EnvironmentAsia
Available online at www.tshe.org/EA Available online at www.tshe.org/EA EnvironmentAsia 25(1) (2012) 39-47 EnvironmentAsia (2009) 50-54
The international journal published by the Thai Society of Higher Education Institutes on Environment
Genotoxicity Assessment of Mercuric Chloride in the Marine Fish Therapon jaruba Acid Rain Examination and Chemical Composition of Atmospheric Precipitation in Nagarajan Nagarani, Arumugam Kuppusamy Kumaraguru, Velmurugan Janaki Devi Tehran, Iran and Chandrasekaran Archana Devi Mohsen Saeedi a and Seyed Pejvak Pajooheshfar b
Center for Marine and Coastal Studies, School of Energy, Environment and Natural Resources, MaduraiSchool Kamaraj University, Madurai-625021, Environmental Research Laboratory, of Civil Engineering, Iran UniversityIndia of Science & Technology, Tehran, 16846, Iran b Post Graduate in Environmental Engineering, School of Civil Engineering, Iran University of Science & Technology, Abstract Tehran, 16846, Iran a
The aim of the present study was to standardize and to assess the predictive value of the cytogenetic analysis by Micronucleus (MN) test in fish erythrocytes as a biomarker for marine environmental contamination. Micronucleus Abstract frequency baseline in erythrocytes was evaluated in and genotoxic potential of a common chemical was determined in experimentally exposed in aquarium under controlled problems conditions. (Therapon jaruba) were exposed forsnow, 96 fish Air pollution is one of the most important environmental in Fish metropolitan cities like Tehran. Rain and hrs to a single heavy metal (mercuric chloride). Chromosomal damage was determined as micronuclei frequency in as natural events, may dissolve and absorb contaminants of the air and direct them onto the land or surface waters which fish erythrocytes. Significant increase in MN frequency was observed in erythrocytes of fish exposed to mercuric become polluted. In the present study, precipitation samples were collected from an urbanized area of Tehran. They were 2- ppm induced the highest MN frequency (2.95 micronucleated cells/1000 cells compared chloride. 0.25 , SO analyzed Concentration for NO3 , PO43 of 4 , pH, turbidity, Electrical Conductivity (EC), Cu, Fe, Zn, Pb, Ni, Cr, and Al. We demonstrate to 1 MNcell/1000 cells in control animals). The that micronucleus as an of of cumulative that snow samples were often more polluted and hadstudy lowerrevealed pH than those from the rain, test, possibly as index an effect adsorption exposure, appears to be a sensitive model to evaluate genotoxic compounds in fish under controlled conditions. capability of snow flakes. Volume weighted average concentrations were calculated and compared with some other studies. Results revealed that Tehran’s precipitations are much more polluted than those reported from other metropolitan cities. Keywords: genotoxicity; mercuric micronucleus Cluster analysis revealed that studiedchloride; parameters such as metals and acidity originated from the same sources, such as fuel combustion in residential and transportation sectors of Tehran. Keywords: wet deposition; heavy metals; acid rain; chemical composition; Tehran
1. Introduction
In India, about 200 tons of mercury and its 1. Introduction compounds are introduced into the environment annually as effluents from industries (Saffi, 1981). Air quality problems in urban areas mainly arise Mercuric chloride has been used in agriculture as a from fuel combustion in transportation, residential and fungicide, in medicine as a topical antiseptic and commercial sectors and industrial activities. Metals in disinfectant, and in chemistry as an intermediate in the atmosphere originate mainly from metal refining, the production of other mercury compounds. The fossil fuel combustion, vehicle exhausts, and other contamination of aquatic ecosystems by heavy human activities, and stay there until they are removed metals and pesticides has gained increasing attention by a variety of cleansing processes including dry in recent decades. Chronic exposure to and deposition, scavenging and washout by wet deposition accumulation of these chemicals in aquatic biota (Church et al., 1990; Alloway, 1990; Sillapapiromsuk can result in tissue burdens that produce adverse and Chantara, 2010). Heavy metals emitted by combuseffects not only in the directly exposed organisms, tion processes usually have relatively high solubility but also in human beings. and reactivity, because of the small sizes of particles Fish provides a suitable model for monitoring on which they are carried (Nriagu, 1984). Thus, they aquatic genotoxicity and wastewater quality dissolve readily in rain, especially under low pH condibecause of its ability to metabolize xenobiotics and tions caused by nitrogen and sulfur oxides in the urban accumulated pollutants. A micronucleus assay has atmosphere, resulting in polluted rainwater. been used successfully in several species (De Flora, Sulphur dioxide (SO2) and oxides of nitrogen are et al., 1993, Al-Sabti and Metcalfe, 1995). The the primary causes of acid rain. These pollutants origimicronucleus (MN) test has been developed nate from human activities such as waste incineration together with DNA-unwinding assays as and fossil fuels combustion in power plants, automoperspective methods for mass monitoring of biles, mineral processing, refineries and industries. The clastogenicity and genotoxicity in fish and mussels levels of NOx are small in comparison to SO2, but its (Dailianis et al., 2003). contribution in the production of acid rain is increasThe MN tests have been successfully used as ing (Singh and Agrawal, 2008; Sillapapiromsuk and a measure of genotoxic stress in fish, under both Chantara, 2010).
