Recent Advances in Applied & Biomedical Informatics and Computational Engineering in Systems Applications

Enrichment of Iron and Manganese in Zayanderoud river sediments () JAVAD TABATABAEI Department of mining and petroleum , branch, Islamic Azad university, Meymeh,Iran [email protected]

Abstract

Zayanderud River, located in Province with a length of about 420 km flowing from west to east, is one of the most important rivers of Iran. The river is very important because of its various applications of its water. However, many heavy industries, including Zovbeahan Steel Company, Foolad Steel Company, Polyacryl and other chemical plants as well as several power plants, refineries, military facilities, etc. discharge their wastewater into the river. In order to study the motion changes of the potentially poisonous elements of Iron and manganese and their effective factors in Zayanderoud river sediments, samples were taken from crosssectional area of each of 12 sampling stations ( up stream to down stream), and then examined using an ICPMS method (Inductive Coupled Plasma Mass Spectrometry) . The results from the analysis of fine grain sediments indicate a high concentrations of Fe and Mn in several stations. The separation of human factors from natural ones was done by comparing Mn and Fe concentrations at Zamankhan bridge station ( as the reference sample ) with those of the other sampling stations by obtaining the enrichment coefficient. These results reveal that EF measured for elements such as Mn and Fe is high in samples and Geoaccumulation index shows that sediments of Zayanderoud river are little contaminated for these elements. Key words: Heavy metal, Enrichment factor, Zayanderoud river, Sediments

1 INTRODUCTION decompose heavy metals [14,15,24]. Hence, such pollutants usually form stable compounds and aggregates in the nature [3, 17, 20, 21]. Pollution of earth’s ecosystems by heavy In a river system, metals are distributed metals is a global problem. Due to population between solution phase (water column and water growth and increasing need for resources such as between sediment particles), solid phase (suspended water, food and energy, dangers associated with this and precipitated) and aquatic plants and animals. problem seem to be increasing every day. Moreover, metals consistently change phase and Because of absorption of pollutants through such changes vary with the environment [26]. breathing, eating, , drinking water and their transfer through food chain, pollutions can have serious effects on health. They, for example, may cause 2 MATERIALS AND memory disabilities, disabilities of various body METHODS organs, cancer, etc [9,10,18,22,23,25]. Polluting sediments in rivers’ basins may 2.1 STUDY SITE cause increasing pollution in downstream aquatic ecosystems. Zayanderud Basin is located in the central Water plays a major role in geochemical and plateau of Iran, comprising of a vast area. Its area is biological processes and is usually considered the about 41,550 square kilometers, 40%, 59% and 1% main carrier of pollutants [27]. Many types of of which is mountainous, foothill and swamp, pollutants do exist, each type of which pollutes respectively [12]. various environments. Heavy metals are considered Zayanderud, flowing from west to east, is the one of the most important water pollutants which not longest river of Iran’s plateau which passes through only pollute surface and ground water resources, but Esfahan City, with a length of about 420 kilometers. also can be absorbed by the soil and sediments It starts in Zardkuh Mountains and dries up in through cation exchange mechanism. As opposed to Gavkhuni Swamp (Fig. 1). most organic pollutants, living species can not

