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Characterization of atmospheric particulate and metallic elements at Taichung Harbor near Taiwan Strait during 2004–2005
Chemosphere 63 (2006) 1912–1923 www.elsevier.com/locate/chemosphere
Characterization of atmospheric particulate and metallic elements at Taichung Harbor near Taiwan Strait during 2004–2005 Guor-Cheng Fang *, Yuh-Shen Wu, Jum-Bo Lin, Chi-Kwong Lin, Jui-Yeh Rau, Shih-Han Huang Air Toxic and Environmental Analysis Laboratory, Hungkuang University, Sha-Lu, Taichung 433, Taiwan Received 13 August 2005; received in revised form 7 October 2005; accepted 7 October 2005 Available online 22 November 2005
Abstract Air aerosol samples for TSP (total suspended particulate), coarse particulate (particle matter with aerodynamical diameter 2.5–10 lm, PM2.5–10), fine particulate (particle matter with aerodynamical diameter <2.5 lm, PM2.5) and metallic elements were collected during March 2004 to January 2005 at TH (Taichung Harbor) in central Taiwan. The seasonal variation average concentration of TSP (total suspended particulate), coarse particulate (particle matter with aerodynamical diameter 2.5–10 lm, PM2.5–10) and fine particulate (particle matter with aerodynamical diameter <2.5 lm, PM2.5) were in the range 132–171.1 lg m 3 and 43–49.5 lg m 3, respectively. Seasonal variation of metallic elements Cu, Mn, Zn and Fe in the TSP (total suspended particulate) shows that higher concentration was observed during spring. Seasonal variation of metallic elements Pb, Cr and Mg in the TSP (total suspended particulate) shows that higher concentration was observed during winter. The average metallic element TSP (total suspended particulate) concentration order was Fe > Zn > Mg > Cu > Cr > Mn > Pb in spring. In addition, at the TH sampling site, the average concentration variation of TSP (total suspended particulate) displayed the following order: spring > winter > autumn > summer. However, the average concentration variation of coarse particulate (particle matter with aerodynamical diameter 2.5–10 lm, PM2.5–10) displayed the following order: spring > winter > summer > autumn. Finally, the average concentration variations of fine particulate (particle matter with aerodynamical diameter <2.5 lm, PM2.5) were in the following order: winter > spring > summer > autumn at the TH sample site. 2005 Elsevier Ltd. All rights reserved. Keywords: Season variation; Metallic; Particulate; Harbor
1. Introduction
* Corresponding author. Tel.: +886 4 2631 8652x1111; fax: +886 4 2350 2102. E-mail address: [email protected] (G.-C. Fang).
The higher values of PM found in summer with respect to winter are in agreement with the abundance of re-suspended material in summer at Buenos Aires, due to the effect of wind. It is very interesting to note that the levels of PM in Buenos Aires decrease from
0045-6535/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2005.10.010
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
summer to autumn-winter, while the opposite behavior was observed in Sa˜o Paulo. This is probably due to the different topography and meteorological characteristics (Bogo et al., 2003). A characteristic seasonal variation can be observed for PM10 and PM2.5 with elevated concentrations during the cold season. The reasons for this are not primarily caused by seasonal fluctuations of the emissions, but rather by meteorological effects. The PM2.5/PM10 ratios are not constant over the year. In general lower values were observed during spring and partly also during summer, indicating presumably the occurrence of coarse biogenic dust (e.g. pollen). At Bern, this seasonal variation of the PM2.5/ PM10 ratios cannot be observed. Obviously, if present at all, it is masked by the massive influence of locally produced exhaust and road dust (Gehrig and Buchmann, 2003). The particle size distribution of PM varies seasonally with the fine fractions prevailing in summer (PM2.5/PM10 = 80–90%) and the coarser increasing in winter (PM2.5/PM10 = 60–70%). As expected, PM levels obtained at the different monitoring sites gradually increased from regional background stations to industrial sites as a result of the addition of local contributions (traffic, industry). The majority of the stations selected are subject to the influence of close industrial and/or traffic PM sources (Viana et al., 2003). In Nanjing city on average, 63–77% of PM10 is in the PM2.5 fraction, which indicates that fine particles are the major component of atmospheric aerosols (Wang et al., 2003). The elements Mg, Al, Si, K, Ca and Fe have been found to form a major fraction of aerosol particles collected in China during dust storms (Fan et al., 1996). High concentrations of As, Mn, V, non-sea-salt sulfate and ammonium N indicate the significant impact of fossil fuel burning, while enhanced Al, Ca, Fe and Mn concentrations show the effect of mineral dusts and crustal materials (Lee and Hills, 2003). In general, airborne fine particles of 1 (PM1) and 2.5 mm (PM2.5) in diameter or less are considered of great health significance (Li and Lin, 2003). The Cu, Pb, and Fe concentrations resembled the median value at different areas around the world. However, the mean Zn and Mn concentrations results in fine particles (PM2.5) ranked as comparable with other areas around the world. The mean Ni, Cr and Cd concentrations ranked highest in both fine particle (PM2.5) and coarse particle (PM2.5–10) concentrations compared with data collected from other world regions (Fang et al., 2003). The concentrations of Cd, Mn, Ni and Zn were significantly higher at the industrial sites and should be attributed to the pyrometallurgical processes (Pb and Zn smelters, non-ferrous metal industries, etc.) taking place in the area, as well as to the manganese ore treating plant. Relatively higher Pb concentrations were found at the urban sites due to higher traffic density (Voutsa and Samara, 2002). The wind and precipitation had the effect of dispersing and dilut-
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ing the aerosol, making the summer concentrations lower (Resina Maura de Miranda et al., 2002). The purpose of this study was to understand metallic element concentrations and their seasonal variations at TH (Taichung Harbor). Two PS-1s (GPS1 PUF Sampler, General Metal Work) and a Universal Air Sampler were used to collect and analyze the above pollutants and their seasonal variations at TH (Taichung Harbor) during March 2004 to January 2005 in this study.
2. Materials and methods 2.1. Sampling site The sampling site of this study was as shown in Fig. 1. Taichung Harbor (TH) was selected as the sampling site. The distance to the nearest traffic road and TH are about 30 km. Atmospheric particulate concentration were collected for 24 consecutive hours at the TH sampling sites by PS-1 and Universal sample simultaneously during March 2004 to January 2005. Taichung Harbor is an artificial harbor with a maximum of 83 docks, which is located on the west coast of central Taiwan. It occupies about 37 600 acres. The sampling height of this sampling site is about 10 m. TH sampling sites were also placed on the highest building in this region. The Taichung Thermal Power Plant was developed on 281 ha located along the coast west of the sampling sites. The Taichung Thermal Power Plant was coal combustion based, and is the largest thermal power plant in Southeast Asia. The Taichung Thermal Power Plant can produce about 4400 MW hours per day to supply the electric requirements of central Taiwan. It was located about 15 km southeast of the TH sampling sites. 2.2. Sampling program 2.2.1. Sample collection 2.2.1.1. Universal air sampler. The Model 310 Universal Air SamplerTM (UASTM) is a general–purpose air sampler for atmospheric aerosol sampling and mass concentration determinations, as well as organic or inorganic analyses. The sampler has a designed inlet sampling flow rate of 300 l/min. It is provided with an omni-directional inlet, a PM10 (10 lm cut) virtual impact classifier, and either a PM2.5 or PM10 virtual impact classifier, or a fine particle filter. This allows the sampler to be operated as a high volume dichotomous sampler for size fractionation of airborne particles in the fine (0–2.5 lm) and coarse (2.5–10 lm) aerodynamic size ranges. Air is aspired at 300 l/min from the ambient atmosphere. Particles greater than 10 lm aerodynamic equivalent diameters are removed from the air stream by the PM10 classifier and discarded. Particles less than 10 lm in diameter flow to the PM2.5 classifier located downstream.
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G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
Fig. 1. The sampling positions and relative location of this study.
Particles in the coarse (2.5–10 lm) range (coarse fraction) are collected on a 62 mm · 165 mm filter and those smaller than fine (2.5 lm) (fine fraction) are collected on a 200 mm · 250 mm final filter (Universal Air Sampler, 1996). Quartz filters (62 mm · 165 mm, 200 mm · 250 mm) were weighed before and after sampling to determine the amounts of particulate collected.
ments were 0.021, 0.007, 0.022, 0.015, 0.017, 0.012 and 0.015 mg/l for Fe, Mg, Cr, Cu, Zn, Mn and Pb, respectively. The method detection limit was determined by selecting the concentration slightly higher than the lowest concentration of the standard line, and repeating this concentration 12 times to estimate the standard deviation (S). The MDL was equal to 3 * S.
