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Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea
MPB-07583; No of Pages 6 Marine Pollution Bulletin xxx (2016) xxx–xxx
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Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea Homira Agah, Abolfazl saleh, Kazem Darvish Bastami ⁎, Neda Sheijooni Fumani Iranian National Institute for Oceanography and Atmospheric Science (INIOAS), No. 3, Etemadzadeh St., Fatemi Ave., 1411813389 Tehran, Islamic Republic of Iran
a r t i c l e
i n f o
Article history: Received 29 December 2015 Received in revised form 15 March 2016 Accepted 19 March 2016 Available online xxxx Keywords: Metals Sediment Chabahar Bay Oman Sea
a b s t r a c t In this study, concentrations of Aluminum (Al), Iron (Fe), Chromium (Cr), Copper (Cu), Nickel (Ni), Vanadium (V), Zinc (Zn), Arsenic (As), Cobalt (Co) and lead (Pb) in the surface sediments from Chabahar Bay were studied to assess the degree of heavy metal pollution as a consequence of natural and anthropogenic sources. Metal contents in the sediments were observed in the order of: Al N Fe N Cr N V N Ni N Zn N CuN N As N Pb N Co. According to enrichment factor (EF), Arsenic was higher than 1.5 at some sites, indicating anthropogenic inputs. Contents of Ni, As and Cr in the some sampling sites were higher than sediment quality guideline implying adverse impacts of these metals. Based on potential ecological risk (PER), the Chabahar Bay had low ecological risk. © 2016 Elsevier Ltd. All rights reserved.
Metals, such as arsenic, cadmium, lead, chromium and nickel, are important environmental pollutants, particularly in areas with high anthropogenic pressure (Islam et al., 2015). Some properties of these contaminants such as being toxic or carcinogenic to humans (Fu and Wang, 2001), persistence, bioaccumulation and non-biodegradable cause a significant concern, especially in coastal and marine environments worldwide (Idris et al., 2007; Ruilian et al., 2008; Cao et al., 2015). Their negative effect on marine ecosystems by reducing species diversity and abundance (Bastami et al., 2014b) and through accumulation of metals in living organisms and food chains is well known (Hosono et al., 2011). In addition to these metals, copper, iron, and zinc are also important heavy micronutrients (Paramasivama et al., 2015). Natural sources, industrial and other anthropogenic activities are the dominant sources of heavy metal pollution (Idris et al., 2007; Fu and Wang, 2001). Capacity of sediments to accumulate compounds makes them one of the most important tools to assess the contamination level and evaluation of continental aquatic ecosystems. More than 90% of heavy metals load in aquatic systems have been found to be associated with suspended particulate matter and sediments (Zheng et al., 2008; Amin et al., 2009). Hence sediment analyses play a crucial role in assessing the degree of heavy metal pollution resulting in health risk associated with impaired food chain. Oman Sea is the input path of fresh water flows to the Persian Gulf via Arabian Sea and Indian Ocean; it is also a vital shipping route for the oil-producing countries in the Persian Gulf. Chabahar Bay, which is situated on the Makran Coastline in Sistan and Baluchestan Province, ⁎ Corresponding author. E-mail addresses: [email protected], [email protected] (K.D. Bastami).
Southeast of Iran, is a free port and industrial zone on the coast of the Gulf of Oman. The special importance of Chabahar Bay is due to its Ω shape and limited water circulation. The Chabahar Bay has humid climate, hot summers and moderate winters. Fishing and marine commerce are the main activities in the study areas. Due to the increasing trade and industrial activities in the recent decade in this area, it is expected that these activities influence the accumulation of anthropogenic pollution on coastal and marine sediments. Very little information is available on extend of metals pollution in the North-West of Oman Sea and also in recent years petrochemical industries have started their activities in the Chabahar Bay. Hence, understanding the pollution levels of the region is an important step towards its protection and sustainable development. The main objectives of the present study were 1) To investigate toxic heavy metals distribution in surface sediments from the Chabahr Bay, Oman Sea and 2) Discover relationships between the elemental levels and sediment characteristics, 3) Detect pollution source(s) and 4) Compare pollution level with other marine ecosystems. Sediment samples from nine sites (Fig. 1 and Table 1) were collected using a Van Veen Grab sampler from Chabahar Bay in April 2012. The selected sampling sites represent the most important harbors, desalination plant and industrial regions in Sistan and Baluchestan Province and also they represent coastal areas that are anticipated to have a relative higher pollution due to higher population. The collected samples were placed in pre-cleaned polyethylene plastic bottles, labeled and were carried to the laboratory in ice-boxes for further treatment. The sediment samples were lyophilized, sieved and fractions smaller than 63 μm were transferred in pre-cleaned dark glass labeled bottles and kept frozen (at − 20 °C) prior to chemical
http://dx.doi.org/10.1016/j.marpolbul.2016.03.042 0025-326X/© 2016 Elsevier Ltd. All rights reserved.
Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
2
H. Agah et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx
Fig. 1. The location of the sampling site in the Chabahr Bay.
analyses (Wolf-Welling et al., 2001). Sediment samples were subjected to wet sieving and Lazer Particle Sizing (HORIBA-LA950, France and Japan) determination. Total organic matter was measured by heating sediment samples in an oven at 530 ± 20 °C for 8 h (Dean, 1974). Total organic matter was calculated by the following equation: Total organic matter ðTOM; %Þ ¼ ½ðB−CÞ=B 100
ð1Þ
where B and C are the weights of dried sediments before and after combustion in the oven, respectively. For digestion of sediment samples, 0.5 g of each sediment sample was added with a mixture of HCl–HNO3–H2O (with the ratio of 1:1:1 v/v) and heated at 95 °C during 1 h. Metal (Al, Co, Ni, Cu, Zn, As, Pb, Fe, Cr and V) analyses were performed using Inductively Coupled Plasma Mass Spectrometry inductively (ICP-MS) after acid digestion at ACME Lab., Canada which is under 17,025 standards. Quality assurance and quality controls were assessed using standard samples (Oreas 45 Pa, DS7 and DS8). The analytical results of the quality control samples show good agreement with the certified values (recoveries ranging 93.25–105.22%). The limits of detection were set as three times of the standard deviation on the procedural blanks (Table 2). To predict detrimental biological effects and conservation of the organisms living inside or near the polluted sediments, sediment quality guidelines (SQGs) were used. In order to classify the sediment, NOAA provides two values for each substance: (1) sediments with rarely adverse biological impacts (beffect range low), (2) sediments with occasionally or frequently adverse biological impacts (N effect range low and b effect range median) (Long et al., 1995).