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The study area is located between Isfahan and could reasonably be polluted. The locations and Baghbahadoran and is part of zayanderoud basin, names of the stations, shown in Fig. 2, are ordered This Basin is located between 31o 15′N and from upstream to downstream. o In each of the twelve stations, a sample of 34 45′N . about 2 kilograms was taken from surface sediments According to above information, Zayanderud (located in sedimentwater contact area). A plastic Basin has a variety of climates and shovel was used for sediment sampling. Then, weathers. There is a cold and mountainous sediments were put in polyethylene containers. It climate in the upper parts and a hot, arid should be noted that the same set of stations were and Mediterranean climate in the lower parts. used for water and sediment sampling. Precipitations occur in early fall until mid spring. 0.2 gram of sediment sample was put into The dry season is from mid spring to early fall. special Teflon container. 5 ml of nitric acid 65%, 2 Zayanderud bed in mountainous area is ml of hydrofluoric acid 48% and 1 ml of covered by coarse particle sediments such as cobble, hydrochloric acid 37% was added to the sample for pebble, granule and sand. A good part of flood plain digestion. Container was sealed and heated. and lowslope banks of the river are used for Digestion process is a multistep process; in each agricultural applications. In eastern parts of the step, power, pressure and time were increased. region, lower slope causes the size of bed sediments to reduce so that final parts of the region are covered 2.3 ANALYSIS by silt and clay. Type and composition of geological We used ICPMS (Inductive Coupled Plasma formations as well as tectonic affect the Mass Spectrometry) instrument equipped with concentration of potentially toxic elements [7]. CCD detectors (V10ES model, Varian Inc.) to Hence, this section examines geological detect and measure heavy metal content in the characteristics of Zayanderud basin. samples. All of samples analysis in LABVEST From the first to the fifth station (Zamankhan laboratory ( Austria). Bridge to Kalleh Bridge), river bed is composed of In order to evaluate river pollution and precambrian metamorphic rocks such as Gneiss, determine concentration and toxicity of heavy Amphibolite and Schist. In Cham aseman station, metals, reliable international standards need to be river bed is composed of Shale, Sandstone and used [5]. The standard developed and recommended Shemshak formation Mudstones (Jurassic) layers. by Kabata Pendias and Mukhrejee [13] is one of the River bed in Zarinshahr station is characterized by most complete ones of its own that establishes an Cretaceous Dolomite and Dolomitic Limestone allowed range for each element found in water, layers. In other stations, river bed is composed of sediment and rock studies (Tab. 1). alluvial terraces and new low foothill alluvial fans . This standard is used to evaluate pollution concerning each element in the basin of the studied 2. 2 SAMPLING river .

Twelve stations were determined for 2.4 Geochemical Background Concentration sampling based on primary studies and field observations and by considering several parameters Geochemical background concentration helps including climatic characteristics, distribution of us better understand environmental dangers of pollution sources, secondary distributaries which pollution levels calculated for water, air and join the mainstream, tectonic features, change in the sediments. In fact, natural concentration of heavy composition of the river floor, slope of the river metals should be distinguished from heavy metal bank, location of industries, municipal and industrial content discharged into the environment by human sewage and wastewater discharge into the river, activities . access to the site, possibility of conducting sampling In order to determine geochemical process and pick up samples from the middle of the background concentration, we may use unpolluted river . First station, Zamankhan Bridge, was used as or lesspolluted samples. In the case of the study, we the reference (blank) sample because of its may use samples taken from upstream parts where unpolluted water. Other stations used for no pollution sources were observed. It seems that environmental sampling were located in areas which the sample taken in Zamankhan Bridge (Station 1)