2.2.1.2. PS-1 sampler. The PS-1 (GPS1 PUF Sampler, General Metal Work) is a complete system designed to simultaneously collect suspended airborne particulates at flow rates up to 280 l/min. The flow rate was adjusted to 200 l/min in this study. The quartz filter (diameter 10.2 cm) is used to filter the suspended particles. The system consists of nine basic assemblies: dual chamber, sampling module, flow vent, electromagnetic gauge, voltage, elapsed time indicator, pump, 7-day skip timer, exhaust hose and aluminum shelter. The filters were first conditioned for 24 h in an electric chamber at humidity 50 ± 5% and temperature 25 ± 5 C prior to weighing. Filters were placed in a sealed CD box during the transport and storage process.
2.2.2.2. Recovery efficiency test. At least 10% of the samples are analyzed by spiking with a known amount of metal to calculate recovery efficiencies. The analysis procedure for the recovery test is the same as that described for the field samples. The recovery tests of metallic elements were 96%, 97%, 97%, 101%, 102%, 105% and 101% for Fe, Zn, Mn, Cu, Pb, Cr and Mg, respectively.
2.2.2. Quality control 2.2.2.1. Detection limit. The detection limit was used to determine the lowest concentration level that can be detected to be statistically different from a blank. The method detection limit (MDL) was determined by selecting the concentration slightly higher than the lowest concentration of the standard line. The procedure of repeating the lowest concentration of standard solution 12 times was also used to estimate the standard deviation (S). The method detection limits for metallic ele-
2.2.2.3. Blank test. The blank test background contamination was monitored by using operational blanks (unexposed projection film and quartz filter) which were processed simultaneously with field samples. Background contamination of heavy metals was accounted for by subtracting field blank values from the concentrations. Field blank values were very low, usually below or around the method detection limits. In this study, the background contamination is insignificant and can be ignored. The results of the blank test are 0.43, 0.36, 0.30, 0.25, 0.21, 0.19 and 0.17 lg for Fe, Zn, Mn, Cu, Pb, Cr and Mg, respectively. 2.3. Sampling information Table 1 show seasonal sampling information for meteorological conditions such as temperature, relative
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
1915
Table 1 Seasonal sampling information meteorological conditions at TH sampling sites during March of 2004 to January of 2005 Seasons
Month
Ta (C)
RHb (%)
PWDc
Pd (hpa)
Spring
March April May Average
18.7 21.6 24.4 21.6
70.5 74.7 75.7 73.6
NNE NNW N
1020.2 1012.4 1009.2 1013.9
Summer
June July August Average
26.6 29.4 27.5 27.8
72.0 75.5 73.0 73.5
NE NE N
1006.2 1006.1 1007.1 1006.5
Autumn
September October November Average
27.6 25.1 22.1 24.9
72.0 71.0 69.5 70.8
SWW NNE NE
1011.1 1012.8 1011.8 1011.9
Winter
December January Average
16.9 14.6 158
77.0 74.0 75.5
NNE NNW
1015.6 1018.2 1016.9
a b c d
Temperatures. Relative humidity. Prevalent wind direction. Air pressure.
humidity, atmospheric pressure and prevalent wind direction at the TH sampling sites during March 2004 to January 2005. In spring, 2004 (March, April, May) the average temperature, relative humidity, prevalent wind direction and atmospheric pressure were 21.4 C, 73.9%, NNW, N, NNW and 1013.8 hpa, respectively. In summer, 2004 (June, July, August) the average temperature, relative humidity, prevalent wind direction and atmospheric pressure were 28.02 C, 75.2%, NE, N and 1006.6 hpa, respectively. In autumn, 2004 (September, October, November) the average temperature, relative humidity, prevalent wind direction and atmospheric pressure were 24.42 C, 71.92%, NE, NNE, SWW and 1009.75 hpa, respectively. In winter, (December) 2004 and (January) 2005 the average temperature, relative humidity, prevalent wind direction and atmospheric pressure were 16 C, 75.2%, NNE, NNW and 1016.18 hpa, respectively. In general, the relative humidity was all higher then that at land sampling sites (traffic, urban, suburban) around central Taiwan. The temperature range for each season in this study was lower than that of land (traffic, urban, suburban) sampling sites around central Taiwan.
3. Results and discussion 3.1. Monthly variation of particulate mass The average concentration and seasonal variation of TSP, coarse particulate and fine particulate for the TH sampling site are displayed in Fig. 2. The TSP and
coarse particulate showed regular seasonal variations, with higher concentration in spring and winter while lower concentration occurred in summer and autumn. For the fine particulate, higher concentration occurred in winter and spring and lower concentration occurred in autumn. At the TH sampling site, the average concentration variations of TSP displayed the following order: spring > winter > autumn > summer. However, the average concentration variation of coarse particulate displayed the following order: spring > winter > summer > autumn. Finally, the average concentration variations of fine particulate were in the following order: winter > spring > summer > autumn at the TH sample site. 3.2. Seasonal variation of particulate mass Table 2 shows the seasonal variation of TSP, coarse particulate and fine particulate average concentrations at the TH sampling sites during March of 2004 to January of 2005. The seasonal average concentrations of TSP were found to be 117.1, 132.0, 160.2 and 170.8 lg m 3 for spring, summer, autumn and winter, respectively. In addition, average coarse particulate concentrations were found to be 37.0, 26.6, 26.2 and 36.0 lg m 3 for spring, summer, autumn and winter. Finally, the average fine particulate concentrations were found to be 49.3, 46.4, 43.0 and 49.5 lg m 3 for spring, summer, autumn and winter, respectively at TH sampling site. The highest seasonal average TSP and coarse particulate concentrations were found in spring (171.1 lg m 3), and (37 lg m 3), respectively. The highest seasonal average
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G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923 200 180
Concentrations (μg m-3)
160 140 120 100 80 60 40 20 0 Mar
Apr
May
Jun
Jul
Aug
Sep
Oct
Nov
Dec
Jan
Month TSP coarse fine
Fig. 2. Monthly variation of TSP, coarse and fine particulate average concentration at the TH site during March 2004 to January 2005.
Table 2 Seasonal variation of mean TSP, coarse and fine concentrations at TH sampling sites during March of 2004 to January of 2005 Seasons
TSP (lg m 3)
Coarse (lg m 3)
Fine (lg m 3)
Spring (March, April, May) Summer (June, July, August) Autumn (September, October, November) Winter (December, January)
171.1 132.0 160.2 170.8
37.0 26.6 26.2 36.0
49.3 46.4 43.0 49.5
concentration of fine particulate was found in the winter (49.5 lg m 3). In general, the highest coarse and fine particulate concentration at TH occurred in the spring and winter season. This phenomenon is opposite opportune to that of the traffic sampling site study (Fang et al., 2005). 3.3. Seasons of metallic elements Fig. 3(A)–(G) indicates the seasonal variation of metallic element (Cu, Mn, Zn, Pb, Cr, Mg and Fe) concentrations for TSP, coarse particulate and fine particle sizes at the TH sampling site during March 2004 to January 2005 for four seasons near the Taiwan Strait in central Taiwan. Fig. 3(A) shows on metallic element Cu in TSP, coarse particulate and fine particulate concentrations vs. seasons in the Taichung Harbor area. The order of seasonal variations was spring > winter > summer P autumn for
TSP, and spring > winter > autumn P summer for coarse particulate. The fine concentrations exhibited no significant seasonal variations for metallic Cu in this study. Fig. 3(B) shows on metallic element Mn in TSP, coarse particulate and fine particulate concentrations vs. seasons in the Taichung Harbor area. The order of seasonal variations was spring > winter > summer > autumn for TSP, and winter > autumn P spring > summer for coarse particulate. The fine concentrations exhibited no significant seasonal variations for metallic Mn in this study. Fig. 3(C) shows on metallic element Zn in TSP, coarse particulate and fine particulate concentrations vs. seasons in the Taichung Harbor area. The order of seasonal variations was spring > winter > autumn > summer for TSP, and autumn > summer P spring > winter for coarse particulate. The season variations of concentration order for metallic Zn was autumn > spring > winter > summer for fine particulate.
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923 Cu - (A)
Mn - (B) 120
concentration (ng m-3)
concentration (ng m-3)
600 500 400 300 200 100
100 80 60 40 20 0
0 Spring TSP coarse fine
Summer
Autumn
Winter
Spring
seasons
TSP coarse fine
Zn - (C)
Autumn
Winter
seasons
50
concentration (ng m-3)
concentration (ng m-3)
Summer
Pb - (D)
1000 800 600 400 200 0 Spring TSP coarse fine
Summer
Autumn
40 30 20 10 0
Winter
seasons
Spring TSP coarse fine
Cr - (E)
Summer
Autumn
Winter
seasons
Mg - (F)
350
800
concentration (ng m-3)
concentration (ng m-3)
1917
300 250 200 150 100 50
600
400
200
0
0 Spring TSP coarse fine
Summer
Autumn
Winter
seasons
Spring TSP coarse fine
Summer
Autumn
Winter
seasons
Fe - (G)
concentration (ng m-3)
1600 1400 1200 1000 800 600 400 200 0 Spring TSP coarse fine
Summer
Autumn
Winter
seasons
Fig. 3. (A)–(G) Seasonal variation of metallic (Cu, Mn, Zn, Pb, Cr, Mg and Fe) concentrations for TSP, coarse particulate and fine particle sizes.