Enrichment factor (EF) technique for determining sedimentary metal sources (Selvaraj et al., 2004; Vald'es et al., 2005; Bastami et al., 2014a, 2014b) was calculated as follow (lee et al., 1998; Woitke et al., 2003): Enrichment factor ðEFÞ ¼ ðCs=CFe Þsample =ðCs=CFe ÞBackground:
ð2Þ
While (Cs/CFe)sample are the average element level and Fe concentrations in our study, respectively, (Cs/CFe)Background are the average element level and Fe concentrations in background sample, respectively. Iron or aluminum is used as a normalization element to reduce the variations produced by heterogeneous sediments; the reference element must have minimum variability of occurrence or large concentrations in the studied environment. In the present study, Iron (CV: 3.73%) had a homogeneous concentration in the selected stations. Also, we used background concentrations of metals in sediment from Iranian waters of the Oman Sea which are 7.4, 63.7, 92.4, 42.17, 99, 78, 15.2, 372,0.21 ppm, 2.80 and 6.05% for As, Ni, Pb, Cu, Zn, V, Co, Cr, Cd, Fe and Al, respectively (Hamzeh et al., 2013). Potential ecological risk index (PER) was also introduced to assess the contamination degree of heavy metals in the present sediments. The equations for calculating the PER were proposed by Hakanson (1980) as the following: E ¼ TC
ð3Þ
C ¼ Ca =Cb
ð4Þ
PER ¼ ∑E ¼ ∑TC
ð5Þ
Table 1 Sampling geographical locations in the Chabahar Bay. No
Stations
Depth (m)
Geographical locations
1 2 3 4 5 6 7 8 9
Tiss Tiss Konarak Konarak Desalination plant Entrance of the Chabahar Bay Posm Posm Ramin
3.8 9.0 5.0 10.5 5.8 13.6 12.10 6.0 4.5
25°21′46″ N 60°35′40″ E 25°22′50″ N 60°33′59″ E 25°19′58″ N 60°15′44″ E 25°22′23″ N 60°28′30″ E 25°26′3″ N 60°30′14″ E 25°17′44″ N 60°32′12″ E 25°19′58″ N 60°15′44″ E 25°22′54″ N 60°15′21″ E 25°15′42″ N 60°46′18″ E
Table 2 Detection limits of the elements (mg kg−1). Element
Detection limit
Element
Detection limit
As *Fe Co Cu Cr Ni
5 0.01 0.5 5 10 5
V Pb Zn *Al
5 5 5 0.1
Elements marked as “*” are reported according to their %.
Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
H. Agah et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx Table 3 Grain size distributions and organic matter content levels of the sediment samples at Chabahar Bay. Station
OM%
1 2 3 4 5 6 7 8 9 Average ± SD
Grain size
2.25 4.5 5 8 3 3.75 3.25 3 2.75 4.06 ± 1.83
Sand%
Silt%
Clay%
91 88 26 18 70 40 59 47 88 60 ± 29.15
7 7 62.2 46.6 25 46.6 37.5 45 4 29.48 ± 22.04
2 5 11.8 35.4 5 13.4 3.5 8 8 10.51 ± 10.81
where C is the single element pollution factor, Ca is the content of the element in samples and Cb is the reference value of the element. The sum of C for all the metals examined represents the integrated pollution degree (C) of the environment. E is the potential ecological risk factor of an individual element. T is the biological toxic factor of an individual element, which is determined for Cu = Pb = 5, Zn = 1, As = 10, Cr = 2 and Ni = 6 (Hakanson, 1980). PER is a comprehensive potential ecological index, which equals to the sum of E. It represents the sensitivity of biological community to toxic substances and illustrates the potential ecological risk caused by the overall contamination. Shapiro–Wilk test was executed to analyze the normality of data distribution. Spearman correlations were calculated between element concentrations. Statistical analyses of the data were carried out by using SPSS V19. Grain size and organic matter contents of the sediment samples at Chabahar Bay are presented at Table 3. Organic matter content in the marine sediment originates from marine and terrestrial sources. Chemical compounds of marine sediment are predominantly proteins (amino acids), carbohydrates (sugars) and lipids, while terrestrial organic matter consists of living biomass, plant litter and soil organic matter. TOM content in sediment of the studied area was 2.25–8% (averaged
3
4.06 ± 1.83%) which exhibited the highest and the lowest amounts at stations 4 and 1, respectively. As proposed by Marin et al. (2008), ecological quality status is classified into three levels according to organic matter content: high-good (less than 5%), moderate (between 5% and 10%) and poor-bad (greater than 10%). As illustrated in Table 3, TOM content of all station was less than the presented above range (2.25– 8%) in sediment of the Chabahar Bay. The sand, silt and clay contents averaged 60 ± 29.15%, 29.48 ± 22.04% and 10.51 ± 10.81% respectively. Depth sampling sites ranges from 3.8 to 13.6 m with an average value of 7.81 ± 3.58 m (Table 3). Results of metal contents at different sampling sites are showed in Tables 4 and 5. Minimum and maximum (Mean ± standard deviations) of element levels in all the sampling sites were as: Al: 0.75–5.54% (3.24 ± 1.58), Fe: 1.15–3.22% (1.80 ± 0.65), Cr: 86.70– 400 ppm (185.01 ± 93.40), V: 24.50–94 ppm (47.21 ± 20.47), Ni: 13.50–81 ppm (40.51 ± 21.73), Zn: 24–69 ppm (37.86 ± 13.27), Cu: b5–26 ppm (14.16 ± 5.76), As: 8.67–21 ppm (13.22 ± 4.82), Pb: 10.30–15.50 ppm (12.87 ± 1.95), Co: 4.25–14.80 ppm (8.91 ± 3.88). The lowest element variation was related to iron (CV: 3.73%), indicating a homogeneous concentration of this element in the selected stations. According to the Table 4, metal contents in the sediments were observed in the order of: Al N Fe N Cr N V N Ni N Zn N Cu N As N Pb N Co. As specified in Table 4, coastal parts of Konarak (site 3) often had higher levels of metals, which could be originated from local wharf, dock, boat repair stations and desalination plants activities. Sediment quality guidelines (SQGs) are an important tool for the assessment of contamination in marine and estuarine sediments (Long et al., 1995). Concentrations of Cu, Pb and Zn in all sampling sites were lower than the corresponding values of effect range low (ERL), effect range median (ERM), probable effect level (PEL) and Interim sediment quality guideline (ISQG). Arsenic contents at all sites, Nickel in sites 3,5,6,7 and 9, were higher than ERL, suggesting that these metals in sediments from the Chabahar Bay would be occasionally expected to cause adverse biological effects on biota. Also, Chromium levels at sites 1 were higher than ERM. These results implicate that negative eco-risk effects frequently occur in this station (Tables 4 and 5).
