Magntic susceptibility as a proxy to heavy metal content in the sediments of Anzali wetland, Iran
© Vesali Naseh et al.; licensee BioMed Central Ltd. 2012
Received: 15 December 2012
Accepted: 16 December 2012
Published: 27 December 2012
Heavy metal concentrations and magnetic susceptibility of sediment samples were analyzed as indicators of urban and industrial contamination in Anzali wetland in Gilan, Iran. The aim was to investigate the suitability of magnetic properties measurements for indicating heavy metal pollution. The concentration of six heavy metals (Ni, Cr, Cd, Zn, Fe, and Pb) was determined in different depths of four sediment core samples within four different regions of the wetland (Abkenar, Hendekhaleh, Shijan and Siakeshim). Average concentration of heavy metals in the sediment cores was higher than the severe effect level (SEL) for Ni, Cr and Fe (77.26, 113.63 ppm and 5.2%, respectively) and lower than SEL for Cd, Zn and Pb (0.84, 137.7, 29.77 ppm, respectively). It was found that the trend of metal concentrations with the depth is different in each core and is related to the pollution discharges into the rivers entering the wetland. Core magnetic susceptibility measurements also showed different magnetic properties in each core. Cluster analysis was applied using Pearson correlation coefficient between heavy metal concentrations and magnetic properties across each core. Significant relationship was found to exist between magnetic susceptibility and the concentration of Ni in Abkenar and the concentration of Fe in other regions. Whereas Abkenar is almost the isolated and uncontaminated region of the wetland, it revealed a difference in magnetic properties between contaminated and uncontaminated sediments. It was concluded that magnetic properties of samples from contaminated zone were mostly related to Fe content. The result of this study demonstrated that magnetic susceptibility measurements could be applied as a proxy method for heavy metal pollution determination in marine environments in Iran especially as a rapid and cost-effective introductory site assessments.
Magnetic susceptibility (MS) measurements are being used as an approximate tool for detecting industrial pollutions, because they are comparatively simple, fast and cost effective analyses. [1–7]). This method also could be applied as a tool for the assessment of heavy metal contamination in sediments , on the other hand as a proxy for heavy metal pollution. Petrovsky′ and Ellwood  discovered that magnetic susceptibility and Zn concentrations show very similar spatial distributions in a 20,000 m2 area at the Litavka River, Czech Republic, where ashes from a lead smelter are weathering in the fluvisols. Chan et al., , revealed that a significant correlation exists between the magnetic susceptibility and the concentration of Pb, Zn and Cu as well as Tomlinson pollution load index (PLI) in seabed sediments of Hong Kong Harbour. Schmidt et al., , investigated the suitability of field magnetic measurements for indicating heavy metal pollution. Geochemical analysis of their soil samples from Bradford, England, showed close correlation of concentrations between Fe, Cu, Mn, and Ni. In addition, Fe concentrations correlated with magnetic susceptibility field measurements. The results of their study demonstrated the potential of magnetic susceptibility field mapping for fast preliminary site assessment, greatly reducing the scale of subsequent geochemical sampling and analysis.
Magnetic susceptibility measurements, in Iran, have been applied for survey on Caspian sea-level fluctuation , but as a proxy for industrial contamination has been employed only in urban topsoils in the arid region of Isfahan . They measured the magnetic susceptibility of 113 collected soil samples from public parks and green strips along the rim of roads with high-density traffic within the city of Isfahan using the Bartington MS2 dual frequency sensor. As, Cd, Cr, Ba, Cu, Mn, Pb, Zn, Sr and V concentrations were also measured in all collected soil samples. They discovered that Pb , Cu, Zn, and Ba have positive significant correlations with magnetic susceptibility, but As, Sr, Cd, Mn, Cr and V have no significant correlation with the magnetic susceptibility. There was also a significant correlation between pollution load index (PLI) and magnetic susceptibility. Finally they indicated the potential of the magnetometric methods to evaluate the heavy metal pollution of soils.
The present study is trying to investigate the suitability of magnetic properties measurements for indicating heavy metal pollution in Anzali wetland at the north of Iran. The result of this study suggests a useful, fast and cost-effective method for assessment of environmental pollutions in Iran.
Materials and methods
The Anzali wetland is shaped from 4 regions: west region (Abkenar), central region (Hendekhaleh), Siakeshim and east region (Shijan). Sampling sites were chosen approximately in the center of each region to represent the situation of each part (Figure 2): St1 in Abkenar, St2 in Hendekhaleh, St3 in Shijan and St4 in Siakeshim. Situation of sampling point in some locations (low depth marsh areas) was also considered for ease of sampling.