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can serve as the blank(i.e.reference)sample. As it can be seen in Fig. 3 and 4, heavy Statistical analysis of this sample is provided in Tab. metals concentrations are highly variable. Highest 2. concentrations were observed postZOVBEAHAN According to Tab. 2, metals concentration in Co. Station (located just after ZOVBEAHAN co. some cases are equal to global average. However, drainage pipeline) as well as Bagh Bahadoran for all elements and in both water and sediment Station, Zarinshahr Station and Bridge samples, concentrations are below international Station. limit. For some elements such as Co, we found no In most cases, concentration variation is due reference value because its concentration was below to geochemical background concentration. LOD. While we recommend using reference values However, in some cases, such variations can be instead of global levels, both international standards attributed to geochemical reactions between water and reference values are plotted in the diagrams of and sediments, such as sedimentation and this study to allow easy comparison. absorption. In other words, sudden increase or In environmental investigations, especially decrease in heavy metals concentration in some when both geological and human factors affect the stations can be due to sedimentation or element concentration of elements, Enrichment Factor (EF) transportation in suspended or dissolved phase (such can better explain the effect of external factors phase changes occur as a response to various (usually caused by human activities). In order to geochemical reactions). determine EF, it’s supposed that concentration of Ti, In order to evaluate the effect of external Fe, Al [4], Y and Sc [11] is completely dependent factors (usually human factors), Enrichment Factors on geochemical characteristics of the ground. were calculated. EF values are available in Tab. 5. Therefore, due to geochemical nature of these These results reveal that EF measured for elements elements, their concentrations in natural geological such as FE and Mn is relatively high in samples environments are almost constant. Hence, these taken from Ghadir Bridge, postZobahan Co. and elements are used as reference elements to Falavarjan stations. As for Muller Geoaccumulation determine EF. Index (Tab. 6), comparing calculated values with the EF is the ratio of relative abundance of standard suggested by Muller can help evaluate chemical elements in soil or sediments to their pollution level. abundance in reference environment [4] and was calculated by the following expression: 4 DISCUSSION []M sample []M ′ As already mentioned in previous sections, EF = , []M there are many applications associated with studying Re ference Material []M ′ potentially toxic elements and their reactions with river water in order to examine pollution with such ′ In this expression EF , M and M are Enrichment elements [2, 6, 17]. For applications such as Factor, studied element and reference element, gathering information about change and aggregation respectively. Furthermore, in order to determine pattern of potentially toxic elements in aquatic pollution level of sediments, Geoaccumulation environments or finding solutions to manage Index ( I geo ) were used: pollution sources in rivers, simultaneous

Igeo = log2 ( cn /1.5 Bn ) (Muller examination of potentially toxic elements in both Geoaccumulation Index, 1979), water and sediments is strongly recommended [8]. However, sampling in just one season can not In this expression Bn is heavy metal concentration provide us with sufficient data to establish general in unpolluted environment and Cn is heavy metal pattern of river water’s pollution. And as previously concentration measured for sediments smaller than mentioned, several parameters such as water 63 . Based on I geo , sediments are categorized in discharge, concentration of wastewaters discharged 6 groups in terms of pollution level (Tab. 3). into rivers, river’s slope, etc. affect the concentration of potentially toxic elements. Hence, 3 RESULTS concentration of such elements in water varies during the day. Given the characteristics of potentially toxic The results of analysis are shown in Tab. 4 elements present in Zayanderud River’s water and