Table 4 Metal content (average ± SD) of the sediments sampled in the studied area. Stations
Al (%)
Fe (%)
Cr (ppm)
Cu (ppm)
Ni (ppm)
V (ppm)
Zn (ppm)
As (ppm)
Co (ppm)
Pb (ppm)
1 2 3 4 5 6 7 8 9
1.61 ± 0.23 1.69 ± 0.09 5.54 ± 1.13 2.91 ± 0.02 4.16 ± 0.03 4.15 ± 0.06 4.28 ± 0.06 0.75 ± 0.23 4.11 ± 0.3
1.24 ± 0.18 1.3 ± 0.04 3.22 ± 0.75 1.35 ± 0.02 1.95 ± 0.02 1.92 ± 0.04 1.97 ± 0.01 1.15 ± 0.25 2.14 ± 0.08
400 ± 127.28 245 ± 7.07 150 ± 47.26 126.67 ± 11.55 216.67 ± 5.77 86.67 ± 5.77 140 ± 0 160 ± 98.99 140 ± 28.28
b5 6±0 13 ± 5.29 10.33 ± 1.53 12 ± 1 15 ± 2 16 ± 0 15 ± 4.24 26 ± 0
19 ± 1.41 19 ± 0 81 ± 9.9 30.67 ± 0.58 50.67 ± 1.15 49.67 ± 1.53 50.5 ± 0.71 13.5 ± 4.95 50.5 ± 4.95
39.5 ± 6.36 31.5 ± 0.71 94 ± 9.9 31 ± 0 51.67 ± 0.58 47.67 ± 1.15 51.5 ± 0.71 24.5 ± 9.19 53.5 ± 4.95
27.67 ± 1.15 28 ± 0 69 ± 4.24 24 ± 0 37.67 ± 1.15 39.33 ± 2.08 38.5 ± 3.54 33.5 ± 0.71 43 ± 5.66
17.33 ± 2.52 20 ± 0 10 ± 0 11.67 ± 0.58 8.67 ± 0.58 10.33 ± 0.58 9.5 ± 0.71 21 ± 0 10.5 ± 0.71
5.05 ± 0.64 4.25 ± 0.21 14.8 ± 2.98 6.8 ± 0 10.57 ± 0.21 10.63 ± 0.25 12.1 ± 0.28 4.3 ± 0.57 11.7 ± 0.85
15.5 ± 0.71 11.5 ± 0.71 15 ± 1.73 10.33 ± 0.58 12.33 ± 0.58 11.67 ± 0.58 11.5 ± 0.71 12.5 ± 2.12 15.5 ± 0.71
Table 5 Sediment quality guidelines from NOAA (Long et al., 1995) and Environment Canada (ISQG, 1995). Metal
As (ppm)
Cr (ppm)
Cu (ppm)
Ni (ppm)
Pb (ppm)
Zn (ppm)
ERLa ERMb ISQGc PELd This study
8.2 70 7.24 41.6 13.22 ± 4.82 (8.67–21)
81 370 52.3 160 185.01 ± 93.40 (86.70–400)
34 270 18.7 108 14.16 ± 5.76 (b5–26)
21 52 – – 40.51 ± 21.73 (13.50–81)
46.7 218 30.2 112 12.87 ± 1.95 (10.30–15.50)
150 410 124 271 37.86 ± 13.27 (24–69)
a b c d
ERL = effect range low (NOAA). ERM = effect range medium (NOAA). ISQG = Interim sediment quality guideline (Environment Canada). PEL = probable effect level (Environment Canada).
Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
4
H. Agah et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx
Table 6 Metals concentrations in various sediments of the marine environments. Sampling area
Cr (ppm)
V (ppm)
Ni (ppm)
Zn (ppm)
Cu (ppm)
As (ppm)
Pb (ppm)
Co (ppm)
References
Chabahar Bay
86.70–400 (185.01 ± 93.40) 372 ± 473 (68–2370) 85.2 ± 15.3 (59.6–128) –
24.50–94 (47.21 ± 20.47) 78 ± 24 (45–130) 116 ± 20.5 (76.5–145) 26.46 ± 10.25 (13–41) –
13.50–81 (40.51 ± 21.73) 63.7 ± 26.5 (31.1–116) 51.6 ± 11.8 (29.4–67.8) 29.20 ± 14.68 (10.3–50.4) 26.90 ± 2.72
24–69 (37.86 ± 13.27) 99 ± 104 (36–547) 85.3 ± 17.9 (55.9–146) 42.1 ± 22.15 (13–75) –
b5–26 (14.16 ± 5.76) 42.17 ± 51.34 (12.50–287) 34.7 ± 11.9 (13.2–50.9) 18 ± 8.83 (3.8–31.12) 38.28 ± 0.37
8.67–21 (13.22 ± 4.82) 7.4 ± 2.4 (4–14) 12.5 ± 3.04 (6.97–20.1) 7.77 ± 2.12 (4.4–11.8)⁎
10.30–15.50 (12.87 ± 1.95) 92.4 ± 329.5 (10.40–1780) 18.0 ± 4.17 (11.3–24.6) 11.5 ± 4.88 (4.1–18.3) 50.37 ± 2.41
4.25–14.80 (8.91 ± 3.88)
This study
15.2 ± 4.1 (9.9–22.8) 15.9 ± 4 (6.9–24.2) 10.56 ± 14.68 (3.5–20.8) –
Hamzeh et al. (2013) De Mora et al. (2004) Bastami et al. (2012, 2014a) Sistani et al. (2015) Sistani et al. (2015) Agah et al. (2011) ROPME (1997) Agah et al. (2012) Nguyen et al. (2005) Zwolsman et al. (1996)
Oman Sea Caspian Sea (Iran) Gorgan Bay (Iran) Chabahar Bay, summer Chabahar Bay, winter Caspian Sea North Oman Sea Persian Gulf
–
14.68 ± 1.93 –
–
95
21
Lake Balaton Hungary Scheldt Estuarine, Netherlands Izmir bay Turkey
–
16.45 ± 1.77 60 (46–75)
13.56 ± 1.24
42 (33–51) 329 111 (20–192) 4.4–55
37 (4–79) 13–250
19 (13–27) 8.7 20 (5–33) 0.7–36
3–220
9–1500
1–2600
4–455
13–146
22–311
4–79
7–103
Numerous studies have been conducted on heavy metal contamination throughout world (Zwolsman et al., 1996; ROPME, 1997; Kucuksezgin, 2001; De Mora et al., 2004; Nguyen et al., 2005; Agah et al., 2011, 2012; Bastami et al., 2012; Hamzeh et al., 2013; Bastami et al., 2014a; Sistani et al., 2015). Data in Table 6 shows concentration of heavy metals in sediment of other locations. Contents of some heavy metals in this study were higher than those found in some aquatic environments but were lower than those in other locations. Furthermore, comparison of the present results with previous studies in this area suggested that levels of all heavy metal exception As are lower than those reported by Hamzeh et al. (2013) (Table 6). Also, Sistani et al. (2015) measured contents of nickel, copper and lead in intertidal sediment of Chabahar Bay during summer and winter. Copper and lead concentrations in intertidal sediments were higher than our results in Chabahar Bay, while nickel level in their study was lower than our results (Table 6). Although a quantitative comparison across reported metal data is difficult because of variances in the number sample collected in each study, the sediment fraction analyzed, and the analytical methods used.
11 (7.6–14.6)
13 (10–17)
15 (11–17)
7 (4–21)
7 (3–10) 2–160
14 (3–22) 1.7–17
Kucuksezgin (2001)
In order to know the impact of sediment characteristics on the metals concentrations in the Chabahar Bay sediment, correlation analysis was carried out between them and the correlation coefficient matrix is shown in Table 7. The major factors affecting spatial variation of heavy metals in the sediment are TOM and the grain size. The fine grains, representing the higher rate of surface to volume and ionic absorption power, are more capable in the absorption of contaminated organic and inorganic materials (McCave, 1984; Horowitz and Elrick, 1987). Generally, fine-grained sediments carrying lots of organic matter are more contaminated than coarse-grained sediments. According to the results of Pearson's correlation test (Table 7), the elements of Cr, Fe, V, Zn, As and Pb showed negative correlation with TOM (P N 0.05). There was positive correlation between Cr, V, Zn, Fe, Ni, As, Pb with sand. Clay was positively correlated with Al and Co (P N 0.05). Because of less correlation with metals, contents of TOM, sand, clay and silt are not significant for the metal content of Chabahar Bay. This study, suggest that the distribution and concentration of metals in sediments of Chabahar Bay may depend on offshore industry, shipping, maritime activities, water and sediment movement.