laboratory and field conditions. In 2006 Soumendra et al., made an attempt to detect genetic biomarkers in two fish species, Labeo bata and Oreochromis Some studies examined acidity of rainfalls in mossambica, by MN and binucleate (BN) conjunction with concentrations of chemical species erythrocytes in the gill and kidney erythrocytes which influence the pH value of rain. All of them conexposed to thermal power plant discharge at sidered the rain with pH values lower than 5.6 as acid Titagarh Thermal Power Plant, Kolkata, India. rain (Kobori et al., 2005; Sillapapiromsuk and Chantara, The present study was conducted to determine 2010; Smith et al., 1984; Singh and Agrawal, 2008). the acute genotoxicity of the heavy metal compound Monitoring the concentrations of heavy metals in HgCl2 in static systems. Mercuric chloride is toxic, the atmosphere (aerosols and rain events) can provide solvable in water hence it can penetrate the aquatic important information about the sources of these metals animals. Mutagenic studies with native fish species and enables budget and flux calculations to be made represent an important effort in determining the (Alloway, 1990). Large volumes of various types of potential effects of toxic agents. This study was pollutants from different sources are emitted into the carried out to evaluate the use of the micronucleus Tehran’s atmosphere. However, there have not been any test (MN) for the estimation of aquatic pollution reports on average concentrations and environmental using marine edible fish under lab conditions. geochemistry of wet depositions in Tehran, the most populated and polluted city of Iran. In the present study, 2. Materials and methods contents of dissolved metals (Al, Cr, Ni, Pb, Zn, Fe, and 23Cu) and ions (SO4 , PO4 , NO3 ) along with Electri2.1. Sample Collection cal Conductivity (EC), Turbidity, and pH of rain and snow samples from an urbanized area of Tehran from The fish species selected for the present study December 23, 2008 to July, 1 2009 were investigated. was collected from Pudhumadam coast of Gulf of There was no precipitation event from July 1, 2009 to Mannar, Southeast Coast of India. Therapon December 23, 2009. jarbua belongs to the order Perciformes of the family Theraponidae. The fish species, Therapon 2. Materials and Methods jarbua (6-6.3 cm in length and 4-4.25 g in weight) was selected for the detection of genotoxic effect 2.1. Sampling
M. Saeedi et al. / EnvironmentAsia 5(1) (2012) 39-47
Samples were obtained at Elahieh located in north Tehran near Gholhak valley which is one of the polluted areas of Tehran (Fig.1). The samples were collected using a bulk sampler equipped with a plastic funnel that was set on the roof of a building at about 30 meters from ground level and separated from other buildings and structures to avoid undesirable effects. After a precipitation event, the samples were immediately transported to the laboratory keeping them at 4°C. Snow samples were collected in the sampling funnel and allowed to melt at room temperature. All sampling apparatus (buckets and funnels) were acid washed and rinsed with distilled water prior to sampling.