Sediment cores were collected in slosh mode using a piston gravity corer in May 2011. The core lengths were 70, 70, 80 and 50 cm and the diameter was 6 cm. All the samples were sealed by nylon and transferred to sediment laboratory of Iranian National Institute for Oceanography, Tehran, Iran, for magnetic susceptibility analysis. For geochemical analyses, they were transferred to sediment and chemistry laboratory of Water Research Institute, Tehran, Iran. After the polyethylene tube was cut off carefully, the sediment columns were sectioned into slices in depths of 0, 2, 6, 10, 15, 30, 50 and 70 cm along core 1 and core 2; 0, 2, 6, 10, 15, 20, 40, 60 and 80 cm along core 3 and 0, 2, 6, 10, 15, 30 and 50 cm along core 4.
Magnetic susceptibility measurements
Magnetic susceptibility (MS) is a measure that particular sediments are magnetized when subjected to a magnetic field. The ease of magnetization is ultimately related to the concentration and composition (size, shape and mineralogy) of magnetizable material contained within the sample. Any sediment core possessing downcore variation per unit volume in the concentration and composition of magnetizable minerals will yield a MS curve reflecting these changes .
Magnetic susceptibility measurements are a non-destructive and cost effective method of determining the presence of iron-bearing minerals within the sediments. The whole cores, or individual sediment samples, are exposed to an external magnetic field which causes the sediments to become magnetized according to the amount of Fe-bearing minerals present in the samples.
In our system, using Bartington MS2 System  whole cores are moved incrementally (generally in 1 cm) by a track motor through a susceptibility loop (of varying size) in which a magnetic field is generated and which magnetizes the sample susceptible substances (minerals or mineraloids) within the sediment. Samples that are rich, per unit volume, in magnetizable substances will yield high readings.Samples that are poor in magnetizable substances, or contain diamagnetic minerals, will yield lower or negative values.
Subsamples for geochemical analysis were chosen incrementally in different depths along core samples, dried and powdered in agate mortar. Digestion of organic matter and dissolution of silicates for total elemental analysis were done as described below: 1.0 g of the 100-mesh (0.15 mm) sediment was weighed into a 100-mL Teflon beaker and 10 mL of HNO3 and 10 mL of HClO4 were added. The beaker was covered with a Teflon watch cover and heated at 200°C for 1 h. The cover was removed and heating was continued until the volume became 2 to 3 mL. After cooling the sample, 5 mL of HClO4 and 10 ml of HF were added; Teflon cover was put and heated at 200°C until all siliceous materials had been dissolved. Then the cover removed and heating continued until the volume was 2 to 3 mL. The digest was cooled, 10 mL of 50% HCl was added, Teflon cover put and heated at 100°C for 30 min. After cooling the sample brought to 50-mL volume. The solution is then ready for ICP determination . The concentrations of heavy metals were determined by Varian 710-ES Inductively Coupled Plasma Mass Spectrometry (ICP-MS) according to APHA AWWA, WEF . Each sample was duplicated and the average was reported.
To assess metal concentrations in sediment, the New York State Department of Environmental Conservation  guideline was applied. It proposed the lowest effect screening levels (LEL) for Ni, Cr, Cd, Zn, Pb, and Fe of 31, 26, 0.6, 120, 31 mg/kg and 2%, respectively, and severe effect screening levels (SEL) of 75, 110, 9, 270, 110 mg/kg, and 4%, respectively. The pollution extent was assessed by two threshold values of LEL and SEL. If the LEL was exceeded, the metal could moderately impact biota health. If the SEL was exceeded, the metal could severely impact biota health .
Concentration of heavy metals in subsamples
Core 1 (Abkenar)
Core 2 (Hendekhaleh)
Core 3 (Shijan)
Core 4 (Siakeshim)
The average value of Ni concentration was above SEL (50 mg/kg) at all cores. The maximum Ni concentration appeared at the depth of 50 cm at core 4 (Siakeshim), which was more than two times the SEL. A relatively constant Ni concentration was detected across core 1 (Abkenar), but in core 2 it increases with the depth increase to concentration of 105 ppm at the depth of 50 cm and decreases to 98 ppm at the depth of 70 cm. The minimum value of Ni concentration appeared at the depth of 15 cm in core 3.