Table 7 Correlation between metals and general characteristics of sediments in the in the studied areas.
Sand Silt Clay Depth Al Cr Fe Ni V Zn As Co Pb Cu
TOM
Sand
Silt
Clay
Depth
Al
Cr
Fe
Ni
V
Zn
As
Co
Pb
−0.697* 0.473 0.905** 0.809** 0.152 −0.381 −0.119 0.019 −0.183 −0.237 −0.271 0.149 −0.599 0.000
−0.947** −0.738* −0.632 −0.076 0.400 0.086 0.016 0.195 0.119 0.068 −0.115 0.354 −0.241
0.481 0.543 0.028 −0.465 −0.090 −0.039 −0.223 −0.086 0.001 0.066 −0.306 0.289
0.580 0.148 −0.116 −0.045 0.040 −0.065 −0.144 −0.188 0.176 −0.322 0.070
0.150 −0.553 −0.127 0.019 −0.222 −0.246 −0.232 0.064 −0.796* −0.288
−0.496 0.900** 0.974** 0.850** 0.742* −0.922** 0.974** 0.152 0.319
−0.386 −0.466 −0.203 −0.338 0.479 −0.504 0.416 −0.497
0.972** 0.979** 0.954** −0.685* 0.927** 0.400 0.292
0.935** 0.873** −0.830** 0.977** 0.266 0.306
0.942** −0.627 0.876** 0.495 0.218
−0.470 0.816** 0.488 0.288
−0.873** −0.004 −0.358
0.262 0.465
0.649
TOM = Total organic matter. ⁎ Correlation is significant at the 0.05 level. ⁎⁎ Correlation is significant at the 0.01 level.
Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
H. Agah et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx Table 8 Enrichment factor of different metals of sampling site in the surface sediments from Chabahar Bay. Sampling sites
As
Co
Cr
Cu
Ni
Pb
V
Zn
1 2 3 4 5 6 7 8 9 Average ±
5.29 5.82 1.18 3.27 1.68 2.04 1.82 6.91 1.86 3.32 ±
0.75 0.60 0.85 0.93 1.00 1.02 1.13 0.69 1.01 0.89 ±
2.43 1.42 0.35 0.71 0.84 0.34 0.53 1.05 0.49 0.91 ±
– 0.31 0.27 0.51 0.41 0.52 0.54 0.87 0.81 0.53 ±
0.68 0.65 1.12 1.01 1.15 1.15 1.14 0.52 1.05 0.94 ±
0.37 0.26 0.14 0.23 0.19 0.18 0.17 0.32 0.21 0.24 ±
1.14 0.87 1.05 0.82 0.95 0.89 0.94 0.76 0.90 0.93 ±
0.63 0.61 0.61 0.50 0.55 0.58 0.55 0.82 0.57 0.60 ±
2.13
0.17
0.66
0.21
0.25
0.07
0.11
0.09
SD
Correlation matrix demonstrated that there were no significant correlations between Cr and As with other elements (P N 0.05). The significant and positive correlations between Co, Zn, Fe, V and Al (P b 0.01) represents the same input source (human or natural) (Bastami et al., 2015) for these metals in the Chabahar Bay. Many researchers have applied enrichment factor (EF) index in contamination assessments of heavy metals (Feng et al., 2004; Reddy et al., 2004; Çevik et al., 2009; Bastami et al., 2012).EF values were interpreted as; EF ≤ 2 — deficiency to minimal enrichment, 2 b EF ≤ 5 — moderate enrichment, 5 b EF ≤ 20 — significant enrichment, 20 b EF ≤ 40 — very high enrichment and EF N 40 — extremely high enrichment (Grant and Middleton, 1990; Loska et al., 1997). Results of enrichment factor for different metals are shown in Table 8. EF ranged between 1.18–6.91, 0.60–1.02, 0.34–2.43, 0.31– 0.87, 0.65–1.15, 0.14–0.37, 0.76–1.14 and 0.50–0.82 for As, Co, Cr, Cu, Ni, Pb, V and Zn respectively. As revealed the highest while Pb had the lowest enrichment factor. Zn, Pb and Cu had an enrichment factor of b1 at all sites, indicating no Enrichment. Ni at sites 3, 4, 5, 6, 7 and 9, Cr at sites 1, 2 and 8, Co at sites 5, 6, 7 and 9, V at site 1 and As at sites 3, 5, 6, 7, and 9 had an enrichment factor from 1 to 3 which represent the low enrichment in the Chabahar Bay. Also, As at sites 1, 2 and 8 was higher than 5, suggesting significant enrichment. When 0.5 ≤ EF ≤ 1.5, it suggests that the heavy metals may be entirely from crustal materials or natural weathering processes. When EF N 1.5, it proposes that a significant portion of heavy metals are provided by human activities (Zhang et al., 2007). In this study concentration of As was higher than 1.5 at some sites, indicating anthropogenic inputs. According to Hakanson (1980), the potential ecological risk of coastal sediments posed by heavy metals can be classified into the following categories: Low risk: E b 40, PER b 150. Moderate risk: 40 ≤ E b 80, 150 ≤ PER b 300. Considerable risk: 80 ≤ E b 160, 300 ≤ PER b 600. Table 9 Classification of sediment samples based on the potential ecological risk factor (E) in the surface sediments from Chabahar Bay. Sampling sites
As
Cr
Cu
Ni
Pb
Zn
1 2 3 4 5 6 7 8 9 Average ± SD
23.42 27.02 13.51 15.76 11.71 13.96 12.83 28.37 14.18 17.86 ± 6.52
2.15 1.31 0.80 0.68 1.16 0.46 0.75 0.86 0.75 0.99 ± 0.50
– 0.70 1.52 1.20 1.40 1.75 1.87 1.75 3.04 1.65 ± 0.67
1.78 1.78 7.62 2.89 4.77 4.68 4.75 1.27 4.75 3.81 ± 2.04
0.83 0.62 0.81 0.55 0.66 0.63 0.62 0.67 0.83 0.69 ± 0.10
0.27 0.28 0.69 0.24 0.38 0.39 0.38 0.33 0.43 0.38 ± 0.13
5
High risk: 160 ≤ E b 320, PER ≥ 600. Very high risk: E ≥ 320. The calculated E values are shown in Table 9. Single risk factors (E) ranged 17.86 ± 6.52, 0.99 ± 0.50, 1.65 ± 0.67, 3.81 ± 2.04, 0.69 ± 0.10 and 0.38 ± 0.13 for As, Cr, Cu, Ni, Pb and Zn, respectively (Table 9). As and Zn had highest and lowest single risk factors, respectively. The average ecological risk of E value for all metals at most surface sediments were less 40, indicating a low risk to local ecosystem. The results of this study revealed that Chromium, nickel and arsenic levels in the sampling area were higher than sediment guidelines, while copper, zinc and lead concentrations in the sediment appeared to be lower than ERL, thus no pollution risk for these elements exist. Coastal parts of site 3 had higher levels of heavy metals (V, Ni, Pb, Co and Zn). High elements levels at site 3 could be due to local wharf, dock, boat repair stations and also desalination plant activities. 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Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
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Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea Homira Agah, Abolfazl saleh, Kazem Darvish Bastami ⁎, Neda Sheijooni Fumani Iranian National Institute for Oceanography and Atmospheric Science (INIOAS), No. 3, Etemadzadeh St., Fatemi Ave., 1411813389 Tehran, Islamic Republic of Iran
a r t i c l e
i n f o
Article history: Received 29 December 2015 Received in revised form 15 March 2016 Accepted 19 March 2016 Available online xxxx Keywords: Metals Sediment Chabahar Bay Oman Sea
a b s t r a c t In this study, concentrations of Aluminum (Al), Iron (Fe), Chromium (Cr), Copper (Cu), Nickel (Ni), Vanadium (V), Zinc (Zn), Arsenic (As), Cobalt (Co) and lead (Pb) in the surface sediments from Chabahar Bay were studied to assess the degree of heavy metal pollution as a consequence of natural and anthropogenic sources. Metal contents in the sediments were observed in the order of: Al N Fe N Cr N V N Ni N Zn N CuN N As N Pb N Co. According to enrichment factor (EF), Arsenic was higher than 1.5 at some sites, indicating anthropogenic inputs. Contents of Ni, As and Cr in the some sampling sites were higher than sediment quality guideline implying adverse impacts of these metals. Based on potential ecological risk (PER), the Chabahar Bay had low ecological risk. © 2016 Elsevier Ltd. All rights reserved.