of rain were collected in a plastic bucket during the first hour of a rainfall. Each rainfall was treated as one sample and the samples were not a mixture of different rains of the same day. Annual precipitation in Tehran province in the studied year 2008 and 2009 was about 307.41 and 297.2 mm respectively and a fifty year average is 232.8 mm. Heavy metals along with other studied parameter concentrations are presented in Table 1. Some samples were highly polluted in terms of almost all studied contaminants. This may be due to a long time gap between precipitations and heavy air pollution. For instance, on July 1, 2009, rain had 21.5 NTU turbidity, 167 μs EC, 0.21 mg/L Ni, 1.61 mg/L Al, 32.2. Chemical analyses and 1.19 mg/L PO4 . This was one of the most polluted precipitations of the studied time period. Snow samples pH and Electrical Conductivity (EC) of the samples were usually more polluted than rains. Mean pH value nd Methods was measured by a pH-EC meter (Cyberscan 510 of snow samples was lower than those of rain. In most model) following calibration. A HACH 2100N Turbidi- of the samples the pH value was less than 5.5 in autumn meter (USA) was used to measure samples turbidity. and winter time while it was in higher values in spring 23Concentrations of Fe2+ and anions (SO4 , PO4 , and time. This could be explained by the fact that the air pollution in is Tehran more extensive in cold seasons NO3 )atwere measured byin a DR/4000U HACH es were obtained Elahieh located north Tehran near SpectroGholhak valley which one ofis the the year with (i.e. autumn photometer. of Tehran (Fig.1). The samples were collected using a bulk samplerofequipped a plasticand winter) than that of warm seasons. Fossilfrom fuel other combustion in autumn and winter of Acidifying concentrations of metals s set on the roof a buildingsamples, at about 30 meters from ground level and separated structures to undesirable After a precipitation the samples wereduring cold seasons to warm in Tehran is increased (Al,avoid Cr, Ni, Pb, and Zn)effects. were determined by Graphite event, ansported to the laboratory keeping them Spectrophotometer at 4°C. Snow samples were collected the the sampling the homesinand traffic is heavier during this time. Furnace Atomic Absorption (Buck owed to meltScientific at room 210 temperature. and funnels) were acid frequently occurs in cold seasons in Tehran VGP). All sampling apparatus (bucketsInversion nsed with distilled water prior to sampling. preventing vertical mixing of the atmosphere. Overall, the rain and snow in Tehran within the time period of 3. Results and discussion analyses study was nearly acidic (mean rain pH; 5.9 and mean snow pH; 5.08) which may have negative impact on 3.1. Concentrations d Electrical Conductivity (EC) of the samples was measured by a pH-EC metersoils ( Cyberscan structures, and quality of groundwater and surface ollowing calibration. A HACH 2100N Turbidimeter (USA) was used to measure samples Acid precipitation in Tehran is pri 2+Twenty one precipitation from waters in the area. 23- events occurred centrations ofJuly Fe 2008 and to anions (SO 4 , PO4 , and NO3 ) were measured by a DR/4000U HACH October 2009 at Elahieh-Tehran. Samples marily caused by a mixture of strong acids, H2SO4 and meter. HNO3, resulting from fossil fuel combustion mainly by transport sector. 3.2. Precipitation volume weighted-average concentration of elements
The precipitation volume weighted – average values for pH, studied elements and three ions are sum2marized in Table 2. SO4 has the highest value. Nitrate is the second most concentrated pollutant. Aluminum, Cu, Ni, Zn and Pb have much higher values in comparison with other parts of the world (Galloway et al., 1982; Barrie et al., 1987; Horvath et al., 1994; Landis and Keeler, 1997; Takeda et al., 2000). Therefore, we consider Tehran as a highly polluted city in the world. A comparison of concentration of trace elements in the wet deposition samples reported in the literature is presented in Table 3. The higher concentrations of 1. Sampling site rain and snow collections in studied elements in Tehran may be mainly due to emising site for rainFigure and snow collections in for Tehran Tehran sions from residential and transportation sectors and samples, concentrations of metals (Al, Cr, Ni, Pb, and Zn) were determined by Graphite ic Absorption Spectrophotometer (Buck Scientific 210 VGP).