Fig. 3(D) shows on metallic Pb in TSP, coarse particulate and fine particulate concentrations vs. seasons at Taichung Harbor area. The season variations of concen-
tration order for metallic element was winter > spring > autumn P summer for TSP. And the seasonal variations of concentration order for metallic element was
1918
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spring > summer > winter > autumn for coarse particulate. Besides, the seasonal variations of concentration order for metallic element was winter > spring > autumn > summer for fine particulate. Fig. 3(E) shows on metallic element Cr in TSP, coarse particulate and fine particulate concentrations vs. seasons in the Taichung Harbor area. The order at season variations was winter > spring > autumn P summer for TSP and winter > spring > autumn > summer for coarse particulate. The seasonal variations of concentration order for metallic element was spring > winter > summer > autumn for fine particulate. Fig. 3(F) shows on metallic element Mg in TSP, coarse particulate and fine particulate concentrations vs. seasons at Taichung Harbor area. The order at seasonal variations was winter > spring > autumn P summer for TSP and spring > summer > autumn > winter for coarse particulate. The seasonal variations of concentration order for metallic element was winter > spring > autumn > summer for fine particulate. Fig. 3(G) shows on metallic element Fe in TSP, coarse particulate and fine particulate concentrations vs. seasons at Taichung Harbor area. The order at seasonal variations of concentration order for metallic element was spring P winter > autumn P summer for TSP and spring > summer > winter > autumn for coarse particulate. The seasonal variations of concentration order for metallic element was spring > autumn P summer > winter for fine particulate. In general, the order at average metallic element TSP concentrations was Fe > Zn > Mg > Cu > Cr > Mn > Pb in spring Fe > Zn > Mg > Cu > Cr > Mn > Pb in summer Fe > Zn > Mg > Cu > Cr > Mn > Pb in autumn and Fe > Zn > Mg > Cu > Cr > Mn > Pb in winter at the TH sampling sites. 3.4. Comparison with other studies Table 3 summarizes the atmospheric studies at different sites around the world. The discussions of those metallic elements were as follows. Copper is a reddish metal that occurs naturally in soil, water, sediment, and, at low levels in air. The average spring concentration of Cu in fine particulates and coarse particulates were 88.4 and 113.4 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Cu observed in the coarse particulates mode is higher than that of the fine particulates mode in spring. The average summer concentrations of Cu in fine particulates and coarse particulates were 86.9 and 79.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average Cu concentration observed in the fine particulates mode is higher than that of the coarse particulates mode in summer. The average autumn concentrations for Cu in fine particulates and coarse particulates were 84.8 and 81.5 ng m 3 at TH (Taichung
Harbor), respectively. The seasonal average concentration of Cu observed in fine particulates is slightly higher than that of coarse particulates in autumn. The average winter concentrations of Cu in fine particulates and coarse particulates were 89.6 and 85 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentrations of Cu observed in the fine particulates is higher than that of the coarse particulates in autumn. In general, the average concentrations of metallic Cu were riched in the fine particulates mode for all seasons except spring at the TH samples site. In addition, the data of metallic element Cu obtained in the study were ranked as the highest concentrations compared with other regions around the world. Manganese is a naturally occurring substance found in many types of rock. The average spring concentration of Mn in fine particulates and coarse particulates were 21.1 and 32.5 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentrations of Mn observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Mn in fine particulates and coarse particulates were 19.6 and 27.2 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentrations of Mn observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentration of Mn in fine particulates and coarse particulates were 22.1 and 33.2 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mn observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Mn in fine particulates and coarse particulates were 19.6 and 43.5 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentrations of Mn observed in coarse particulates is higher than that of fine particulates in winter. Compared with other studies in Table 3, the results indicated that metallic Mn at TH (Taichung Harbor) was ranked as the third highest concentration around the world. In other words, the concentrations of metallic Mn in the winter season of Milan (102 ng m 3; Henryk Bem et al., 2003) and metallic of Korea (Ki-Hyun Kim et al., 2002) have the highest metallic Mn concentrations during the years 2000–2004. Zinc is one of the most common elements on earthÕs crust. It is found in the air, soil, and water and is also present in all foods. The average spring concentrations of Zn in fine particulates and coarse particulates were 142.8 and 151.3 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Zn observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Zn in fine particulates and coarse particulates were 118.5 and 156.8 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Zn observed in coarse particulates is higher than that of fine
Table 3 Comparisons of atmospheric metallic element concentrations at different sites around the world (ng m 3) Sampling site
Character
Survey year
Particle size
Season
Cu
Mn
Zn
Pb
Cr
Mg
Lodz Milan Korea
Zeromskieqoa Taeion cityb
Urban Downtown Urban
2001 2001 2000–2001
TSP TSP TSP
Japan
Matsuec
Urban
1989–1996
TSP
Ube
Urban
TSP
Chikugo-O
Urban
TSP
Ohmuta
Urban
TSP
Brazil USA Hungary Italy USA Japan USA
Riode Janeirod Argentinae Debrecenf Tito Scalog Rondvilleh Kanazawai South Floridaj
Japan
Miami Yamaauchihk
Industrial downtown Urban Industrial Rural Suburban Station Industrial Urban Urban
2001–2002 2000 1998 2001 1992 2003 1995 1995 1995 2001
Osakail
Traffic
1999–2002 1999–2002 1999–2002 1999–2002 2000–2001
Winter Winter Spring Summer Fall Winter Spring Summer Winter Spring Summer Winter Spring Summer Winter Spring Summer Winter – – – – – – – – – – – – – – – – – – – – – – –
– – 33.2 31.6 47.8 56.6 – – – – – – – – – – – – 335 8.9–73 11 58 5.4 18.04 3.1 5.1 11.6 – – 13 ± 3.5 21 ± 4.1 12 ± 30 18 ± 51 13.1 3.5 0.7 8.7 5.05 ± 4.07 13.2 ± 43.4 1.67 ± 0.5 2.58 ± 1.86
16.3 102.0 55.7 25.3 61.1 75.9 – – – – – – – – – – – – 1216 8.8–92 23 27 10.1 34.69 3.5 5.6 5.1 – 88.0 17 ± 4.3 34 ± 10 12 ± 3.1 17 ± 6.2 10.6 2.3 3.8 12.8 8.87 ± 5.57 30.7 ± 18.8 5.12 ± 3.89 28.7 ± 15.6
71.7 290.0 208.0 129.0 273.0 298.0 49.75 ± 14.46 29.0 ± 5.12 47.9 ± 15.44 133.4 ± 57.1 79.8 ± 34.9 130.5 ± 41.9 183.7 ± 144.3 47.4 ± 9.55 270.9 ± 212.0 245.2 ± 89.06 97.8 ± 43.0 360.0 ± 104.1 2120 20–1049 56 304 28.5 1386.17 10.5 27.4 24 100.0 – 140 ± 42 250 ± 74 130 ± 31 92 ± 40 35.2 4.4 12.5 11.7 272 ± 247 375 ± 367 16.7 ± 9.43 27.4 ± 16.1
41.2 775.0 251.0 204.0 262.0 251.0 32.0 ± 8.71 15.2 ± 3.76 29.3 ± 6.82 52.5 ± 13.4 33.1 ± 23.2 85.8 ± 61.6 43.7 ± 8.19 24.8 ± 7.28 58.4 ± 23.2 73.6 ± 16.1 29.3 ± 11.0 104.9 ± 50.1 101 44–268 72 60 22.4 5.75 3.5 7.4 6.8 – – 37 ± 11 40 ± 14 30 ± 10 14 ± 6.9 1.3 0.2 4.1 3.0 164 ± 557 124 ± 350 14.7 ± 4.59 16.2 ± 8.48
4.1 49.0 18.3 13.2 35.9 30.8 2.73 ± 1.22 3.17 ± 2.28 3.10 ± 1.82 4.46 ± 4.14 3.21 ± 2.26 3.73 ± 1.72 4.18 ± 2.21 2.30 ± 0.92 4.13 ± 1.82 3.92 ± 2.52 4.60 ± 2.77 4.74 ± 2.98 421 3.5–12 18 13 1.9 – – – – – – – – – – 5.0 1.1 0.9 1.2 7.99 ± 7.76 25.2 ± 127 4.55 ± 3.35 9.34 ± 5.44
– 677.0 – 4500.0 – 2171.0 – 1024.0 – 1626.0 – 1782.0 – 572.9 ± 371.6 – 116.8 ± 30.0 – 247.3 ± 82.4 – 725.0 ± 964.9 – 254.0 ± 84.6 – 404.7 ± 188.4 – 292.9 ± 160.6 – 97.9 ± 52.1 – 216 ± 115.6 – 853.3 ± 313.5 – 246.7 ± 79.2 – 730.0 ± 151.2 6643 38 903 – 747–5967 – 911 – 521 – 233 379.84 869.25 – 216 – 345 – 324 – 400.0 2000.0 3900.0 – 220 ± 40 – 1100 ± 290 – 190 ± 51 – 830 ± 240 – 295.7 – 150.9 – 169.7 – 737.6 433 ± 228 207 ± 132 919 ± 412 1306 ± 766 314 ± 112 114 ± 70.6 812 ± 306 1119 ± 675 (Continued on next page)
Residential m
USA
Los Angeles
Bangladesh
Dhakaon
Semi-urban
Rajshahi
Urban
Industrial Traffic Riverside
2001–2002
TSP TSP TSP TSP TSP TSP TSP TSP TSP Fine (62.1 lm) Coarse (P2.1 lm) Fine (62.1 lm) Coarse (P2.1 lm) Fine (62.1 lm) Coarse (P2.1 lm) PM2.5 PM2.5–10 PM2.5 PM2.5–10 PM2.5 PM2.5–10 PM2.5 PM2.5–10
Fe
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
Country
1919
1920
Table 1 (Continued) Country
Sampling site o
Survey year
Particle size
Season
Cu
Mn
Zn
Pb
Cr
Mg
Fe
PM2.5 PM2.5 PM2.5–10 Fine (62.1 lm)
– – – Spring Summer Autumn Winter spring Summer Autumn Winter
23.0 3±2 4±3 88.4 86.9 84.8 89.6 113.4 79.6 81.5 85.0
14.0 2±3 7±8 21.1 19.6 22.1 19.6 32.5 27.2 33.2 43.5
