Health Promotion Perspectives, Vol. 1, No. 1, 2011; P: 62-70

ORIGINAL ARTICLE Open Access Effects of Abandoned Arsenic Mine on Water Resources Pollution in North West of

Behzad Hajalilou1, *Mohammad Mosaferi2, Fazel Khaleghi3, Sakineh Jadidi1, Bahram Vosugh1, Esmail Fatehifar4

1Department of Geology, Payame Noor University of Iran, , Iran 2National Public Health Management Center (NPMC), Department of Environmental Health Engineering, Tabriz University of Medical Sciences, Tabriz, Iran 3Department of Geology, Islamic Azad University, Tabriz Branch, Tabriz, Iran 4Environmental Engineering Research Center (EERC), Sahand University of Technology, Tabriz, Iran

(Received: 10 March 2011/ Accepted: 07 July 2011) ABSTRACT

Background: Pollution due to mining activities could have an important role in health and welfare of people who are living in mining area. When mining operation finishes, environ- ment of mining area can be influenced by related pollution e.g. heavy metals emission to wa- ter resources. The present study was aimed to evaluate Valiloo abandoned arsenic mine ef- fects on drinking water resources quality and possible health effects on the residents of min- ing area in the North West of Iran. Methods: Water samples and some limited composite wheat samples in downstream of min- ing area were collected. Water samples were analyzed for chemical parameters according to standard methods. For determination of arsenic in water samples, Graphite Furnace Atomic Absorption Spectrometric Method (GFAAS) and for wheat samples X – Ray Fluorescence (XRF) and Inductively Coupled Plasma Method (ICP) were used. Information about possible health effects due to exposure to arsenic was collected through interviews in studied villages and health center of Herris City. Results: The highest concentrations of arsenic were measured near the mine (as high as 2000 µg/L in Valiloo mine opening water). With increasing distance from the mine, concentration was decreased. Arsenic was not detectable in any of wheat samples. Fortunately, no health effects had been reported between residents of studied area due to exposure to arsenic. Conclusion: Valiloo abandoned arsenic mine has caused release of arsenic to the around en- vironment of the mine, so arsenic concentration has been increased in the groundwater and also downstream river that requires proper measures to mitigate spread of arsenic. Keywords: Arsenic mine; Pollution; Water; Health; Heydrogeochemistry; Iran

Introduction

Based on the definitions, environ- environmental burden of disease for high- mental pollutants e.g. heavy metals, which income, developed countries may range lead to disease, are those substances that from as low as 1 – 5% to as high as 15 - introduce in food, air, water, soil, or the 22% [4]. Between pollution sources of the home environment originally from human environment, mining activities has an im- [1-3]. According to available data, the total portant role in health and welfare of people

*Corresponding author: Dr Mohammad Mosaferi. Tel/fax:+98 411 335 5952) 1 Email: [email protected] Hajalilou et al.: Effects of Abandoned Arsenic Mine …