d discussion
40
M. Saeedi et al. / EnvironmentAsia 5(1) (2012) 39-47
Table 1. Sampling date of Tehran precipitations and their chemical and physical compositions Sample Jan 8, 2009
NO3 PO4 SO4 (mg/L) (mg/L) (mg/L) 1.1
0.046
12
pH
Tur. EC Cu Fe Zn Pb Ni Cr Al (NTU) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
4.65
4.78
56.7
0.19
0.141
0.123
0.877
0.077
0.740
Jan 12, 2009
0.7
0.045
5.5
4.99
1.12
20.6
0.12
0.085
0.023
0.409
0.101
0.008
0.966
Jan 15, 2009
2.2
0.095
30.7
5.03
2.6
107.2
0.21
0.197
0.298
0.649
0.048
0.007
1.095
Jan 21, 2009
0.8
0.018
2.3
5.45
1.25
22
0.137
0.022
0.153
0.950
0.100
0.003
0.891
Jan 29, 2009
1.4
0.037
13.6
5.29
2.2
42.5
0.371
0.078
0.079
0.425
0.132
0.079
1.517
Mean Snow
1.24
0.048
12.820
5.082
2.390
49.800
0.206
0.105
0.135
0.662
0.091
0.024
1.042
Max
2.2
0.095
30.700
5.450
4.780 107.200 0.371
0.197
0.298
0.950
0.132
0.079
1.517
Min
0.7
0.018
2.300
4.650
1.120
0.022
0.023
0.409
0.048
0.003
0.740
20.600
0.120
Dec 23, 2008
0.9
0.057
6.9
5.88
1.6
23.6
0.222
0.063
0.052
0.497
0.121
0.033
0.497
Dec 25, 2008
0.7
0.028
2.7
5.55
2.15
20.8
0.125
0.062
0.009
0.363
0.030
0.016
0.106
Jan 25, 2009
0.5
0.036
6.2
5.52
1.55
11.3
0.115
0.051
0.042
0.128
0.014
0.451
Feb 4, 2009
0.9
0.042
13.1
5.72
2.15
42.4
0.198
0.037
0.071
0.621
0.138
0.157
Feb 7, 2009
0.9
0.202
12.4
5.89
2.9
49.6
0.124
0.026
0.065
0.309
0.026
0.038
0.206
Feb 8, 2009
0.5
0.035
3.1
4.73
3
39.3
0.156
0.072
0.042
0.280
0.053
0.042
0.469
0.009
Feb 8, 2009
0.5
0.043
2.3
5.66
0.8
12.69
0.12
0.03
0.024
0.262
0.085
Feb 14, 2009
0.8
0.34
16.3
5.81
4.3
43.5
0.326
0.181
0.019
0.406
0.099
0.435
1.055
Feb 15, 2009
0.6
0.066
8
5.51
1.4
19.03
0.229
0.002
0.022
0.454
0.014
0.928
Mar 28, 2009
0.6
0.058
5.2
5.89
0.9
39.8
0.125
0.012
0.004
0.096
0.037
0.019
0.443
Mar 29, 2009
0.6
0.091
4.6
5.93
0.87
25.6
0.256
0.052
0.020
0.190
0.088
0.010
1.360
Apr 26, 2009
1.4
0.894
18.4
6.48
ND
101.4
0.269
0.055
0.090
0.900
0.166
0.016
1.301
Apr 26, 2009
0.9
0.28
8.7
6.13
39
75.7
0.321
0.147
0.059
0.358
0.011
0.011
1.476
Apr 26, 2009
0.8
0.253
10.6
5.98
11.7
63.6
0.316
0.177
0.016
0.288
0.084
0.038
0.910
May 17, 2009
4.5
0.266
74.3
7.75
26
521
0.459
0.296
0.275
0.829
0.147
0.063
4.404
July 1, 2009
3.1
1.191
25.5
6.51
21.5
167
0.29
0.134
0.094
0.781
0.213
0.045
1.611
Mean Rain
1.138
0.243
13.644
5.934
7.988
78.520
0.228
0.087
0.056
0.423
0.083
0.028
0.988
Max
4.500
1.191
74.300
7.750
39.000 521.000 0.459
0.296
0.275
0.900
0.213
0.063
4.404
Min
0.500
0.028
2.300
4.730
0.800
0.002
0.004
0.096
0.011
0.009
0.106
11.300
utilization of heavy liquid fuel oil in many industries and power plants within and around Tehran. It should be pointed out that lower precipitation in Tehran compared to most of the other studied sites would eventually results in higher metal concentrations. Lower rain volumes in Tehran and longer time periods between rain and snow events in addition to the high amounts of pollutants in the air would result in higher dissolution and absorption of contaminants in lower volumes of water making rain and snow highly polluted in terms of metals and acidic ions.