178.0 23 ± 20 17 ± 16 142.8 118.5 156.0 127.0 151.3 156.8 159.8 130.0
130.0 9 ± 10 6±7 5.5 4.1 5.3 6.7 10.6 7.6 6.2 6.8
6.0 – – 45.5 39.8 36.8 43.0 62.6 50.4 62.6 63.0
80.0 86 ± 16 147 ± 57 189.1 146.3 162.7 198.0 402.3 356.6 338.2 343.0
260.0 63 ± 60 332 ± 330 285.7 244.7 245.8 220.0 957.7 802.3 670.3 703.5
Spain New Zealand
Cataloniac Aucklandbp
Urban Campus
1999–2000 2000–2001
This study (Taiwan)
Taichung
Harbor
2004
Coarse (P2.1 lm)
a b c d e f g h i j k l m n o p
Henryk Bem et al. (2003). Ki-Hyun Kim et al. (2002). Figen Var et al. (2000). Simone Lorena Quiterio et al. (2004). Bilos et al. (2001). Boberly-Kiss et al. (1999). Ragosta et al. (2002). Sweet et al. (1993). XilongWanga et al. (2005). Joseph et al. (2004). Mori et al. (2003).
Funasaka et al. (2003). Singh et al. (2002). Begum et al. (2004). Querol et al. (2001). Senaratne and Shooter (2004).
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
Character
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
particulates in summer. The average autumn concentrations of Zn in fine particulates and coarse particulates were 156 and 159.8 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Zn observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Zn in fine particulates and coarse particulates were 127 and 130 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Zn observed in coarse particulates is higher than that of fine particulates in winter. In general, the average concentrations of Zn in coarse particulates were slightly higher than those of fine particulates in all four seasons in this study. Lead occurs naturally in the environment. However, most of the lead found throughout the environment comes from human activities. The average spring concentration of Pb in fine particulates and coarse particulates were 5.5 and 10.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Pb observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Pb in fine particulates and coarse particulates were 4.1 and 7.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Pb observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentrations of Pb in fine particulates and coarse particulates were 5.3 and 6.2 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Pb observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Pb in fine particulates and coarse particulates were 6.7 and 6.8 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Pb observed in coarse particulates is higher than that of fine particulates in winter. The study obtained here found that metallic Pb has lower concentrations compared with other regions around the world since the year 2000. There were no significant seasonal concentration variations for Pb. Chromium is a naturally occurring element found in animals, plants, soil, and in volcanic dust and gases. The average spring concentrations of Cr in fine particulates and coarse particulates were 45.5 and 62.6 ngm 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Cr observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Cr in fine particulates and coarse particulates were 39.8 and 50.4 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Cr observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentrations of Cr in fine particulates and coarse particulates were 36.8 and 62.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average
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concentration of Cr observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Cr in fine particulates and coarse particulates were 43 and 63 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Cr observed in coarse particulates is higher than that of fine particulates in winter. In general, the average concentrations of metallic Cr were richest in the coarse particulates mode for all seasons at the TH samples site. In addition, the data of metallic Cr obtained in this study ranked as the second highest concentration compared with other regions except Brazil (421 ng m 3; Simone Lorena Quiterio et al., 2004) around the world. There were no significant seasonal concentration variations for Cr. The average spring concentrations of Mg in fine particulates and coarse particulates were 189.1 and 402.3 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mg observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Mg in fine particulates and coarse particulates were 146.3 and 356.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mg observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentrations of Mg in fine particulates and coarse particulates were 162.7 and 338.2 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mg observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentration of Mg in fine particulates and coarse particulates were 198 and 343 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mg observed in coarse particulates is higher than that of fine particulates in winter. In general, the concentration of Mg in the coarse particulate mode was higher than that of the fine particulate mode for all four seasons. Iron is the most abundant metallic element among all selected elements. The average spring concentrations of Fe in fine particulates and coarse particulates were 285.7 and 957.7 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Fe observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Fe in fine particulates and coarse particulates were 244.7 and 802.3 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Fe observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentrations of Fe in fine particulates and coarse particulates were 245.8 and 670.3 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Fe observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Fe in
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fine particulates and coarse particulates were 220 and 703.5 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Fe observed in coarse particulates is higher than that of fine particulates in winter. In general, the seasonal concentrations of Fe in the coarse particulate mode were all higher than those of the fine particulate mode. In general, the average anthropogenic concentrations of Cu, Mn, Zn, Pb, Cr, Mg and Fe at the traffic site (Fang et al., 2005) were higher than those at the TH (Taichung Harbor) sampling site for various particulate sizes except Mn in the coarse particulate mode. In addition, the anthropogenic elements (Mn, Zn, Pb, Cr, Mg and Fe) obtained in this study were found to be associated with the coarse particulate size while Cu tended to be associated with fine particulates. From the point of view of seasonal distributions, metallic Cu, Pb, Mg and Fe exhibited high concentrations in spring for the coarse particulate size range while spring has higher concentrations compared with the other seasons. This phenomenon also occurred for the elements Cu, Pb and Mg among the other seasons at the TH (Taichung Harbor) sampling site. However, the average metallic elements Cu and Pb exhibited no significant seasonal variations for either coarse particulate or fine particulate at the TH (Taichung Harbor) sampling site. The average concentrations for Fe in the coarse particulate size mode were about 3.15 times those in the fine particulate size mode for all four seasons at TH (Taichung Harbor). This value was about 2.07 for metallic Mg. There two ratios were higher than those for the traffic sampling site (Fang et al., 2005).
4. Conclusions The average elemental concentrations for Fe in the coarse particulate size mode were about 3.15 times the average concentration of this element in the fine particulate size mode for all four seasons at TH (Taichung Harbor). This value was about 2.07 for elemental Mg. In addition, the anthropogenic elements (Mn, Zn, Pb, Cr, Mg and Fe) obtained in this study were found to be associated with coarse particulate size while element Cu tended to be associated with fine particulates. From the point of view of seasonal distributions, metallic elements Cu, Pb, Mg and Fe exhibited high concentrations in spring for the coarse particulate size range while spring has higher concentrations compared with the other seasons at TH sampling site. The order of average metallic TSP concentrations order was Fe > Zn > Mg > Cu > Cr > Mn > Pb in spring at the TH sampling sites. The highest TSP, coarse and fine particulate concentration at TH occurred in the spring and winter seasons. In addition, at the TH sampling site, the average concentration variations of TSP displayed the following order: spring > winter > autumn > summer. However, the vari-
ations of average coarse particulate concentration displayed the following order: spring > winter > summer > autumn. Finally, the order of average concentration variations of fine particulates was: winter > spring > summer > autumn.
Acknowledgments The authors gratefully acknowledge the National Science Council of the R.O.C. (Taiwan) for financial support under project No. NSC 93-2211-E-241-007.