Metals, such as arsenic, cadmium, lead, chromium and nickel, are important environmental pollutants, particularly in areas with high anthropogenic pressure (Islam et al., 2015). Some properties of these contaminants such as being toxic or carcinogenic to humans (Fu and Wang, 2001), persistence, bioaccumulation and non-biodegradable cause a significant concern, especially in coastal and marine environments worldwide (Idris et al., 2007; Ruilian et al., 2008; Cao et al., 2015). Their negative effect on marine ecosystems by reducing species diversity and abundance (Bastami et al., 2014b) and through accumulation of metals in living organisms and food chains is well known (Hosono et al., 2011). In addition to these metals, copper, iron, and zinc are also important heavy micronutrients (Paramasivama et al., 2015). Natural sources, industrial and other anthropogenic activities are the dominant sources of heavy metal pollution (Idris et al., 2007; Fu and Wang, 2001). Capacity of sediments to accumulate compounds makes them one of the most important tools to assess the contamination level and evaluation of continental aquatic ecosystems. More than 90% of heavy metals load in aquatic systems have been found to be associated with suspended particulate matter and sediments (Zheng et al., 2008; Amin et al., 2009). Hence sediment analyses play a crucial role in assessing the degree of heavy metal pollution resulting in health risk associated with impaired food chain. Oman Sea is the input path of fresh water flows to the Persian Gulf via Arabian Sea and Indian Ocean; it is also a vital shipping route for the oil-producing countries in the Persian Gulf. Chabahar Bay, which is situated on the Makran Coastline in Sistan and Baluchestan Province, ⁎ Corresponding author. E-mail addresses: [email protected], [email protected] (K.D. Bastami).
Southeast of Iran, is a free port and industrial zone on the coast of the Gulf of Oman. The special importance of Chabahar Bay is due to its Ω shape and limited water circulation. The Chabahar Bay has humid climate, hot summers and moderate winters. Fishing and marine commerce are the main activities in the study areas. Due to the increasing trade and industrial activities in the recent decade in this area, it is expected that these activities influence the accumulation of anthropogenic pollution on coastal and marine sediments. Very little information is available on extend of metals pollution in the North-West of Oman Sea and also in recent years petrochemical industries have started their activities in the Chabahar Bay. Hence, understanding the pollution levels of the region is an important step towards its protection and sustainable development. The main objectives of the present study were 1) To investigate toxic heavy metals distribution in surface sediments from the Chabahr Bay, Oman Sea and 2) Discover relationships between the elemental levels and sediment characteristics, 3) Detect pollution source(s) and 4) Compare pollution level with other marine ecosystems. Sediment samples from nine sites (Fig. 1 and Table 1) were collected using a Van Veen Grab sampler from Chabahar Bay in April 2012. The selected sampling sites represent the most important harbors, desalination plant and industrial regions in Sistan and Baluchestan Province and also they represent coastal areas that are anticipated to have a relative higher pollution due to higher population. The collected samples were placed in pre-cleaned polyethylene plastic bottles, labeled and were carried to the laboratory in ice-boxes for further treatment. The sediment samples were lyophilized, sieved and fractions smaller than 63 μm were transferred in pre-cleaned dark glass labeled bottles and kept frozen (at − 20 °C) prior to chemical
http://dx.doi.org/10.1016/j.marpolbul.2016.03.042 0025-326X/© 2016 Elsevier Ltd. All rights reserved.
Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
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H. Agah et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx
Fig. 1. The location of the sampling site in the Chabahr Bay.
analyses (Wolf-Welling et al., 2001). Sediment samples were subjected to wet sieving and Lazer Particle Sizing (HORIBA-LA950, France and Japan) determination. Total organic matter was measured by heating sediment samples in an oven at 530 ± 20 °C for 8 h (Dean, 1974). Total organic matter was calculated by the following equation: Total organic matter ðTOM; %Þ ¼ ½ðB−CÞ=B 100
ð1Þ
where B and C are the weights of dried sediments before and after combustion in the oven, respectively. For digestion of sediment samples, 0.5 g of each sediment sample was added with a mixture of HCl–HNO3–H2O (with the ratio of 1:1:1 v/v) and heated at 95 °C during 1 h. Metal (Al, Co, Ni, Cu, Zn, As, Pb, Fe, Cr and V) analyses were performed using Inductively Coupled Plasma Mass Spectrometry inductively (ICP-MS) after acid digestion at ACME Lab., Canada which is under 17,025 standards. Quality assurance and quality controls were assessed using standard samples (Oreas 45 Pa, DS7 and DS8). The analytical results of the quality control samples show good agreement with the certified values (recoveries ranging 93.25–105.22%). The limits of detection were set as three times of the standard deviation on the procedural blanks (Table 2). To predict detrimental biological effects and conservation of the organisms living inside or near the polluted sediments, sediment quality guidelines (SQGs) were used. In order to classify the sediment, NOAA provides two values for each substance: (1) sediments with rarely adverse biological impacts (beffect range low), (2) sediments with occasionally or frequently adverse biological impacts (N effect range low and b effect range median) (Long et al., 1995).