0.115
Table 2. Precipitation volume weighted-average concentrations of elements and ions in Tehran’s wet depositions
pH NO3- (mg/L) PO43- (mg/L) SO42- (mg/L) Cu (mg/L) Fe (mg/L) Zn (mg/L) Pb (mg/L) Ni (mg/L) Cr (mg/L) Al (mg/L)
3.3. Acid rain comparisons Acid rain occurs in Tehran, Iran (Table 1). A rainfall of pH 4.65 was measured on Jan 8, 2009. It is shown that all snow samples have lower pH than rainfalls and all of them are acidic with the pH value of 5.6. Forty three
41
Mean Volume Weighted 5.4741 0.8376 0.1026 8.0640 0.1849 0.0721 0.0519 0.4057 0.0659 0.0164 0.7612
(Min)
(Max)
4.65 0.5 0.018 2.3 0.115 0.002 0.0043 0.0957 0.0105 0.0031 0.1058
7.75 4.5 1.191 74.3 0.459 0.296 0.2977 0.95 0.2134 0.0789 4.4038
M. Saeedi et al. / EnvironmentAsia 5(1) (2012) 39-47
percent of all samples showed to have pH values lower than 5.6. The average pH value in of samples was about 5.7 and the mean volume weighted value was around 5.47. All of these results showed that precipitation in Tehran is acidic and it must be considered as a risk that has to be taken care in the view of atmospheric corrosion and its effects on structures, impacts on soil and waters, impacts on plants and crops. Fig. 2 shows the scatter plot of pH values of samples.
correlation among the ions and elements may be indicative of existence of same sources of their emission into Tehran’s atmosphere. 3.6. Relationship between rainfall intervals and concentrations
Our data (Table 1) clearly show that concentrations of metals and ions increase whenever the time betweenand twoions precipitations is longer. Therefore, Table 2. Precipitation volume weighted-average concentrationslap of elements in Tehran’s wet depositions 3.4. Relationships between precipitation volume and the correlation coefficients between rainfall intervals concentrations of chemical species and quantity of parameters were calculated. Results 3 showed that some parameters like NO3-, PO4 -, pH, and Mean Volume Weighted (Min) (Max) The relationships between the concentrations of Ni had significant correlation coefficients which are pH 5.4741 4.65 7.75 2per event 0.49, 0.66, 0.45, and 0.52 respectively. The obtained Al and SO4 and the volume of precipitation NO 0.8376 4.5 has higher metal, but lower ion, 3 (mg/L) are shown in Fig. 3. Increasing volumes of precipitation data reveal0.5 that snow 3PO (mg/L) 0.1026 0.018 1.191 4 would result in a decrease of pollutant concentrations concentrations when compared with rain. This may be 2SOto (mg/L) effect. 8.0640 74.3 which may be reasonable due explained 2.3 by the adsorption capacity of snow flakes 4 dilution All correlation coefficients between chemical metals and capability of rain (especially in Cu (mg/L) 0.1849 data to uptake 0.115 0.459 and the volume of precipitation were -0.4148, -0.3921, lower pH valued) to dissolve ions. The pH, turbidity Fe (mg/L) 0.0721 0.002 0.296 -0.42866, -0.49027, -0.32529, -0.34134, -0.28432, and electrical conductivity (EC) of rain are also higher Zn (mg/L) 0.0519 0.0043 0.2977 -0.43522, -0.33402, -0.47766, -0.2258 and -0.34672 for than of snow. Probably ions are more easily soluble in Pb (mg/L) 0.4057 0.0957 0.95 32NO3-, PO4 , SO4 , Cu, Fe, Zn, Pb, Ni, Al, pH, Turbidity rain than snow. Ni (mg/L) 0.0105 0.2134 and Electrical conductivity, respectively. It0.0659 means that Cr led (mg/L) 0.0031 0.0789 higher volume of precipitation to lower0.0164 concentra- 3.7. Cluster analysis Al (mg/L) 0.7612 0.1058 4.4038 tions in precipitations. Data in Table 1 are used to portrait cluster a den3.3. Relationship Acid rain comparisons 3.5. between anions and metals drogram of ions and heavy metals in all the samples those were collected (Fig. 6). All studied parameters Acid rain occurs Tehran, Iran (Tableanions 1). A rainfall of pH 4.65 was measured on