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Characterization of atmospheric particulate and metallic elements at Taichung Harbor near Taiwan Strait during 2004–2005 Guor-Cheng Fang *, Yuh-Shen Wu, Jum-Bo Lin, Chi-Kwong Lin, Jui-Yeh Rau, Shih-Han Huang Air Toxic and Environmental Analysis Laboratory, Hungkuang University, Sha-Lu, Taichung 433, Taiwan Received 13 August 2005; received in revised form 7 October 2005; accepted 7 October 2005 Available online 22 November 2005
Abstract Air aerosol samples for TSP (total suspended particulate), coarse particulate (particle matter with aerodynamical diameter 2.5–10 lm, PM2.5–10), fine particulate (particle matter with aerodynamical diameter <2.5 lm, PM2.5) and metallic elements were collected during March 2004 to January 2005 at TH (Taichung Harbor) in central Taiwan. The seasonal variation average concentration of TSP (total suspended particulate), coarse particulate (particle matter with aerodynamical diameter 2.5–10 lm, PM2.5–10) and fine particulate (particle matter with aerodynamical diameter <2.5 lm, PM2.5) were in the range 132–171.1 lg m 3 and 43–49.5 lg m 3, respectively. Seasonal variation of metallic elements Cu, Mn, Zn and Fe in the TSP (total suspended particulate) shows that higher concentration was observed during spring. Seasonal variation of metallic elements Pb, Cr and Mg in the TSP (total suspended particulate) shows that higher concentration was observed during winter. The average metallic element TSP (total suspended particulate) concentration order was Fe > Zn > Mg > Cu > Cr > Mn > Pb in spring. In addition, at the TH sampling site, the average concentration variation of TSP (total suspended particulate) displayed the following order: spring > winter > autumn > summer. However, the average concentration variation of coarse particulate (particle matter with aerodynamical diameter 2.5–10 lm, PM2.5–10) displayed the following order: spring > winter > summer > autumn. Finally, the average concentration variations of fine particulate (particle matter with aerodynamical diameter <2.5 lm, PM2.5) were in the following order: winter > spring > summer > autumn at the TH sample site. 2005 Elsevier Ltd. All rights reserved. Keywords: Season variation; Metallic; Particulate; Harbor
1. Introduction
* Corresponding author. Tel.: +886 4 2631 8652x1111; fax: +886 4 2350 2102. E-mail address: [email protected] (G.-C. Fang).
The higher values of PM found in summer with respect to winter are in agreement with the abundance of re-suspended material in summer at Buenos Aires, due to the effect of wind. It is very interesting to note that the levels of PM in Buenos Aires decrease from
0045-6535/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2005.10.010
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
summer to autumn-winter, while the opposite behavior was observed in Sa˜o Paulo. This is probably due to the different topography and meteorological characteristics (Bogo et al., 2003). A characteristic seasonal variation can be observed for PM10 and PM2.5 with elevated concentrations during the cold season. The reasons for this are not primarily caused by seasonal fluctuations of the emissions, but rather by meteorological effects. The PM2.5/PM10 ratios are not constant over the year. In general lower values were observed during spring and partly also during summer, indicating presumably the occurrence of coarse biogenic dust (e.g. pollen). At Bern, this seasonal variation of the PM2.5/ PM10 ratios cannot be observed. Obviously, if present at all, it is masked by the massive influence of locally produced exhaust and road dust (Gehrig and Buchmann, 2003). The particle size distribution of PM varies seasonally with the fine fractions prevailing in summer (PM2.5/PM10 = 80–90%) and the coarser increasing in winter (PM2.5/PM10 = 60–70%). As expected, PM levels obtained at the different monitoring sites gradually increased from regional background stations to industrial sites as a result of the addition of local contributions (traffic, industry). The majority of the stations selected are subject to the influence of close industrial and/or traffic PM sources (Viana et al., 2003). In Nanjing city on average, 63–77% of PM10 is in the PM2.5 fraction, which indicates that fine particles are the major component of atmospheric aerosols (Wang et al., 2003). The elements Mg, Al, Si, K, Ca and Fe have been found to form a major fraction of aerosol particles collected in China during dust storms (Fan et al., 1996). High concentrations of As, Mn, V, non-sea-salt sulfate and ammonium N indicate the significant impact of fossil fuel burning, while enhanced Al, Ca, Fe and Mn concentrations show the effect of mineral dusts and crustal materials (Lee and Hills, 2003). In general, airborne fine particles of 1 (PM1) and 2.5 mm (PM2.5) in diameter or less are considered of great health significance (Li and Lin, 2003). The Cu, Pb, and Fe concentrations resembled the median value at different areas around the world. However, the mean Zn and Mn concentrations results in fine particles (PM2.5) ranked as comparable with other areas around the world. The mean Ni, Cr and Cd concentrations ranked highest in both fine particle (PM2.5) and coarse particle (PM2.5–10) concentrations compared with data collected from other world regions (Fang et al., 2003). The concentrations of Cd, Mn, Ni and Zn were significantly higher at the industrial sites and should be attributed to the pyrometallurgical processes (Pb and Zn smelters, non-ferrous metal industries, etc.) taking place in the area, as well as to the manganese ore treating plant. Relatively higher Pb concentrations were found at the urban sites due to higher traffic density (Voutsa and Samara, 2002). The wind and precipitation had the effect of dispersing and dilut-
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ing the aerosol, making the summer concentrations lower (Resina Maura de Miranda et al., 2002). The purpose of this study was to understand metallic element concentrations and their seasonal variations at TH (Taichung Harbor). Two PS-1s (GPS1 PUF Sampler, General Metal Work) and a Universal Air Sampler were used to collect and analyze the above pollutants and their seasonal variations at TH (Taichung Harbor) during March 2004 to January 2005 in this study.
2. Materials and methods 2.1. Sampling site The sampling site of this study was as shown in Fig. 1. Taichung Harbor (TH) was selected as the sampling site. The distance to the nearest traffic road and TH are about 30 km. Atmospheric particulate concentration were collected for 24 consecutive hours at the TH sampling sites by PS-1 and Universal sample simultaneously during March 2004 to January 2005. Taichung Harbor is an artificial harbor with a maximum of 83 docks, which is located on the west coast of central Taiwan. It occupies about 37 600 acres. The sampling height of this sampling site is about 10 m. TH sampling sites were also placed on the highest building in this region. The Taichung Thermal Power Plant was developed on 281 ha located along the coast west of the sampling sites. The Taichung Thermal Power Plant was coal combustion based, and is the largest thermal power plant in Southeast Asia. The Taichung Thermal Power Plant can produce about 4400 MW hours per day to supply the electric requirements of central Taiwan. It was located about 15 km southeast of the TH sampling sites. 2.2. Sampling program 2.2.1. Sample collection 2.2.1.1. Universal air sampler. The Model 310 Universal Air SamplerTM (UASTM) is a general–purpose air sampler for atmospheric aerosol sampling and mass concentration determinations, as well as organic or inorganic analyses. The sampler has a designed inlet sampling flow rate of 300 l/min. It is provided with an omni-directional inlet, a PM10 (10 lm cut) virtual impact classifier, and either a PM2.5 or PM10 virtual impact classifier, or a fine particle filter. This allows the sampler to be operated as a high volume dichotomous sampler for size fractionation of airborne particles in the fine (0–2.5 lm) and coarse (2.5–10 lm) aerodynamic size ranges. Air is aspired at 300 l/min from the ambient atmosphere. Particles greater than 10 lm aerodynamic equivalent diameters are removed from the air stream by the PM10 classifier and discarded. Particles less than 10 lm in diameter flow to the PM2.5 classifier located downstream.
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Fig. 1. The sampling positions and relative location of this study.
Particles in the coarse (2.5–10 lm) range (coarse fraction) are collected on a 62 mm · 165 mm filter and those smaller than fine (2.5 lm) (fine fraction) are collected on a 200 mm · 250 mm final filter (Universal Air Sampler, 1996). Quartz filters (62 mm · 165 mm, 200 mm · 250 mm) were weighed before and after sampling to determine the amounts of particulate collected.
ments were 0.021, 0.007, 0.022, 0.015, 0.017, 0.012 and 0.015 mg/l for Fe, Mg, Cr, Cu, Zn, Mn and Pb, respectively. The method detection limit was determined by selecting the concentration slightly higher than the lowest concentration of the standard line, and repeating this concentration 12 times to estimate the standard deviation (S). The MDL was equal to 3 * S.
2.2.1.2. PS-1 sampler. The PS-1 (GPS1 PUF Sampler, General Metal Work) is a complete system designed to simultaneously collect suspended airborne particulates at flow rates up to 280 l/min. The flow rate was adjusted to 200 l/min in this study. The quartz filter (diameter 10.2 cm) is used to filter the suspended particles. The system consists of nine basic assemblies: dual chamber, sampling module, flow vent, electromagnetic gauge, voltage, elapsed time indicator, pump, 7-day skip timer, exhaust hose and aluminum shelter. The filters were first conditioned for 24 h in an electric chamber at humidity 50 ± 5% and temperature 25 ± 5 C prior to weighing. Filters were placed in a sealed CD box during the transport and storage process.