Enrichment factor (EF) technique for determining sedimentary metal sources (Selvaraj et al., 2004; Vald'es et al., 2005; Bastami et al., 2014a, 2014b) was calculated as follow (lee et al., 1998; Woitke et al., 2003): Enrichment factor ðEFÞ ¼ ðCs=CFe Þsample =ðCs=CFe ÞBackground:
ð2Þ
While (Cs/CFe)sample are the average element level and Fe concentrations in our study, respectively, (Cs/CFe)Background are the average element level and Fe concentrations in background sample, respectively. Iron or aluminum is used as a normalization element to reduce the variations produced by heterogeneous sediments; the reference element must have minimum variability of occurrence or large concentrations in the studied environment. In the present study, Iron (CV: 3.73%) had a homogeneous concentration in the selected stations. Also, we used background concentrations of metals in sediment from Iranian waters of the Oman Sea which are 7.4, 63.7, 92.4, 42.17, 99, 78, 15.2, 372,0.21 ppm, 2.80 and 6.05% for As, Ni, Pb, Cu, Zn, V, Co, Cr, Cd, Fe and Al, respectively (Hamzeh et al., 2013). Potential ecological risk index (PER) was also introduced to assess the contamination degree of heavy metals in the present sediments. The equations for calculating the PER were proposed by Hakanson (1980) as the following: E ¼ TC
ð3Þ
C ¼ Ca =Cb
ð4Þ
PER ¼ ∑E ¼ ∑TC
ð5Þ
Table 1 Sampling geographical locations in the Chabahar Bay. No
Stations
Depth (m)
Geographical locations
1 2 3 4 5 6 7 8 9
Tiss Tiss Konarak Konarak Desalination plant Entrance of the Chabahar Bay Posm Posm Ramin
3.8 9.0 5.0 10.5 5.8 13.6 12.10 6.0 4.5
25°21′46″ N 60°35′40″ E 25°22′50″ N 60°33′59″ E 25°19′58″ N 60°15′44″ E 25°22′23″ N 60°28′30″ E 25°26′3″ N 60°30′14″ E 25°17′44″ N 60°32′12″ E 25°19′58″ N 60°15′44″ E 25°22′54″ N 60°15′21″ E 25°15′42″ N 60°46′18″ E
Table 2 Detection limits of the elements (mg kg−1). Element
Detection limit
Element
Detection limit
As *Fe Co Cu Cr Ni
5 0.01 0.5 5 10 5
V Pb Zn *Al
5 5 5 0.1
Elements marked as “*” are reported according to their %.
Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
H. Agah et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx Table 3 Grain size distributions and organic matter content levels of the sediment samples at Chabahar Bay. Station
OM%
1 2 3 4 5 6 7 8 9 Average ± SD
Grain size
2.25 4.5 5 8 3 3.75 3.25 3 2.75 4.06 ± 1.83
Sand%
Silt%
Clay%
91 88 26 18 70 40 59 47 88 60 ± 29.15
7 7 62.2 46.6 25 46.6 37.5 45 4 29.48 ± 22.04
2 5 11.8 35.4 5 13.4 3.5 8 8 10.51 ± 10.81
where C is the single element pollution factor, Ca is the content of the element in samples and Cb is the reference value of the element. The sum of C for all the metals examined represents the integrated pollution degree (C) of the environment. E is the potential ecological risk factor of an individual element. T is the biological toxic factor of an individual element, which is determined for Cu = Pb = 5, Zn = 1, As = 10, Cr = 2 and Ni = 6 (Hakanson, 1980). PER is a comprehensive potential ecological index, which equals to the sum of E. It represents the sensitivity of biological community to toxic substances and illustrates the potential ecological risk caused by the overall contamination. Shapiro–Wilk test was executed to analyze the normality of data distribution. Spearman correlations were calculated between element concentrations. Statistical analyses of the data were carried out by using SPSS V19. Grain size and organic matter contents of the sediment samples at Chabahar Bay are presented at Table 3. Organic matter content in the marine sediment originates from marine and terrestrial sources. Chemical compounds of marine sediment are predominantly proteins (amino acids), carbohydrates (sugars) and lipids, while terrestrial organic matter consists of living biomass, plant litter and soil organic matter. TOM content in sediment of the studied area was 2.25–8% (averaged
3
4.06 ± 1.83%) which exhibited the highest and the lowest amounts at stations 4 and 1, respectively. As proposed by Marin et al. (2008), ecological quality status is classified into three levels according to organic matter content: high-good (less than 5%), moderate (between 5% and 10%) and poor-bad (greater than 10%). As illustrated in Table 3, TOM content of all station was less than the presented above range (2.25– 8%) in sediment of the Chabahar Bay. The sand, silt and clay contents averaged 60 ± 29.15%, 29.48 ± 22.04% and 10.51 ± 10.81% respectively. Depth sampling sites ranges from 3.8 to 13.6 m with an average value of 7.81 ± 3.58 m (Table 3). Results of metal contents at different sampling sites are showed in Tables 4 and 5. Minimum and maximum (Mean ± standard deviations) of element levels in all the sampling sites were as: Al: 0.75–5.54% (3.24 ± 1.58), Fe: 1.15–3.22% (1.80 ± 0.65), Cr: 86.70– 400 ppm (185.01 ± 93.40), V: 24.50–94 ppm (47.21 ± 20.47), Ni: 13.50–81 ppm (40.51 ± 21.73), Zn: 24–69 ppm (37.86 ± 13.27), Cu: b5–26 ppm (14.16 ± 5.76), As: 8.67–21 ppm (13.22 ± 4.82), Pb: 10.30–15.50 ppm (12.87 ± 1.95), Co: 4.25–14.80 ppm (8.91 ± 3.88). The lowest element variation was related to iron (CV: 3.73%), indicating a homogeneous concentration of this element in the selected stations. According to the Table 4, metal contents in the sediments were observed in the order of: Al N Fe N Cr N V N Ni N Zn N Cu N As N Pb N Co. As specified in Table 4, coastal parts of Konarak (site 3) often had higher levels of metals, which could be originated from local wharf, dock, boat repair stations and desalination plants activities. Sediment quality guidelines (SQGs) are an important tool for the assessment of contamination in marine and estuarine sediments (Long et al., 1995). Concentrations of Cu, Pb and Zn in all sampling sites were lower than the corresponding values of effect range low (ERL), effect range median (ERM), probable effect level (PEL) and Interim sediment quality guideline (ISQG). Arsenic contents at all sites, Nickel in sites 3,5,6,7 and 9, were higher than ERL, suggesting that these metals in sediments from the Chabahar Bay would be occasionally expected to cause adverse biological effects on biota. Also, Chromium levels at sites 1 were higher than ERM. These results implicate that negative eco-risk effects frequently occur in this station (Tables 4 and 5).