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sediments, which were pointed out in previous increasingdecreasing (alternatingsinus) pattern. sections, the data should be combined so that special Maximum concentration of manganese belongs to contribution of each parameter to mobility or fourth station and is 940 ppm. However, immobility of such elements can be established and geochemical background concentration in reference stations polluted with them can be located. In this station is 750 ppm. This maximum value is above section, we examine the pattern of change of both the standard level and geochemical background potentially toxic elements (with high concentrations) concentration value. Manganese is most correlated in the sediments of Zayanderud River in order to with Ti, Cu and V. With regards to Al, its determine respective effect of each parameter on correlation coefficient is 0.89. sediment characteristics as well as their possible Since manganese is naturally found in some effect on distribution of potentially toxic elements particular forms and doesn’t have a uniform along the river. distribution, manganese concentration varies with sampling location. Calculated manganese 4.1 Ferrous in Sediments concentrations in sediments can be seriously questioned in several ways. Therefore, no firm In general, ferrous concentration depends on conclusion can be made in this regard (Fig. 6). the type of parent rocks of river bed. This can be easily observed in our study on Zayanderud river. 5 Conclusion According to statistics calculated in this study, ferrous is most correlated with cobalt, titanium, vanadium and chromium. Ferrous content of Concentrations of some heavy metals were sediments often varies with absorption parameters compared with lithology of the river formation and of ferrous and/or its precipitation. Maximum ferrous geochemical parameters , which indicated that concentration is 41,075 ppm in Cham aseman Dam heavy metal concentration in sediments was as station. After this station, the ferrous content of expected. sediments decreases continuously. This decrease is Based on geologic and stratigraphic studies, mainly associated with parent rocks of river bed. As type and composition of geological formations of pointed out earlier, in some parts of the river, parent the region in general and river bed in particular can rock is composed of Shale and mafic Igneous rocks have a major effect on the concentration of which contain a high amount of ferrous. However, potentially toxic elements. This effect is due to in other parts of the river, parent rock is mainly redistribution of absorbing rocks and presence of composed of lime and Neogen alluvium which strong absorbers such as microparticles. contain a much lower amount of ferrous. This helps Our study shows that concentration of explain why ferrous concentration in final stations potentially toxic elements varies with lithological reaches background concentration value (Fig. 5). characteristics of geological formations. Some other parameters such as EC, pH and Eh were determined 4.2 Manganese in Sediments . These parameters were almost constant throughout the river and thus had no effect on the concentration Manganese concentration in sediments is of potentially toxic elements. highly variable. Higher concentrations of In comparing analysis results with manganese are associated with mafic parent rocks as international standards (which were developed well as arid and semiarid climate. Manganese based on several credible international standards content of sediments can be in the form of nodule, such as EEC and EPA), it was shown that almost no point or veins. This element is usually in the form of element had concentration above the allowed limit. oxides and hydroxides and is mostly observed as In comparing water/sediment analysis results with coating. Pattern of change of manganese geochemical background concentration values, it concentration in sample sediments is shown in Fig. was found that respective concentrations of some 3. The standard allowed range for manganese in elements (e.g. As, Pb, Cu, Cr, Ni) were higher than river sediments, with regards to river formations geochemical background concentrations. However, which are usually shale and schist in the case of based on international standards, these values were Zayanderud River, is from 400 to 850 ppm. not considered to be in polluted range and thus had Concentration of manganese follows a variable no serious environmental consequence. It should be pattern through the river, generally showing an noted that sampling was conducted in humid season, and conducting the same procedure in arid months