2.2.2.2. Recovery efficiency test. At least 10% of the samples are analyzed by spiking with a known amount of metal to calculate recovery efficiencies. The analysis procedure for the recovery test is the same as that described for the field samples. The recovery tests of metallic elements were 96%, 97%, 97%, 101%, 102%, 105% and 101% for Fe, Zn, Mn, Cu, Pb, Cr and Mg, respectively.
2.2.2. Quality control 2.2.2.1. Detection limit. The detection limit was used to determine the lowest concentration level that can be detected to be statistically different from a blank. The method detection limit (MDL) was determined by selecting the concentration slightly higher than the lowest concentration of the standard line. The procedure of repeating the lowest concentration of standard solution 12 times was also used to estimate the standard deviation (S). The method detection limits for metallic ele-
2.2.2.3. Blank test. The blank test background contamination was monitored by using operational blanks (unexposed projection film and quartz filter) which were processed simultaneously with field samples. Background contamination of heavy metals was accounted for by subtracting field blank values from the concentrations. Field blank values were very low, usually below or around the method detection limits. In this study, the background contamination is insignificant and can be ignored. The results of the blank test are 0.43, 0.36, 0.30, 0.25, 0.21, 0.19 and 0.17 lg for Fe, Zn, Mn, Cu, Pb, Cr and Mg, respectively. 2.3. Sampling information Table 1 show seasonal sampling information for meteorological conditions such as temperature, relative
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
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Table 1 Seasonal sampling information meteorological conditions at TH sampling sites during March of 2004 to January of 2005 Seasons
Month
Ta (C)
RHb (%)
PWDc
Pd (hpa)
Spring
March April May Average
18.7 21.6 24.4 21.6
70.5 74.7 75.7 73.6
NNE NNW N
1020.2 1012.4 1009.2 1013.9
Summer
June July August Average
26.6 29.4 27.5 27.8
72.0 75.5 73.0 73.5
NE NE N
1006.2 1006.1 1007.1 1006.5
Autumn
September October November Average
27.6 25.1 22.1 24.9
72.0 71.0 69.5 70.8
SWW NNE NE
1011.1 1012.8 1011.8 1011.9
Winter
December January Average
16.9 14.6 158
77.0 74.0 75.5
NNE NNW
1015.6 1018.2 1016.9
a b c d
Temperatures. Relative humidity. Prevalent wind direction. Air pressure.
humidity, atmospheric pressure and prevalent wind direction at the TH sampling sites during March 2004 to January 2005. In spring, 2004 (March, April, May) the average temperature, relative humidity, prevalent wind direction and atmospheric pressure were 21.4 C, 73.9%, NNW, N, NNW and 1013.8 hpa, respectively. In summer, 2004 (June, July, August) the average temperature, relative humidity, prevalent wind direction and atmospheric pressure were 28.02 C, 75.2%, NE, N and 1006.6 hpa, respectively. In autumn, 2004 (September, October, November) the average temperature, relative humidity, prevalent wind direction and atmospheric pressure were 24.42 C, 71.92%, NE, NNE, SWW and 1009.75 hpa, respectively. In winter, (December) 2004 and (January) 2005 the average temperature, relative humidity, prevalent wind direction and atmospheric pressure were 16 C, 75.2%, NNE, NNW and 1016.18 hpa, respectively. In general, the relative humidity was all higher then that at land sampling sites (traffic, urban, suburban) around central Taiwan. The temperature range for each season in this study was lower than that of land (traffic, urban, suburban) sampling sites around central Taiwan.
3. Results and discussion 3.1. Monthly variation of particulate mass The average concentration and seasonal variation of TSP, coarse particulate and fine particulate for the TH sampling site are displayed in Fig. 2. The TSP and
coarse particulate showed regular seasonal variations, with higher concentration in spring and winter while lower concentration occurred in summer and autumn. For the fine particulate, higher concentration occurred in winter and spring and lower concentration occurred in autumn. At the TH sampling site, the average concentration variations of TSP displayed the following order: spring > winter > autumn > summer. However, the average concentration variation of coarse particulate displayed the following order: spring > winter > summer > autumn. Finally, the average concentration variations of fine particulate were in the following order: winter > spring > summer > autumn at the TH sample site. 3.2. Seasonal variation of particulate mass Table 2 shows the seasonal variation of TSP, coarse particulate and fine particulate average concentrations at the TH sampling sites during March of 2004 to January of 2005. The seasonal average concentrations of TSP were found to be 117.1, 132.0, 160.2 and 170.8 lg m 3 for spring, summer, autumn and winter, respectively. In addition, average coarse particulate concentrations were found to be 37.0, 26.6, 26.2 and 36.0 lg m 3 for spring, summer, autumn and winter. Finally, the average fine particulate concentrations were found to be 49.3, 46.4, 43.0 and 49.5 lg m 3 for spring, summer, autumn and winter, respectively at TH sampling site. The highest seasonal average TSP and coarse particulate concentrations were found in spring (171.1 lg m 3), and (37 lg m 3), respectively. The highest seasonal average
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G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923 200 180
Concentrations (μg m-3)
160 140 120 100 80 60 40 20 0 Mar
Apr
May
Jun
Jul
Aug
Sep
Oct
Nov
Dec
Jan
Month TSP coarse fine
Fig. 2. Monthly variation of TSP, coarse and fine particulate average concentration at the TH site during March 2004 to January 2005.
Table 2 Seasonal variation of mean TSP, coarse and fine concentrations at TH sampling sites during March of 2004 to January of 2005 Seasons
TSP (lg m 3)
Coarse (lg m 3)
Fine (lg m 3)
Spring (March, April, May) Summer (June, July, August) Autumn (September, October, November) Winter (December, January)
171.1 132.0 160.2 170.8
37.0 26.6 26.2 36.0
49.3 46.4 43.0 49.5
concentration of fine particulate was found in the winter (49.5 lg m 3). In general, the highest coarse and fine particulate concentration at TH occurred in the spring and winter season. This phenomenon is opposite opportune to that of the traffic sampling site study (Fang et al., 2005). 3.3. Seasons of metallic elements Fig. 3(A)–(G) indicates the seasonal variation of metallic element (Cu, Mn, Zn, Pb, Cr, Mg and Fe) concentrations for TSP, coarse particulate and fine particle sizes at the TH sampling site during March 2004 to January 2005 for four seasons near the Taiwan Strait in central Taiwan. Fig. 3(A) shows on metallic element Cu in TSP, coarse particulate and fine particulate concentrations vs. seasons in the Taichung Harbor area. The order of seasonal variations was spring > winter > summer P autumn for
TSP, and spring > winter > autumn P summer for coarse particulate. The fine concentrations exhibited no significant seasonal variations for metallic Cu in this study. Fig. 3(B) shows on metallic element Mn in TSP, coarse particulate and fine particulate concentrations vs. seasons in the Taichung Harbor area. The order of seasonal variations was spring > winter > summer > autumn for TSP, and winter > autumn P spring > summer for coarse particulate. The fine concentrations exhibited no significant seasonal variations for metallic Mn in this study. Fig. 3(C) shows on metallic element Zn in TSP, coarse particulate and fine particulate concentrations vs. seasons in the Taichung Harbor area. The order of seasonal variations was spring > winter > autumn > summer for TSP, and autumn > summer P spring > winter for coarse particulate. The season variations of concentration order for metallic Zn was autumn > spring > winter > summer for fine particulate.
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923 Cu - (A)
Mn - (B) 120
concentration (ng m-3)
concentration (ng m-3)
600 500 400 300 200 100
100 80 60 40 20 0
0 Spring TSP coarse fine
Summer
Autumn
Winter
Spring
seasons
TSP coarse fine
Zn - (C)
Autumn
Winter
seasons
50
concentration (ng m-3)
concentration (ng m-3)
Summer
Pb - (D)
1000 800 600 400 200 0 Spring TSP coarse fine
Summer
Autumn
40 30 20 10 0
Winter
seasons
Spring TSP coarse fine
Cr - (E)
Summer
Autumn
Winter
seasons
Mg - (F)
350
800
concentration (ng m-3)
concentration (ng m-3)
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300 250 200 150 100 50
600
400
200
0
0 Spring TSP coarse fine
Summer
Autumn
Winter
seasons
Spring TSP coarse fine
Summer
Autumn
Winter
seasons
Fe - (G)
concentration (ng m-3)
1600 1400 1200 1000 800 600 400 200 0 Spring TSP coarse fine
Summer
Autumn
Winter
seasons
Fig. 3. (A)–(G) Seasonal variation of metallic (Cu, Mn, Zn, Pb, Cr, Mg and Fe) concentrations for TSP, coarse particulate and fine particle sizes.