Table 4 Metal content (average ± SD) of the sediments sampled in the studied area. Stations
Al (%)
Fe (%)
Cr (ppm)
Cu (ppm)
Ni (ppm)
V (ppm)
Zn (ppm)
As (ppm)
Co (ppm)
Pb (ppm)
1 2 3 4 5 6 7 8 9
1.61 ± 0.23 1.69 ± 0.09 5.54 ± 1.13 2.91 ± 0.02 4.16 ± 0.03 4.15 ± 0.06 4.28 ± 0.06 0.75 ± 0.23 4.11 ± 0.3
1.24 ± 0.18 1.3 ± 0.04 3.22 ± 0.75 1.35 ± 0.02 1.95 ± 0.02 1.92 ± 0.04 1.97 ± 0.01 1.15 ± 0.25 2.14 ± 0.08
400 ± 127.28 245 ± 7.07 150 ± 47.26 126.67 ± 11.55 216.67 ± 5.77 86.67 ± 5.77 140 ± 0 160 ± 98.99 140 ± 28.28
b5 6±0 13 ± 5.29 10.33 ± 1.53 12 ± 1 15 ± 2 16 ± 0 15 ± 4.24 26 ± 0
19 ± 1.41 19 ± 0 81 ± 9.9 30.67 ± 0.58 50.67 ± 1.15 49.67 ± 1.53 50.5 ± 0.71 13.5 ± 4.95 50.5 ± 4.95
39.5 ± 6.36 31.5 ± 0.71 94 ± 9.9 31 ± 0 51.67 ± 0.58 47.67 ± 1.15 51.5 ± 0.71 24.5 ± 9.19 53.5 ± 4.95
27.67 ± 1.15 28 ± 0 69 ± 4.24 24 ± 0 37.67 ± 1.15 39.33 ± 2.08 38.5 ± 3.54 33.5 ± 0.71 43 ± 5.66
17.33 ± 2.52 20 ± 0 10 ± 0 11.67 ± 0.58 8.67 ± 0.58 10.33 ± 0.58 9.5 ± 0.71 21 ± 0 10.5 ± 0.71
5.05 ± 0.64 4.25 ± 0.21 14.8 ± 2.98 6.8 ± 0 10.57 ± 0.21 10.63 ± 0.25 12.1 ± 0.28 4.3 ± 0.57 11.7 ± 0.85
15.5 ± 0.71 11.5 ± 0.71 15 ± 1.73 10.33 ± 0.58 12.33 ± 0.58 11.67 ± 0.58 11.5 ± 0.71 12.5 ± 2.12 15.5 ± 0.71
Table 5 Sediment quality guidelines from NOAA (Long et al., 1995) and Environment Canada (ISQG, 1995). Metal
As (ppm)
Cr (ppm)
Cu (ppm)
Ni (ppm)
Pb (ppm)
Zn (ppm)
ERLa ERMb ISQGc PELd This study
8.2 70 7.24 41.6 13.22 ± 4.82 (8.67–21)
81 370 52.3 160 185.01 ± 93.40 (86.70–400)
34 270 18.7 108 14.16 ± 5.76 (b5–26)
21 52 – – 40.51 ± 21.73 (13.50–81)
46.7 218 30.2 112 12.87 ± 1.95 (10.30–15.50)
150 410 124 271 37.86 ± 13.27 (24–69)
a b c d
ERL = effect range low (NOAA). ERM = effect range medium (NOAA). ISQG = Interim sediment quality guideline (Environment Canada). PEL = probable effect level (Environment Canada).
Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
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H. Agah et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx
Table 6 Metals concentrations in various sediments of the marine environments. Sampling area
Cr (ppm)
V (ppm)
Ni (ppm)
Zn (ppm)
Cu (ppm)
As (ppm)
Pb (ppm)
Co (ppm)
References
Chabahar Bay
86.70–400 (185.01 ± 93.40) 372 ± 473 (68–2370) 85.2 ± 15.3 (59.6–128) –
24.50–94 (47.21 ± 20.47) 78 ± 24 (45–130) 116 ± 20.5 (76.5–145) 26.46 ± 10.25 (13–41) –
13.50–81 (40.51 ± 21.73) 63.7 ± 26.5 (31.1–116) 51.6 ± 11.8 (29.4–67.8) 29.20 ± 14.68 (10.3–50.4) 26.90 ± 2.72
24–69 (37.86 ± 13.27) 99 ± 104 (36–547) 85.3 ± 17.9 (55.9–146) 42.1 ± 22.15 (13–75) –
b5–26 (14.16 ± 5.76) 42.17 ± 51.34 (12.50–287) 34.7 ± 11.9 (13.2–50.9) 18 ± 8.83 (3.8–31.12) 38.28 ± 0.37
8.67–21 (13.22 ± 4.82) 7.4 ± 2.4 (4–14) 12.5 ± 3.04 (6.97–20.1) 7.77 ± 2.12 (4.4–11.8)⁎
10.30–15.50 (12.87 ± 1.95) 92.4 ± 329.5 (10.40–1780) 18.0 ± 4.17 (11.3–24.6) 11.5 ± 4.88 (4.1–18.3) 50.37 ± 2.41
4.25–14.80 (8.91 ± 3.88)
This study
15.2 ± 4.1 (9.9–22.8) 15.9 ± 4 (6.9–24.2) 10.56 ± 14.68 (3.5–20.8) –
Hamzeh et al. (2013) De Mora et al. (2004) Bastami et al. (2012, 2014a) Sistani et al. (2015) Sistani et al. (2015) Agah et al. (2011) ROPME (1997) Agah et al. (2012) Nguyen et al. (2005) Zwolsman et al. (1996)
Oman Sea Caspian Sea (Iran) Gorgan Bay (Iran) Chabahar Bay, summer Chabahar Bay, winter Caspian Sea North Oman Sea Persian Gulf
–
14.68 ± 1.93 –
–
95
21
Lake Balaton Hungary Scheldt Estuarine, Netherlands Izmir bay Turkey
–
16.45 ± 1.77 60 (46–75)
13.56 ± 1.24
42 (33–51) 329 111 (20–192) 4.4–55
37 (4–79) 13–250
19 (13–27) 8.7 20 (5–33) 0.7–36
3–220
9–1500
1–2600
4–455
13–146
22–311
4–79
7–103
Numerous studies have been conducted on heavy metal contamination throughout world (Zwolsman et al., 1996; ROPME, 1997; Kucuksezgin, 2001; De Mora et al., 2004; Nguyen et al., 2005; Agah et al., 2011, 2012; Bastami et al., 2012; Hamzeh et al., 2013; Bastami et al., 2014a; Sistani et al., 2015). Data in Table 6 shows concentration of heavy metals in sediment of other locations. Contents of some heavy metals in this study were higher than those found in some aquatic environments but were lower than those in other locations. Furthermore, comparison of the present results with previous studies in this area suggested that levels of all heavy metal exception As are lower than those reported by Hamzeh et al. (2013) (Table 6). Also, Sistani et al. (2015) measured contents of nickel, copper and lead in intertidal sediment of Chabahar Bay during summer and winter. Copper and lead concentrations in intertidal sediments were higher than our results in Chabahar Bay, while nickel level in their study was lower than our results (Table 6). Although a quantitative comparison across reported metal data is difficult because of variances in the number sample collected in each study, the sediment fraction analyzed, and the analytical methods used.
11 (7.6–14.6)
13 (10–17)
15 (11–17)
7 (4–21)
7 (3–10) 2–160
14 (3–22) 1.7–17
Kucuksezgin (2001)
In order to know the impact of sediment characteristics on the metals concentrations in the Chabahar Bay sediment, correlation analysis was carried out between them and the correlation coefficient matrix is shown in Table 7. The major factors affecting spatial variation of heavy metals in the sediment are TOM and the grain size. The fine grains, representing the higher rate of surface to volume and ionic absorption power, are more capable in the absorption of contaminated organic and inorganic materials (McCave, 1984; Horowitz and Elrick, 1987). Generally, fine-grained sediments carrying lots of organic matter are more contaminated than coarse-grained sediments. According to the results of Pearson's correlation test (Table 7), the elements of Cr, Fe, V, Zn, As and Pb showed negative correlation with TOM (P N 0.05). There was positive correlation between Cr, V, Zn, Fe, Ni, As, Pb with sand. Clay was positively correlated with Al and Co (P N 0.05). Because of less correlation with metals, contents of TOM, sand, clay and silt are not significant for the metal content of Chabahar Bay. This study, suggest that the distribution and concentration of metals in sediments of Chabahar Bay may depend on offshore industry, shipping, maritime activities, water and sediment movement.
Table 7 Correlation between metals and general characteristics of sediments in the in the studied areas.