Janas8, coefficients 2009. It is Linear regression wasincomputed amongst have positive similarity coefficients - that2-all snow 32shown samples have lower pH than rainfalls and all of them are acidic with the pH value (NO3 , SO4 and PO4 ) and metals in samples. Almost between NO3 and SO4 , Al and Cu, Al and Fe,of Fe5.6. and Forty threehad percent all samples showed to have values 5.6.0.939, The average pH value in and of all of them good of R-squared values indicating rea-pH Cu, andlower Zn andthan Pb are 0.725, 0.675, 0.675, 2samples was about 5.7 and the mean volume weighted value was around 5.47. All of these results showed sonable relationships between quantities of measured 0.662, respectively. Nitrate, SO4 , Al, Fe and Cu form that precipitation in Tehran is acidic and it must be considered a risk thatsimilarities. has to be taken care in and the Pb-Zn view parameters. For instance, relationships between metals a clusteraswith higher Nickel-PO 4 of atmospheric corrosion and its effects on structures, impacts on soil and waters, impacts on plants than against the ions are shown in Fig. 4 and Fig. 5. A direct also form other clusters with similarities higher and crops. Fig. 2 shows the scatter plot of pH values of samples.
Figure Figure 2. 2. Scatter Scatter plot plot of of pH pH values values in in Tehran Tehran precipitation precipitation (2008-2009) (2008-2009)
3.4. Relationships between precipitation volume and concentrations of chemical species The relationships between the concentrations42of Al and SO42- and the volume of precipitation per event are shown in Fig. 3. Increasing volumes of precipitation would result in a decrease of pollutant
M. Saeedi et al. / EnvironmentAsia 5(1) (2012) 39-47
Table 3. Comparison of concentration of trace elements in the wet deposition reported in literature (µg/L) Table 3. Comparison of concentration of trace elements in the wet deposition reported in literature (µg/L)
Sites (rural or urban, bulk or wet)
Al
Sites (rural or urban, bulk or wet)
Fe Al
Cu Fe
Cu
Rural area ( Galloway et al., 1982) Rural(Barrie area ( Galloway et al., 1982) Rural area et al., 1987)
Hungary 3 sites Rural Rural area (Barrie et al., 1987) (Horvath et al., 1994) 3 sites Rural (Horvath et al., DexterHungary Michigan, USA semi-rural 57 (Landis1994) and Keeler, 1997) Dexter Michigan, USA semi-rural Hiroshima Japan 0.06 (Landis Keeler, 1997) (Takeda et al.,and 2000) Ajlune,Hiroshima Jordan Rural Japan (Takeda et al., 2000)382 (Al-Momani, 2003) Ajlune, Rural (Al-Momani, 2003) Paradise, NewJordan Zealand Rural (Halstead et al., 2000) Paradise, New Zealand Rural (Halstead et al., 2000) New Castle, USA Urban 24 (Pike and Moran, 2001)Urban (Pike and New Castle, USA Moran, 2001) Montreal Island, Canada Urban 18 (Poissant et al.,Island, 1994)Canada Urban (Poissant Montreal et al.,Urban 1994) Singapore 18.4 Singapore Urban (Hu and (Hu and Balasubramanian, 2003) Balasubramanian, North Atlantic Ocean 2003) 47 North Atlantic (Church et al., 1990)Ocean (Church et al., 1990) Tsukuba, Japan Suburban Japan Suburban (Hou et al., 34 (Hou etTsukuba, al., 2005) 2005) Tehran, Iran (This study) 761.17 Tehran, Iran (This study)
Pb Pb
Ni Ni
12
2.4
36
0.68 - 5.4 24
3.0 - 12 14.0
0.792.4- 17
36 - 50 4.7
3.0-- 17 14.0 3.6 0.68 - 11- 24 13
0.79- -4.6 17 1.7
4.7 34- 50- 51
13 - 17 1.4
1.7 - 4.6
0.23
57
0.620.86
1.4 1.24
0.23 0.29
0.06
3.10.62
1.24
0.29
92
2.1
92
25
47
7.5
34
7.5
72.1 761.17
4.0
28
5.6
7.2
7.2 1.7
0.38
1.7
18
2.5
184.94
18
405.71 405.71
65.88 65.88
51.89 51.89
232.8 232.8
(b)
-2
SO4 (mg/L)
(a)
Al (mg/L)
1433
28
0.38 2.5
1433
26 26
184.94 72.1
6.5
1.3
5.6 24 25
4.77
0.038
4.0
24 18.4
7.7 4.77
0.013
91
435 - 659
0.038
1.3
91 18
435 - 659
7.7
6.5
23
yr)
34 - 51
3.1
0.013
2.1
23 24
Zn
5.4
3.6 - 11 0.86
382
Zn