Fig. 3(D) shows on metallic Pb in TSP, coarse particulate and fine particulate concentrations vs. seasons at Taichung Harbor area. The season variations of concen-
tration order for metallic element was winter > spring > autumn P summer for TSP. And the seasonal variations of concentration order for metallic element was
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G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
spring > summer > winter > autumn for coarse particulate. Besides, the seasonal variations of concentration order for metallic element was winter > spring > autumn > summer for fine particulate. Fig. 3(E) shows on metallic element Cr in TSP, coarse particulate and fine particulate concentrations vs. seasons in the Taichung Harbor area. The order at season variations was winter > spring > autumn P summer for TSP and winter > spring > autumn > summer for coarse particulate. The seasonal variations of concentration order for metallic element was spring > winter > summer > autumn for fine particulate. Fig. 3(F) shows on metallic element Mg in TSP, coarse particulate and fine particulate concentrations vs. seasons at Taichung Harbor area. The order at seasonal variations was winter > spring > autumn P summer for TSP and spring > summer > autumn > winter for coarse particulate. The seasonal variations of concentration order for metallic element was winter > spring > autumn > summer for fine particulate. Fig. 3(G) shows on metallic element Fe in TSP, coarse particulate and fine particulate concentrations vs. seasons at Taichung Harbor area. The order at seasonal variations of concentration order for metallic element was spring P winter > autumn P summer for TSP and spring > summer > winter > autumn for coarse particulate. The seasonal variations of concentration order for metallic element was spring > autumn P summer > winter for fine particulate. In general, the order at average metallic element TSP concentrations was Fe > Zn > Mg > Cu > Cr > Mn > Pb in spring Fe > Zn > Mg > Cu > Cr > Mn > Pb in summer Fe > Zn > Mg > Cu > Cr > Mn > Pb in autumn and Fe > Zn > Mg > Cu > Cr > Mn > Pb in winter at the TH sampling sites. 3.4. Comparison with other studies Table 3 summarizes the atmospheric studies at different sites around the world. The discussions of those metallic elements were as follows. Copper is a reddish metal that occurs naturally in soil, water, sediment, and, at low levels in air. The average spring concentration of Cu in fine particulates and coarse particulates were 88.4 and 113.4 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Cu observed in the coarse particulates mode is higher than that of the fine particulates mode in spring. The average summer concentrations of Cu in fine particulates and coarse particulates were 86.9 and 79.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average Cu concentration observed in the fine particulates mode is higher than that of the coarse particulates mode in summer. The average autumn concentrations for Cu in fine particulates and coarse particulates were 84.8 and 81.5 ng m 3 at TH (Taichung
Harbor), respectively. The seasonal average concentration of Cu observed in fine particulates is slightly higher than that of coarse particulates in autumn. The average winter concentrations of Cu in fine particulates and coarse particulates were 89.6 and 85 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentrations of Cu observed in the fine particulates is higher than that of the coarse particulates in autumn. In general, the average concentrations of metallic Cu were riched in the fine particulates mode for all seasons except spring at the TH samples site. In addition, the data of metallic element Cu obtained in the study were ranked as the highest concentrations compared with other regions around the world. Manganese is a naturally occurring substance found in many types of rock. The average spring concentration of Mn in fine particulates and coarse particulates were 21.1 and 32.5 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentrations of Mn observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Mn in fine particulates and coarse particulates were 19.6 and 27.2 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentrations of Mn observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentration of Mn in fine particulates and coarse particulates were 22.1 and 33.2 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mn observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Mn in fine particulates and coarse particulates were 19.6 and 43.5 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentrations of Mn observed in coarse particulates is higher than that of fine particulates in winter. Compared with other studies in Table 3, the results indicated that metallic Mn at TH (Taichung Harbor) was ranked as the third highest concentration around the world. In other words, the concentrations of metallic Mn in the winter season of Milan (102 ng m 3; Henryk Bem et al., 2003) and metallic of Korea (Ki-Hyun Kim et al., 2002) have the highest metallic Mn concentrations during the years 2000–2004. Zinc is one of the most common elements on earthÕs crust. It is found in the air, soil, and water and is also present in all foods. The average spring concentrations of Zn in fine particulates and coarse particulates were 142.8 and 151.3 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Zn observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Zn in fine particulates and coarse particulates were 118.5 and 156.8 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Zn observed in coarse particulates is higher than that of fine
Table 3 Comparisons of atmospheric metallic element concentrations at different sites around the world (ng m 3) Sampling site
Character
Survey year
Particle size
Season
Cu
Mn
Zn
Pb
Cr
Mg
Lodz Milan Korea
Zeromskieqoa Taeion cityb
Urban Downtown Urban
2001 2001 2000–2001
TSP TSP TSP
Japan
Matsuec
Urban
1989–1996
TSP
Ube
Urban
TSP
Chikugo-O
Urban
TSP
Ohmuta
Urban
TSP
Brazil USA Hungary Italy USA Japan USA
Riode Janeirod Argentinae Debrecenf Tito Scalog Rondvilleh Kanazawai South Floridaj
Japan
Miami Yamaauchihk
Industrial downtown Urban Industrial Rural Suburban Station Industrial Urban Urban
2001–2002 2000 1998 2001 1992 2003 1995 1995 1995 2001
Osakail
Traffic
1999–2002 1999–2002 1999–2002 1999–2002 2000–2001
Winter Winter Spring Summer Fall Winter Spring Summer Winter Spring Summer Winter Spring Summer Winter Spring Summer Winter – – – – – – – – – – – – – – – – – – – – – – –
– – 33.2 31.6 47.8 56.6 – – – – – – – – – – – – 335 8.9–73 11 58 5.4 18.04 3.1 5.1 11.6 – – 13 ± 3.5 21 ± 4.1 12 ± 30 18 ± 51 13.1 3.5 0.7 8.7 5.05 ± 4.07 13.2 ± 43.4 1.67 ± 0.5 2.58 ± 1.86
16.3 102.0 55.7 25.3 61.1 75.9 – – – – – – – – – – – – 1216 8.8–92 23 27 10.1 34.69 3.5 5.6 5.1 – 88.0 17 ± 4.3 34 ± 10 12 ± 3.1 17 ± 6.2 10.6 2.3 3.8 12.8 8.87 ± 5.57 30.7 ± 18.8 5.12 ± 3.89 28.7 ± 15.6
71.7 290.0 208.0 129.0 273.0 298.0 49.75 ± 14.46 29.0 ± 5.12 47.9 ± 15.44 133.4 ± 57.1 79.8 ± 34.9 130.5 ± 41.9 183.7 ± 144.3 47.4 ± 9.55 270.9 ± 212.0 245.2 ± 89.06 97.8 ± 43.0 360.0 ± 104.1 2120 20–1049 56 304 28.5 1386.17 10.5 27.4 24 100.0 – 140 ± 42 250 ± 74 130 ± 31 92 ± 40 35.2 4.4 12.5 11.7 272 ± 247 375 ± 367 16.7 ± 9.43 27.4 ± 16.1
41.2 775.0 251.0 204.0 262.0 251.0 32.0 ± 8.71 15.2 ± 3.76 29.3 ± 6.82 52.5 ± 13.4 33.1 ± 23.2 85.8 ± 61.6 43.7 ± 8.19 24.8 ± 7.28 58.4 ± 23.2 73.6 ± 16.1 29.3 ± 11.0 104.9 ± 50.1 101 44–268 72 60 22.4 5.75 3.5 7.4 6.8 – – 37 ± 11 40 ± 14 30 ± 10 14 ± 6.9 1.3 0.2 4.1 3.0 164 ± 557 124 ± 350 14.7 ± 4.59 16.2 ± 8.48
4.1 49.0 18.3 13.2 35.9 30.8 2.73 ± 1.22 3.17 ± 2.28 3.10 ± 1.82 4.46 ± 4.14 3.21 ± 2.26 3.73 ± 1.72 4.18 ± 2.21 2.30 ± 0.92 4.13 ± 1.82 3.92 ± 2.52 4.60 ± 2.77 4.74 ± 2.98 421 3.5–12 18 13 1.9 – – – – – – – – – – 5.0 1.1 0.9 1.2 7.99 ± 7.76 25.2 ± 127 4.55 ± 3.35 9.34 ± 5.44
– 677.0 – 4500.0 – 2171.0 – 1024.0 – 1626.0 – 1782.0 – 572.9 ± 371.6 – 116.8 ± 30.0 – 247.3 ± 82.4 – 725.0 ± 964.9 – 254.0 ± 84.6 – 404.7 ± 188.4 – 292.9 ± 160.6 – 97.9 ± 52.1 – 216 ± 115.6 – 853.3 ± 313.5 – 246.7 ± 79.2 – 730.0 ± 151.2 6643 38 903 – 747–5967 – 911 – 521 – 233 379.84 869.25 – 216 – 345 – 324 – 400.0 2000.0 3900.0 – 220 ± 40 – 1100 ± 290 – 190 ± 51 – 830 ± 240 – 295.7 – 150.9 – 169.7 – 737.6 433 ± 228 207 ± 132 919 ± 412 1306 ± 766 314 ± 112 114 ± 70.6 812 ± 306 1119 ± 675 (Continued on next page)
Residential m
USA
Los Angeles
Bangladesh
Dhakaon
Semi-urban
Rajshahi
Urban
Industrial Traffic Riverside
2001–2002
TSP TSP TSP TSP TSP TSP TSP TSP TSP Fine (62.1 lm) Coarse (P2.1 lm) Fine (62.1 lm) Coarse (P2.1 lm) Fine (62.1 lm) Coarse (P2.1 lm) PM2.5 PM2.5–10 PM2.5 PM2.5–10 PM2.5 PM2.5–10 PM2.5 PM2.5–10
Fe
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
Country
1919
1920
Table 1 (Continued) Country
Sampling site o
Survey year
Particle size
Season
Cu
Mn
Zn
Pb
Cr
Mg
Fe
PM2.5 PM2.5 PM2.5–10 Fine (62.1 lm)
– – – Spring Summer Autumn Winter spring Summer Autumn Winter
23.0 3±2 4±3 88.4 86.9 84.8 89.6 113.4 79.6 81.5 85.0
14.0 2±3 7±8 21.1 19.6 22.1 19.6 32.5 27.2 33.2 43.5
178.0 23 ± 20 17 ± 16 142.8 118.5 156.0 127.0 151.3 156.8 159.8 130.0