who are living in mining area. Although 1:a). Mining activities in which started mining activities have considerable effects since 1933 have been continued until 1997 in job creation and economic of a region, [22]. The main objective of this study was however such activities not only during to evaluate Valiloo abandoned mine effects operation phase, but also after mine clo- on drinking water resources quality and sure can result in pollution of soil, water, possible health effects between residents plants etc. When the mining operation will who are living in mining area. end, activities in the region be terminated, but its effects remain, and if not controlled Materials and Methods and reconstructed properly, environment of mining area can be influenced by related The study area, with surface over 95 pollution e.g. heavy metals [3,5], therefore, km2 is located in 103 km North East of it is necessary to take corrective measures Tabriz, Center of East Prov- to reduce related risks of mines [6]. ince. This area is a part of geological map From geological aspects, arsenopy- of Khajeh (Khoja) [22]. rite is the most abundant ore mineral of the To evaluate impact of abandoned arsenic and arsenic can be achieved from Valiloo arsenic (Zarnikh) mine, water roasting of arsenopyrite as well as smelter samples was collected in mining area dust of some metals like as gold, copper, (around and downstream of it). The sam- and lead [7]. Global resources of copper ples include sample from inside the mine and lead contain approximately 11 million opening, drinking water sources of villages tons of arsenic. World total production of around the mine and non-potable surface arsenic trioxide has been 59000 tons in and groundwater as following: 5 samples 2007 [8]. Arsenic is highly toxic mineral from wells, 3 samples from surface water, that founds in the earth crust and can intro- 2 samples of mine drainage water and 4 duce to food chain via soil, water, and samples of water distribution network plants [9, 10]. Consumption of water con- especially in downstream of the mine (Fig. taminated by arsenic is one of the main 1:b). Polyethylene acid washed containers sources of human exposure [11, 12]. It is with volume of 1 liter was used for sam- reported that contamination of groundwa- pling. Prepared samples were transferred to ter and drinking water by arsenic and re- the environmental chemistry laboratory of lated human health outcomes is a growing faculty of health and nutrition at Tabriz global concern [13]. Among arsenic spe- University Of Medical Sciences during cies, inorganic As (v) and As (III) in water several hours and were analyzed for physi- have highest toxicity comparing to organic cal and chemical parameters (hardness, species [9]. Chronic exposure to arsenic alkalinity, electric conductivity, Ca2+, via drinking water causes different disor- 2+ + + 2- - - - Mg , Na , K , SO4 , Cl , NO3 , F and ders like as skin lesions (hyperpigmenta- - HCO3 according to standard methods for tion and keratosis) [14,15], blood pressure the examination of water and wastewater [16], diabetes mellitus, internal and skin [23]. To determine the arsenic concentra- cancers [17], cardiovascular diseases [18], tion of samples, Graphite Furnace Atomic neurological disorders [14], pregnancy Absorption Spectrometric Method [19], metabolism [20], genetic [21] and (GFAAS) Buck scientific model was used. etc. Considering toxicity of arsenic, atten- Results of water samples chemical tion to arsenic mines during operation analysis were processed by Hydrochem phase and after closure takes more impor- and Surfer-8 software and Piper and Wil- tance. coks diagrams to determine the region-nal Valiloo arsenic mine has located in water quality and hydro geochem-istry of the North West of Iran (Heris city) (Fig. aquifers.

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In order to ensure the amount of ar- For collecting information about senic in wheat cultivated in the region as a possible health effects due to exposure to limited pilot study, composite samples of arsenic e.g. skin lesions (hyperpigmenta- wheat from different parts of 4 fields, were tion and keratosis), local investigations collected and analyzed for presence of As were performed through interviews in and also Ba, Cu, Zn, Pb, Ni, Ce, La, Nb studied villages and health center of Herris and Zr [24]. The samples were dried, pow- City. dered and finally analyzed with XRF [25] and ICP methods.

a)

b) Fig. 1: A: Location of study area on map of Iran (source: Google earth) , b: Sampling points on geological map of Khoja (1:100000)

64 Hajalilou et al.: Effects of Abandoned Arsenic Mine …

Results

According to our filed observations for ering sodium absorption rate (SAR), in geological aspects, host rock minerals 93% of samples, SAR was < 10 that means introducing arsenic in Valiloo region are excellent. However for EC, 33% of sam- sand stone, conglomerate, and red Miocene ples was unsuitable (2250 < EC <2500 silt that suffered from alteration near µs/cm). mineral zones construction. In faults and Most of waters in Valiloo district are bi- fractures of Valiloo region, small or big carbonate Calcic type that have temporary streaks contain orpiment and realgar hardness. Some samples are calcium chlo- (arsenic bearing material) is frequently ride and calcium sulfate with permanent observed. Deposit of arsenic in Valiloo is hardness and one sample was brine with epithermal sub-volcanic type. high content of NaCl. Considering type of Results of water samples analysis are stone of piper diagram, it appears that presented in Table 1. Based on the table, Valiloo region waters are different and also hardness was measured from 100 to 1500 have been affected by stone types. A group mg/L CaCO3. For electric conductivity, of water which include permanent hard- 2+ 2+ - 2- range was measured from 271 to 4600 ness and rich in Ca , Mg , Cl and SO4 µs/cm and for total dissolved solids (TDS) have located in region 1 of piper diagram from 168 to 2852 mg/L. pH value was > 7 and showing water have passed from rocks in all of samples. The highest containing gypsum (sulfate). Other waters concentration of Ca 2+ and Mg2+ was in with temporary hardness, which are rich in mine tunnel and For Na+ and Cl- was in Ca2+, Mg2+, HCO3-, are located in re- Yengjeh village water. gions 2, 3 and 5 of piper diagram that Arsenic concentration ranged from zero in originated from calcareous, dolomite some villages up to 2000 µg/L in mine stones. opening. Fig. 2 shows distribution of Waters of saline area are rich in Na+, K+, - 2- arsenic concentration in the studied region. Cl , SO4 , which located in region 6, 7 and As can be seen in figure, the highest con- 8 of piper diagram. Those waters have centrations of arsenic were inside and near originated and passed from the Chile and the mine that with increasing distance from brine rocks. the mine, the concentrations were de- Fig. 3 illustrates that arsenic was not creased. detectable in none of the wheat samples. Based on Wilcox diagram, most of water However, other analyzed element con- in the region was located in class C2S1 that centrations were higher in comparison with are almost suitable for agriculture. How- standard levels. ever, deep-well water (A13) in the south- Fortunately, during the interviews with the ern region has significantly higher salinity, residents of studied villages, none of per- placed in the class C3S2. Surface water sons complained from any routine arsenic- and water of mine tunnel have high salinity related health effects. so are not suitable for agriculture. Consid-