Annual precipitation Annual volume precipitation (mm/ yr) volume(mm/
2Figure 4 2Figure3.3.Relationship Relationshipbetween betweenprecipitation precipitationvolumes volumesand andconcentrations concentrationsofof(a)(a)Al, Al,(b)(b)SO SO 4
3.5. Relationship between anions and metals Linear regression was computed amongst anions (NO3-, SO42- and PO43-) and metals in samples. Almost all of them had good R-squared values indicating reasonable relationships between quantities of measured parameters. For instance, relationships between metals against the ions are shown in Fig. 4 and 43
M. Saeedi et al. / EnvironmentAsia 5(1) (2012) 39-47
Fig. 5. A direct correlation among the ions and elements may be indicative of existence of same sources of their emission into Tehran’s atmosphere. (b)
Fe (mg/L)
Zn (mg/L)
(a)
(d)
Cu (mg/L)
Nl (mg/L)
(c)
(f)
Pb (mg/L)
Al (mg/L)
(e)
Figure 4. Relationship between NO 3 and metals concentrations Figure 4. Relationship between NO3 and metals concentrations
44
M. Saeedi et al. / EnvironmentAsia 5(1) (2012) 39-47
(b)
Fe (mg/L)
Zn (mg/L)
(a)
(d)
Cu (mg/L)
Nl (mg/L)
(c)
(f)
Pb (mg/L)
Al (mg/L)
(e)
22Figure 5. Relationship between and metals concentrations Figure 5. Relationship between SO4 SO and4 metals concentrations
45
between NO3 and SO4 , Al and Cu, Al and Fe, Fe and Cu, and Zn and Pb are 0.939, 0.725, 0.675, 0.675, and 0.662, respectively. Nitrate, SO42-, Al, Fe and Cu form a cluster with higher similarities. Nickel-PO4 and Pb Zn also form other clusters with similarities higher than 0.6 which connect to ions cluster in 0.4-0.5 similarity coefficients. On the of similarity5(1) coefficients M. Saeedi et al.basis / EnvironmentAsia (2012) 39-47all studied parameters may originate from same sources which seem to be the combustion of fossil fuels (particularly liquid fuels) in Tehran.
Figure 6. Dendrogram of studied parameters in Tehran precipitation samples Figure 6. Dendrogram of studied parameters in Tehran precipitation samples
0.6 which connect to ions cluster in 0.4-0.5 similarity Al-Momani IF. Trace elements in atmospheric precipitation at 4. Conclusions Northern Jordan measured by ICP-MS: acidity and coefficients. On the basis of similarity coefficients all possible sources. Atmospheric Environment 2003; 37: studied parameters mayTwenty originate same sources onefrom precipitation samples were collected and analyzed for different constituents within a half 4507–15. which seem to year be the combustion fuels (par- revealed period of timeof infossil Tehran. Results that rain and snow samples are more polluted than those of Barrie LA, Lindberg SE, Chan WH, Ross HB, Arimoto R, ticularly liquid other fuels)studies in Tehran. around the world. Snow samples are mostly than rain samples in in terms of heavy Church TM. more On thepolluted concentration of trace metals metal contents. Long intervals between precipitations result in increased pollution. The pH of precipitation. Atmospheric Environment 1987; 21:snow samples 4. Conclusionshad more acidity than that of rain. Larger precipitations 1133–35. resulted in dilution of contaminant concentrations in samples and lower concentrations. We show that precipitations considerably more Church Tehran’s TM, Veron A, Pattersonare CC, Settle D, Erel Y, polluted than that of other metropolitan of the world. BasedHR, onFlegal the results of this studyinand effects of Twenty one precipitation samples werecities collected Maring AR. Trace elements the negative North polluted/acidic rains, some measures efficient energy consumption andofair pollution control of and analyzed for different constituents within a half like more Atlantic troposphere: shipboard results precipitatransportation vehiclesrevealed should be tion and aerosols. Global Biogeochemical Cycles 1990; year period of time in Tehran. Results thattaken rain in Tehran. 