130.0 9 ± 10 6±7 5.5 4.1 5.3 6.7 10.6 7.6 6.2 6.8
6.0 – – 45.5 39.8 36.8 43.0 62.6 50.4 62.6 63.0
80.0 86 ± 16 147 ± 57 189.1 146.3 162.7 198.0 402.3 356.6 338.2 343.0
260.0 63 ± 60 332 ± 330 285.7 244.7 245.8 220.0 957.7 802.3 670.3 703.5
Spain New Zealand
Cataloniac Aucklandbp
Urban Campus
1999–2000 2000–2001
This study (Taiwan)
Taichung
Harbor
2004
Coarse (P2.1 lm)
a b c d e f g h i j k l m n o p
Henryk Bem et al. (2003). Ki-Hyun Kim et al. (2002). Figen Var et al. (2000). Simone Lorena Quiterio et al. (2004). Bilos et al. (2001). Boberly-Kiss et al. (1999). Ragosta et al. (2002). Sweet et al. (1993). XilongWanga et al. (2005). Joseph et al. (2004). Mori et al. (2003).
Funasaka et al. (2003). Singh et al. (2002). Begum et al. (2004). Querol et al. (2001). Senaratne and Shooter (2004).
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
Character
G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
particulates in summer. The average autumn concentrations of Zn in fine particulates and coarse particulates were 156 and 159.8 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Zn observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Zn in fine particulates and coarse particulates were 127 and 130 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Zn observed in coarse particulates is higher than that of fine particulates in winter. In general, the average concentrations of Zn in coarse particulates were slightly higher than those of fine particulates in all four seasons in this study. Lead occurs naturally in the environment. However, most of the lead found throughout the environment comes from human activities. The average spring concentration of Pb in fine particulates and coarse particulates were 5.5 and 10.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Pb observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Pb in fine particulates and coarse particulates were 4.1 and 7.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Pb observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentrations of Pb in fine particulates and coarse particulates were 5.3 and 6.2 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Pb observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Pb in fine particulates and coarse particulates were 6.7 and 6.8 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Pb observed in coarse particulates is higher than that of fine particulates in winter. The study obtained here found that metallic Pb has lower concentrations compared with other regions around the world since the year 2000. There were no significant seasonal concentration variations for Pb. Chromium is a naturally occurring element found in animals, plants, soil, and in volcanic dust and gases. The average spring concentrations of Cr in fine particulates and coarse particulates were 45.5 and 62.6 ngm 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Cr observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Cr in fine particulates and coarse particulates were 39.8 and 50.4 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Cr observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentrations of Cr in fine particulates and coarse particulates were 36.8 and 62.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average
1921
concentration of Cr observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Cr in fine particulates and coarse particulates were 43 and 63 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Cr observed in coarse particulates is higher than that of fine particulates in winter. In general, the average concentrations of metallic Cr were richest in the coarse particulates mode for all seasons at the TH samples site. In addition, the data of metallic Cr obtained in this study ranked as the second highest concentration compared with other regions except Brazil (421 ng m 3; Simone Lorena Quiterio et al., 2004) around the world. There were no significant seasonal concentration variations for Cr. The average spring concentrations of Mg in fine particulates and coarse particulates were 189.1 and 402.3 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mg observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Mg in fine particulates and coarse particulates were 146.3 and 356.6 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mg observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentrations of Mg in fine particulates and coarse particulates were 162.7 and 338.2 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mg observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentration of Mg in fine particulates and coarse particulates were 198 and 343 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Mg observed in coarse particulates is higher than that of fine particulates in winter. In general, the concentration of Mg in the coarse particulate mode was higher than that of the fine particulate mode for all four seasons. Iron is the most abundant metallic element among all selected elements. The average spring concentrations of Fe in fine particulates and coarse particulates were 285.7 and 957.7 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Fe observed in coarse particulates is higher than that of fine particulates in spring. The average summer concentrations of Fe in fine particulates and coarse particulates were 244.7 and 802.3 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Fe observed in coarse particulates is higher than that of fine particulates in summer. The average autumn concentrations of Fe in fine particulates and coarse particulates were 245.8 and 670.3 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Fe observed in coarse particulates is higher than that of fine particulates in autumn. The average winter concentrations of Fe in
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G.-C. Fang et al. / Chemosphere 63 (2006) 1912–1923
fine particulates and coarse particulates were 220 and 703.5 ng m 3 at TH (Taichung Harbor), respectively. The seasonal average concentration of Fe observed in coarse particulates is higher than that of fine particulates in winter. In general, the seasonal concentrations of Fe in the coarse particulate mode were all higher than those of the fine particulate mode. In general, the average anthropogenic concentrations of Cu, Mn, Zn, Pb, Cr, Mg and Fe at the traffic site (Fang et al., 2005) were higher than those at the TH (Taichung Harbor) sampling site for various particulate sizes except Mn in the coarse particulate mode. In addition, the anthropogenic elements (Mn, Zn, Pb, Cr, Mg and Fe) obtained in this study were found to be associated with the coarse particulate size while Cu tended to be associated with fine particulates. From the point of view of seasonal distributions, metallic Cu, Pb, Mg and Fe exhibited high concentrations in spring for the coarse particulate size range while spring has higher concentrations compared with the other seasons. This phenomenon also occurred for the elements Cu, Pb and Mg among the other seasons at the TH (Taichung Harbor) sampling site. However, the average metallic elements Cu and Pb exhibited no significant seasonal variations for either coarse particulate or fine particulate at the TH (Taichung Harbor) sampling site. The average concentrations for Fe in the coarse particulate size mode were about 3.15 times those in the fine particulate size mode for all four seasons at TH (Taichung Harbor). This value was about 2.07 for metallic Mg. There two ratios were higher than those for the traffic sampling site (Fang et al., 2005).
4. Conclusions The average elemental concentrations for Fe in the coarse particulate size mode were about 3.15 times the average concentration of this element in the fine particulate size mode for all four seasons at TH (Taichung Harbor). This value was about 2.07 for elemental Mg. In addition, the anthropogenic elements (Mn, Zn, Pb, Cr, Mg and Fe) obtained in this study were found to be associated with coarse particulate size while element Cu tended to be associated with fine particulates. From the point of view of seasonal distributions, metallic elements Cu, Pb, Mg and Fe exhibited high concentrations in spring for the coarse particulate size range while spring has higher concentrations compared with the other seasons at TH sampling site. The order of average metallic TSP concentrations order was Fe > Zn > Mg > Cu > Cr > Mn > Pb in spring at the TH sampling sites. The highest TSP, coarse and fine particulate concentration at TH occurred in the spring and winter seasons. In addition, at the TH sampling site, the average concentration variations of TSP displayed the following order: spring > winter > autumn > summer. However, the vari-
ations of average coarse particulate concentration displayed the following order: spring > winter > summer > autumn. Finally, the order of average concentration variations of fine particulates was: winter > spring > summer > autumn.
Acknowledgments The authors gratefully acknowledge the National Science Council of the R.O.C. (Taiwan) for financial support under project No. NSC 93-2211-E-241-007.
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