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could reveal much higher values for element [6] Forstner U. and Salomons W. Trace concentrations. metal analysis on polluted sediments. Part I: Ferrous concentration in sediments is above Assessment of sources and intensities. standard limit throughout the river. However, since Environ. Technol. Lett., 1980, v. 1, p. 494– geochemical background concentration of ferrous is 505. high as well, measured values could not be [7] Forstner U. Inorganic pollutants, considered pollution. Hence, parent material is the particularly heavy metals in estuaries. In: most important factor affecting ferrous content of Chemistry and biogeochemistry of sediment samples. Estuaries. Olausson E. and Cato I. (eds.). Pattern of change of potentially toxic John Willey and Sons, 1981. elements concentration is completely irregular, [8] Forstner U. Contaminated sediments being associated with sampling station’s distance ,Lecture notes in Earth Sciences. Germany, from polluted sources (e.g. industrial towns and Berlin: Springer, 1989. wastewater drainage pipes). Furthermore, the type [9] Goyer,R,A. and Mehjaman, M.A. and characteristics of pollutions depend on the type (editors), Toxicology of trace elements john of industrial activities and their respective wiley and sons, new york,1977. wastewaters discharged into the river. In areas [10] Hamdard,M, E. and Vohora S.B., located far from polluted sources, where no more Medical Elementology: Practical wastewater is discharged into the river, Applications, Institute of history of Medi concentration of potentially toxic elements reaches Cine and Medical research, new Dehli,1989. geochemical background concentration. This can [11] Hernandez L., Probst J.L. and Ulrich E. indicate the role that sediments and their texture Heavy metal distribution in some French parameters play in reducing or even eliminating forest soils: Evidence for atmospheric humanrelated pollutions, called river self contamination. The science of the total refinement. environment, 2003, v. 312, p. 195–212. [12] Jamab Conductor Engineers, Climate Acknowledgements: I would be delighted to and Water resources condition in Gavkhoni express my gratitude to Isfahan regional water watershed, now and future, national company and Islamic Azad university , Majlesi management office (water affairs), 1978, branch for their financial and other support during 229 p. this research. [13] KabataPendias A., Sadurski W. Trace elements and compounds in soil. In: Merian REFERENCES E., Anke M., Ihnat M., Stoepppler M. (eds.). Elements and their compounds in the [1] AStrom M.and Astrom J. Geochemistry environment, WileyVCH, Weinheim, 2nd of stream water in a catchment in Finland ed., 2004, p. 79–99. affected by sulphidic fine sediments. [14] Kumar R(editor) Environmental Applied Geochemistry, 1997, v. 12, p. 593– pollution and health hazards in India, 605. Ashish publishing house, New Dehli,1987. [2] Chapman D. Water quality assessment. [15] Levis,A.J.and Walz, D.T., London: Chapman and Hall, 1992, 284 p. Immunopharmacology of gold, Prog. Med. [3] Delgado M., Bigeriegs M. and Guardida Chem,1988, v.19,158. E. Uptake of Zn and Cd by water hyacinths. [16] Mclean J.E and Bledsoe B.E. Behavior Wat. Res., 1993, qw of Metals in Soils. Umschau, 1992, v. 79, p. [4] Eby G.N. Principle of environmental 778–783. Geochemistry. Thompson, 2004, 515 p. [17] Miller J. Contaminated rivers. [5] Forstner U., Heise S., Schwartz R., SperingerVerlag, 2007, 418 p. Westrich B., Ahlf W. Historical [18] Nath,R., Environmental pollution of contaminated sediments and soils at the cadmium: Biological , Physiological and river basin scale E examples from the Elbe health effects, interprint,New Dehli,1986. River catchment area. Journal of soils and [19] Nriagu, J.O., Global metal pollution: sediments, 2004, v. 4 (4), p. 247–260. poisoning the biosphere? Environment, 32(7),733,1990.

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[20] Odzak N. and Zvonaric T. Cadmium and lead uptake from food by the fish DUCENTRARCHUS LABREX. Wat. Sci. Tech., 1995, v. 32 (9–10), p. 49–55. [21] Pardo R., Barrado E., Perez L. and Vega M. Determination and speciation of heavy metals in sediments of the Pisuerga river. Wat. Sci., 1990, v. 24 (3), p. 373–379. [22] Prasad, A.S., Trace elements and Iron in Human metabolism, plenum medical book co., New York,1978. [23] Schroeder, H.A, The trace elements and nutrition : some positive and negative aspects, faber and faber, London,1976. [24] Siegel,H. (editor), Metal Ions in biological systems, Vol. 20, Concepts on metal Ion toxicity , Marcel Dekker inc., New York, 1986. [25] Underwood, E.J., Trace elements in human and animal nutrition, Ed. 4, Fig 1. Map of Iran , Esfahan province and study area Academic press, New York,1977. [26] Westrich B. and Kern U. Mobility of contaminants in the sediments of Lock regulated riversfield experiments in the lock reservoir Lauffen. Modelling and estimation of the remobilization risk of older sediment deposits (in German). Germany, Stuttgart, 1996, № 96/23. [27] Westrich B., Forstner U. Sediment Dynamics and Pollutant Mobility in Rivers An Interdisciplinary Approach. Springer Verlag, 2007, 430 p.

Author: BS in geology from Esfahan University (Iran), MSc in petroleum Engineering from Amirkabir university of technology (Tehran, Iran), MSc in sedimentology from Islamic Azad university, North Tehran branch, PhD in field of geoecology from Yerevan state university (Armenia), , vice-president in educational affairs in Islamic Azad Fig. 2. Location and name of stations in the map of university, Meymeh branch and head of young researcher club in Islamic Azad the Zayanderoud watershed. university, Meymeh branch

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Table 1. Allowed range for water, sediment and rock studied [recommended by [13].