4: 431–43. and snow samples are more polluted than those of other Galloway JN, Thornton JD, Norton SA, Volchok HL, McLean Acknowledgement studies around the world. Snow samples are mostly RA. Trace metals in atmospheric deposition: a review more polluted than rain samples in terms of heavy metal This study was partially supported by of research Atmospheric and Enviro-hydroinformatics center deputy and assessment. Environment 1982; 16: of excellence contents. Long intervals between precipitations result in Iran University of Science and Technology. 1677–700. increased pollution. The pH of snow samples had more Halstead JRM, Cunninghame GR, Hunter AK. Wet deposition acidity than that of rain. Larger precipitations resulted of trace metals to a remote site in Fiordland, New in dilution of contaminant concentrations in samples Zealand. Atmospheric Environment 2000; 34: and lower concentrations. We show that Tehran’s pre- 665–76. cipitations are considerably more polluted than that of Horvath Z, Lasztity A, Varga E, Meszaros E, Molnar A. Determination of trace metals and speciation of other metropolitan cities of the world. Based on the chromium ions in atmospheric precipitation by ICPAES results of this study and negative effects of polluted/ and GFAAS. Talanta 1994; 41: 1165–68. acidic rains, some measures like more efficient energy Hou H, Takamatsu T, Koshikawab MK, Hosomi M. Trace consumption and air pollution control of transportation metals in bulk precipitation and throughfall in a vehicles should be taken in Tehran. suburban area of Japan. Atmospheric Environment 2005; 39: 3583–95. Hu GP, Balasubramanian R. Wet deposition of trace metals in Singapore. Water Air & Soil Pollution 2003; 144: 285–300. Kobori H, Kumazawa M, Kai Y, Ham Y. Monitoring Study on Acid Rain in Kanagawa Prefecture, Central Japan. Journal of Environmental and Information Studies 2005; 6: 97-101. Landis M, Keeler GJ. Critical evaluation of a modified automatic wet-only precipitation collector for mercury and trace element determinations. Environmental Science & Technology 1997; 31: 2610–15.
Acknowledgement This study was partially supported by deputy of research and Enviro-hydroinformatics center of excellence, Iran University of Science and Technology. References Alloway BJ. The origins of heavy metals in soils. In: Heavy metals in soils (Ed: Alloway BJ) Blackie and Son Ltd. 1990; 29-39.
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Nriagu JO. Changing Metal Cycles and Human Health. (Ed: Nriagur JO). Springer-Verlag, Heidelberg. 1984; 445-28. Pike SM, Moran SB. Trace elements in aerosol and precipi tation at New Castle, NH, USA. Atmospheric Environ ment 2001; 35: 3361–66. Poissant L, Schmit JP, Beron P. Trace inorganic elements in rainfall in the Montreal Island. Atmospheric Environ ment 1994; 28: 339–46. Singh A, Agrawal M. Acid rain and its ecological conse quences. Journal of Environmental Biology 2008; 29: 15-24. Sillapapiromsuk S, Chantara S. Chemical composition and seasonal variation of acid deposition in Chiang Mai, Thailand. Environmental Engineering Research 2010; 15: 93-98. Takeda K, Marumoto K, Minamikawa T, Sakugawa H, Fujiwara K. Three-year determination of trace metals and the lead isotope ratio in rain and snow depositions collected in Hiroshima, Japan. Atmospheric Environ ment 2000; 34: 4525–35. Smith SJ, Sharpley AN, Menzel RG. The pH of rainfall in the southern plains. Proceedings of the Oklahoma Academy of Science 1984; 64: 40-42. Received 20 August 2011 Accepted 18 September 2011 Correspondence to Professor Dr. Mohsen Saeedi Environmental Research Laboratory, School of Civil Engineering, Iran University of Science & Technology, Tehran, 16846, Iran Email:
[email protected]
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