Sand Silt Clay Depth Al Cr Fe Ni V Zn As Co Pb Cu
TOM
Sand
Silt
Clay
Depth
Al
Cr
Fe
Ni
V
Zn
As
Co
Pb
−0.697* 0.473 0.905** 0.809** 0.152 −0.381 −0.119 0.019 −0.183 −0.237 −0.271 0.149 −0.599 0.000
−0.947** −0.738* −0.632 −0.076 0.400 0.086 0.016 0.195 0.119 0.068 −0.115 0.354 −0.241
0.481 0.543 0.028 −0.465 −0.090 −0.039 −0.223 −0.086 0.001 0.066 −0.306 0.289
0.580 0.148 −0.116 −0.045 0.040 −0.065 −0.144 −0.188 0.176 −0.322 0.070
0.150 −0.553 −0.127 0.019 −0.222 −0.246 −0.232 0.064 −0.796* −0.288
−0.496 0.900** 0.974** 0.850** 0.742* −0.922** 0.974** 0.152 0.319
−0.386 −0.466 −0.203 −0.338 0.479 −0.504 0.416 −0.497
0.972** 0.979** 0.954** −0.685* 0.927** 0.400 0.292
0.935** 0.873** −0.830** 0.977** 0.266 0.306
0.942** −0.627 0.876** 0.495 0.218
−0.470 0.816** 0.488 0.288
−0.873** −0.004 −0.358
0.262 0.465
0.649
TOM = Total organic matter. ⁎ Correlation is significant at the 0.05 level. ⁎⁎ Correlation is significant at the 0.01 level.
Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042
H. Agah et al. / Marine Pollution Bulletin xxx (2016) xxx–xxx Table 8 Enrichment factor of different metals of sampling site in the surface sediments from Chabahar Bay. Sampling sites
As
Co
Cr
Cu
Ni
Pb
V
Zn
1 2 3 4 5 6 7 8 9 Average ±
5.29 5.82 1.18 3.27 1.68 2.04 1.82 6.91 1.86 3.32 ±
0.75 0.60 0.85 0.93 1.00 1.02 1.13 0.69 1.01 0.89 ±
2.43 1.42 0.35 0.71 0.84 0.34 0.53 1.05 0.49 0.91 ±
– 0.31 0.27 0.51 0.41 0.52 0.54 0.87 0.81 0.53 ±
0.68 0.65 1.12 1.01 1.15 1.15 1.14 0.52 1.05 0.94 ±
0.37 0.26 0.14 0.23 0.19 0.18 0.17 0.32 0.21 0.24 ±
1.14 0.87 1.05 0.82 0.95 0.89 0.94 0.76 0.90 0.93 ±
0.63 0.61 0.61 0.50 0.55 0.58 0.55 0.82 0.57 0.60 ±
2.13
0.17
0.66
0.21
0.25
0.07
0.11
0.09
SD
Correlation matrix demonstrated that there were no significant correlations between Cr and As with other elements (P N 0.05). The significant and positive correlations between Co, Zn, Fe, V and Al (P b 0.01) represents the same input source (human or natural) (Bastami et al., 2015) for these metals in the Chabahar Bay. Many researchers have applied enrichment factor (EF) index in contamination assessments of heavy metals (Feng et al., 2004; Reddy et al., 2004; Çevik et al., 2009; Bastami et al., 2012).EF values were interpreted as; EF ≤ 2 — deficiency to minimal enrichment, 2 b EF ≤ 5 — moderate enrichment, 5 b EF ≤ 20 — significant enrichment, 20 b EF ≤ 40 — very high enrichment and EF N 40 — extremely high enrichment (Grant and Middleton, 1990; Loska et al., 1997). Results of enrichment factor for different metals are shown in Table 8. EF ranged between 1.18–6.91, 0.60–1.02, 0.34–2.43, 0.31– 0.87, 0.65–1.15, 0.14–0.37, 0.76–1.14 and 0.50–0.82 for As, Co, Cr, Cu, Ni, Pb, V and Zn respectively. As revealed the highest while Pb had the lowest enrichment factor. Zn, Pb and Cu had an enrichment factor of b1 at all sites, indicating no Enrichment. Ni at sites 3, 4, 5, 6, 7 and 9, Cr at sites 1, 2 and 8, Co at sites 5, 6, 7 and 9, V at site 1 and As at sites 3, 5, 6, 7, and 9 had an enrichment factor from 1 to 3 which represent the low enrichment in the Chabahar Bay. Also, As at sites 1, 2 and 8 was higher than 5, suggesting significant enrichment. When 0.5 ≤ EF ≤ 1.5, it suggests that the heavy metals may be entirely from crustal materials or natural weathering processes. When EF N 1.5, it proposes that a significant portion of heavy metals are provided by human activities (Zhang et al., 2007). In this study concentration of As was higher than 1.5 at some sites, indicating anthropogenic inputs. According to Hakanson (1980), the potential ecological risk of coastal sediments posed by heavy metals can be classified into the following categories: Low risk: E b 40, PER b 150. Moderate risk: 40 ≤ E b 80, 150 ≤ PER b 300. Considerable risk: 80 ≤ E b 160, 300 ≤ PER b 600. Table 9 Classification of sediment samples based on the potential ecological risk factor (E) in the surface sediments from Chabahar Bay. Sampling sites
As
Cr
Cu
Ni
Pb
Zn
1 2 3 4 5 6 7 8 9 Average ± SD
23.42 27.02 13.51 15.76 11.71 13.96 12.83 28.37 14.18 17.86 ± 6.52
2.15 1.31 0.80 0.68 1.16 0.46 0.75 0.86 0.75 0.99 ± 0.50
– 0.70 1.52 1.20 1.40 1.75 1.87 1.75 3.04 1.65 ± 0.67
1.78 1.78 7.62 2.89 4.77 4.68 4.75 1.27 4.75 3.81 ± 2.04
0.83 0.62 0.81 0.55 0.66 0.63 0.62 0.67 0.83 0.69 ± 0.10
0.27 0.28 0.69 0.24 0.38 0.39 0.38 0.33 0.43 0.38 ± 0.13
5
High risk: 160 ≤ E b 320, PER ≥ 600. Very high risk: E ≥ 320. The calculated E values are shown in Table 9. Single risk factors (E) ranged 17.86 ± 6.52, 0.99 ± 0.50, 1.65 ± 0.67, 3.81 ± 2.04, 0.69 ± 0.10 and 0.38 ± 0.13 for As, Cr, Cu, Ni, Pb and Zn, respectively (Table 9). As and Zn had highest and lowest single risk factors, respectively. The average ecological risk of E value for all metals at most surface sediments were less 40, indicating a low risk to local ecosystem. The results of this study revealed that Chromium, nickel and arsenic levels in the sampling area were higher than sediment guidelines, while copper, zinc and lead concentrations in the sediment appeared to be lower than ERL, thus no pollution risk for these elements exist. Coastal parts of site 3 had higher levels of heavy metals (V, Ni, Pb, Co and Zn). High elements levels at site 3 could be due to local wharf, dock, boat repair stations and also desalination plant activities. 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Please cite this article as: Agah, H., et al., Ecological risk, source and preliminary assessment of metals in the surface sediments of Chabahar Bay, Oman Sea, Marine Pollution Bulletin (2016), http://dx.doi.org/10.1016/j.marpolbul.2016.03.042