At core 2 and core 3 (Hendekhale and Shijan), the average value of Cr concentration was above SEL (110 mg/kg) and the maximum value appeared at the depth of 2 cm at core 2. In core 1 and core 4, the average Cr concentrations were below SEL and above LEL (26 mg/kg). The minimum value of Cr concentration appeared at the surface of core 1.
All of the Cd concentrations were below SEL (9 mg/kg) but the average values of Cd concentration in core 2 and core 3 were above LEL (0.6 mg/kg). The maximum concentration appeared at the surface of core 3 and the minimum value appeared at core 1.
Zn concentration in all subsamples was below SEL (270 mg/kg) except for core 2 at the depth of 2 cm. the average value of Zn concentration was near LEL (120 mg/kg) in core 1, core 2 and core 4 and the minimum value appeared at the surface of core 1.
The average concentration of Pb in all sediment columns was below LEL (31 mg/kg) except for core 3 (Shijan), which was above LEL and below SEL (110 mg/kg). A relatively constant Pb concentration was detected across core 1 (Abkenar) but in core 4 it increases with the depth increase. The maximum value of Pb concentration appeared at the depth of 15 cm in core 3 and the minimum value appeared at the surface of core 4.
All of the average values for Fe percentage in sediment columns were above SEL (4%) and the maximum value of appeared at the depth of 10 cm in core 4. A relatively constant Fe concentration was detected across core 1, core 3 and core 4.
Magnetic susceptibility results
Comparison of Ni, Cr, Cd, Zn, Fe and Pb concentrations in Anzali wetland and some other water bodies
Anzali Wetland, Iran
Anzali Wetland, Iran
Anzali Wetland, Iran
Anzali Wetland, Iran
Avsar Dam Lake, Turkey
Storm water retention pond, New York, USA
Kolleru Lake, India
J. A. Alzate Reservoir, Mexican
Concentration of heavy metals in subsamples 
The main objective of this study was to investigate the relationship between the magnetic susceptibility and the contamination of heavy metals in sediments of Anzali wetland. To achieve the aim, four stations in the wetland were chosen considering four different regions of the wetland and core sediment samples were collected. Six heavy metals (Ni, Cr, Cd, Zn, Fe, and Pb) were analyzed across each sediment core by geochemical analysis. Whole-core magnetic susceptibility measurements were done on each sample using Bartington MS2C System. To discover the relationship between magnetic susceptibility and heavy metals content, cluster analysis was applied using Pearson correlation coefficient. Major findings are listed below:
High trace metal concentrations of sediment in Anzali wetland result from rapid urbanization and industrialization, and lack of wastewater treatment plants in surrounding industries. Whereas pollutions haven’t emitted to the wetland continuously, no clear trend could be detected for heavy metal contents in vertical distribution curves at these sediment cores.
Geochemical analysis of soil samples showed different correlations of concentrations in each core: in core 1 there was close correlation between Cd, Pb and Zn; in core 2 there was close correlation between Cd and Ni and in core 4 there was close correlation between Cr, Pb and Ni.
Significant relationship was found to be between magnetic susceptibility and the concentration of Fe in most of core samples. It concluded that magnetic properties of core samples were related to Fe content.
In west part of the wetland, Abkenar region (zone A in Figure 2), the relationship between MS and heavy metals was different with the other parts (zone B in Figure 2). It could be related to the contamination level of each zone. zone A is relatively isolated part of the wetland (only one river inflow) and consequently is less contaminated than zone B. comparison of average heavy metal contents in four sediment cores (Figure 3) confirmed this fact. It can be deduced from this finding that during last decades, before urbanization and industrialization of the wetland basin, the correlation of MS and heavy metals in Anzali wetland have been significant for Ni, Cr and Fe, but during recent years by rapid process of urbanization and industrialization and increasing contamination from rivers inflowing the wetland, this correlation had become significant for Fe.
The result of this study demonstrated that magnetic susceptibility measurements could be applied as a proxy method for heavy metal pollution determination in marine environments in Iran especially as a rapid and inexpensive preliminary site assessment. Such a survey should be accompanied by geochemical data for more accuracy. Although availability of suitable cores is very important in this application, if provided, magnetic susceptibility can offer scientists and engineers a quick and cost-effective tool of surveying seabed contamination by heavy metals.
The authors would like to thank Iran Water Research Management Company who supported this research as a research project (code: ENV1-89015) and Water Research Institute who cooperated in collecting sediment samples and experimental supports.
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