Permissible limit in Permissible limit in sediment Mean in earth crust element

river water (ppb) and sedimentary rocks (ppm) (ppm)

10 0/62/7 0/40/57 Ti

0/025/8 80130 5360 V

0/32/1 80120 126185 Cr

0/260 0/17 12 Mo

0/02130 400850 7161400 Mn

66 3/34/7 %5 Fe

0/15 1420 1012 Co

0/8 4090 20 Ni

0/273/53 4060 2527 Cu

140 0/10/2 0/08 Ag

3/310/3 80120 5280 Zn

0/070/11 0/061/1 0/10/2 Cd

21000 %1%4 %8 Al

0/0073/8 100 14 Pb

0/119/4 513 0/52/5 As

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Table 2. Concentration of heavy metals in water and sediment samples of Zamankhan station (blank) and its

average in earth crust.

station Pole Zamankhan Earth Sediment Water crust Concentration (ppm) (ppb) (ppm) Standard Limit 130 5/8 V 53 Concentration 125 0/8 Standard Limit 7 60 Mo 1 Concentration 0/6 0/9 Standard Limit 12 10/3 Zn 52 Concentration 65/2 2/1 Standard Limit 13 9/4 As 0.5 Concentration 6/8 0/7 Standard Limit 60 3/5 Cu 25 Concentration 38 1/5 Standard Limit 4% 1000 Al 8% Concentration 59875 37/6 Standard Limit 850 130 Mn 716 Concentration 750 37/4 Standard Limit 4/7% 66 Fe 5% Concentration 35250 59/8 Standard Limit 90 0/8 Ni 20 Concentration 44/5 2/9 Standard Limit 100 3/8 Pb 14 Concentration 13/1 1/4 Standard Limit 1/1 0/11 Cd 0/1 Concentration 0/1 0/04 Standard Limit 20 0/11 Co 10 Concentration 14/2 <0/02 Cr Standard Limit 120 2/1 126

Table 3. Pollution levels recommended by [98]. >5 45 34 23 12 01 <0 Geoaccumulatio n index

Extremely much much Little Little Noncon Non Soil contamina cont… contami cont… _ contami taminat conta contamination ted _ nated much nated ed_ minat degree extrem cont… little ed ly cont…

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Table 4. The Analysis results of sediments of Zayanderud river (ppm). DOL for Fe (100) and for Mn (2) Station No Fe Mn 1 35220 750 2 38933 775 3 38560 840 4 39059 940 5 39162 692 6 41975 822 7 28138 542 8 36346 681 9 39600 700 10 28770 561 11 23513 615 12 24720 630

Table 5. The enrichment factor of Fe and Mn in different stations

Station No Station No Fe Mn 2 2 31.067 19.734 3 3 31.053 19.850 4 4 31.072 20.012 5 5 31.076 19.570 6 6 31.144 19.819 7 7 30.599 19.218 8 8 30.968 19.547 9 9 30.900 19.400 10 10 30.631 19.268 11 11 30.340 19.400 12 12 30.340 19.400

Table 6. Geoaccumulation index of Fe and Mn in different stations

Station No Station No Fe Mn 2 2 1,00 1.02 3 3 .97 1.08 4 4 .91 1.13 5 5 .95 .86 6 6 1.04 1.15 7 7 1.32 1.30 8 8 1.02 .97 9 9 1.10 1.01 10 10 1.19 1.19 11 11 1.37 1.90 12 12 1.45 1.95

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Fig 3. Manganese concentration in Zayanderoud river sediments in different stations

Fig 4. Ferrous concentration in Zayanderoud river sediments in different stations

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Fig. 5. Ferrous concentration changes in Zayanderud sediment samples.

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Fig. 6. Manganese concentration changes in sediment of Zayanderud river.

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