric pressure (hPa)

0 0:00 1018

6:00

12:00

0 0:00 80

18:00

(c)

1017

70

RH→

1016

1015

60

50

←Atmos. press. 1014

40

Atmos press. 1013 0:00

6:00

12:00

18:00

RH 30 0:00

140

(d)

PM2.5_X 120

Temp.

Temp.→

100

20

15

80

10 60 40

←PM2.5

5

20 0 0:00

613

0 6:00

12:00

18:00

Relative humidity (%)

Particle number (m−3)

>1.0um


0 0:00 25000

0:00

Time of March 22, 2015


Temperature (℃)

S and Si (ng m−3)

(a)

PM2.5 (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



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

614

Figure 6. Time series of S as an anthropogenic element and Si as a crustal element (a), fine and coarse

615

particles (b), atmospheric pressure, and relative humidity (c), and PM2.5 and temperature (d) on March

616

22, 2015. Elemental and PM2.5 data, and particle number were obtained with a continuous PM2.5 and

617

elemental monitor, and an optical particle counter (Rion), respectively. Meteorological data measured by

618

the Japan Meteorological Agency were used. We note that the atmospheric pressure and relative

619

humidity at Shimonoseki city were plotted except for temperature, because the atmospheric pressure and

620

relative humidity were not measured at Ube city.

621 622 623


Page 44 of 53

Page 45 of 53

120

PM2.5_X Pb/Zn

2 period moving average (Pb/Zn)

1

100

0.8

80 0.6 60

0.4

40

0.2

20 0

0 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

624 625

1.2

Day of March, 2015 Figure 7 Temporal variations in the Pb/Zn ratios.


Pb/Zn

140

PM2.5 (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



(a) 1 2 3 4 5 6 7 Beijing 8 9 10 11 12 13 14 15 16 17

Page 46 of 53

(b)

Sanyo Onoda

Seoul

Ube

Tsushima Tokyo

Sanyo Onoda ACS Paragon Plus Environment 200 km

10 km

14047 of 53 Page 120


PM2.5_Pref.

PM2.5 (µg m−3)

1 2 3 100 4 5 80 6 7 8 60 9 10 40 11 12 20 13 14 15 0 16 11 17 18

PM2.5_X

12

13

14 ACS 15 Paragon 16 17Plus 18Environment 19 20 21

Day of March, 2015

22

23

24

25

26


150

PM2.5_PX-375 (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

Page 48 of 53

y = 0.942x + 2.74 R = 0.931

100

50

0

0

50

100


PM2.5_Pref. (µg m−3)

150

NNE

40

NE

30

ENE

20 10

E

0

WSW

ESE SW

SE

5

Wind direction

N

NW

NNW

W

WNW

WSW

SW

SSW

0

Paragon Plus Environment

S

The distribution of the wind directions ACS during the observation The distribution of the wind directions with high concentrations of PM2.5 High PM2.5 >35 µg m −3

SSE

SSE

SE

S

Westerly

10

E

SSW

Easterly

ESE

W

15

NE

WNW

ACS Earth20and(b) Space Chemistry

ENE

1 2 3 4 5 6 7 8 9 10 11 12

N

NNE

NW

50

Number of high PM2.5

53 (a)Page 49 ofNNW

8000

100 ACS Earth and Space Chemistry Pb

S

80

S (ng m−3)

Pb (ng m−3)

6000

1 2 34000 4 5 62000 7 8 0 9 11 12 13 1400 10 K 1200 11 12 1000 13 14800 15600 16 17400 18200 19 20 0 11 12 13 21300 Ca 22 23250 24 200 25 26150 27 28100 29 3050 31 0 32 11 12 13 3380 Mn 3470 3560 3650 37 3840 3930 4020 41 10 42 43 0 11 12 13 44 45

60

40

20

0 14 15 16 17 18 19 20 21 22 23 24 25 26

5000

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

Si

Si (ng m −3)

K (ng m−3)

4000

3000

2000

1000

14

15

16

17

18

19

20

21

22

23

24

25

0

26

1000

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

Fe

Fe (ng m−3)

800

600

400

200

0

14 15 16 17 18 19 20 21 22 23 24 25 26

600

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

Zn

500 400

Zn (ng m−3)

Mn (ng m−3)

Ca (ng m−3)

Page 50 of 53

300 200 100

ACS Paragon Plus 0Environment

14 15 16 17 18 19 20 21 22 23 24 25 26

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

Day of March, 2015


(a)


Atmospheric pressure (hPa)

PM2.5 (µg m−3)


Crustal

1 element (Si) 2 3 4000 Anthoropogenic 4 element (S) 5 2000 6 7 8 0 0:00 6:00 12:00 18:00 0:00 9 500 1025000 (b) >1.0um 11 >5 um 400 1220000 13 ←Fine 1415000 300 15 Coarse→ 1610000 200 17 185000 100 19 20 0 0 21 0:00 6:00 12:00 18:00 0:00 22 1018 80 (c) 23 24 1017 70 25 26 1016 RH→ 60 27 28 1015 50 29 ←Atmos. press. 30 1014 40 31 32 Atmos press. RH 30 33 1013 0:00 6:00 12:00 18:00 0:00 34 140 20 35 (d) PM2.5_X 36 120 Temp. 37 Temp.→ 15 100 38 39 80 10 40 41 60 42 40 ←PM2.5 5 43 44 20 ACS Paragon Plus Environment 45 0 0 46 0:00 6:00 12:00 18:00 0:00 47 Time of March 22, 2015

Relative humidity (%)

S and Si (ng m−3)

6000

S Si

Temperature (℃)

8000

Page 51 of 53

120

ACS Earth and Space Chemistry 2 period moving average

(Pb/Zn)

Page 521.2 of 53

1 0.8

PM2.5 (µg m−3)

1 2 3 100 4 5 6 80 7 8 60 9 10 11 40 12 13 14 20 15 16 0 17 11 18 19

PM2.5_X Pb/Zn

0.6 0.4 0.2


12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

Day of March, 2015

0

Pb/Zn

140

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


PM2.5 S Pb PM2.5 and Elements

Page 53 of 53

K Si Ca Fe Mn

HORIBA

Zn

Process & Environmental


11

12

13

14

15

16

17

18

19

20

Day of March, 2015

21

22

23

24

25

26

Highly Time-Resolved Atmospheric Observations Using a Continuous

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