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a r s e n i c m rea a b nd o n e d V a lil oo i n Q u a li t y o f n l ze d w er s m p e : T a b l e 1

66 Hajalilou et al.: Effects of Abandoned Arsenic Mine …

Arsenic Concentration (ppb) Valiloo arsenic mine area

a01 a03 a10 a02

42244500000.00 a04a05 N a09 a14 42244400000.00 2000 1900 1800 42244300000.00 1700 1600 1500 1400 42244200000.00 1300 a08 a07 1200 1100 M

T 42244100000.00 1000 U 900 a11 800 42244000000.00 700 600 500 42233900000.00 400 300 200 100 42233800000.00 0

a06 42233700000.00 a13 a12 6666000000.00 662000.00 664000.00 66666000.00 668000.00 UTM Fig. 2: Distribution of arsenic concentration in studied area

Fig. 3: Concentration of analyzed elements in composite wheat samples of Valiloo area in comparison with standard levels

Discussion

Different researches in the world have pollution, and health effects of different been conducted for presence of arsenic in mines and mining activities. Many of these the environment [26], environmental investigations have reported pollution of

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soil, plants and water resources to arsenic drinking water quality in the region has and other heavy metals [27-33]. occurred due to a shift of water supply In the present study, we investigated form springs to wells. As a result, bladder probable water pollution and its health and kidney problems and diarrhea has affects due to Valiloo abandoned arsenic increased in the region. However, for mine. Study showed that in water which better understanding of related problems accumulated in tunnel of mine opening, organized research should be conducted by high concentration of arsenic (200 folds researchers. One of the limitations of higher than national drinking water present study was the lack of information standard [34] (MCL)), high TDS, hardness about water quality over past years. and EC was present. Also in groundwater Fortunately, according to performed inv- around the mine, concentration of arsenic estigations between residents of villages was as high as 50 folds > MCL. It is clear and health center through interviews, there that if such water introduce to the surface were not disorders related to exposure to water of region, arsenic pollution will be arsenic (e.g. hyperpigmentation and dispread to far distance. As a result, proper keratosis) between residents of mine area. actions should be considered for preventing this contamination. Considering Conclusion drinking water standards, springs around the Valiloo mine area are not potable. According to the study, Valiloo abandoned In surface water current in valley between arsenic mine has caused release of arsenic Valiloo village and mine as well as in to the around environment of the mine and water network of this village, concentra- has increased arsenic concentration in tion of arsenic was 35µg/L. However, in groundwater and downstream river that well water in Valiloo Village, concentra- requires proper actions to limit spread of tion was about 10µg/L. In water sample of arsenic. Although no adverse health effects a river downstream the mine; arsenic related to arsenic were reported by resi- concentration was 125µg/L. This high dents during the study, however future concentration was due to transfer of studies should not be neglected. arsenic bearing minerals from mine area to downstream by runoff and dissolution of Acknowledgments arsenic. Low hardness of Valiloo drinking water and presence of arsenic shows that The authors would like to thank the water originated from volcanic rocks with research deputy of Payam-e-Noor low mineral making [35, 36]. Absence of University for funding this study. The aut- arsenic in other analyzed water can be due hors declare that there is no conflict of to the role of natural iron compounds of interests. soil in adsorption of arsenic as a natural barrier [37, 38]. Our study showed that water of villages, References which placed in southern part of the region, had high concentration of magnes- [1] Sanchez M. Causes and effects of ium sulfate and hardness comparing to the heavy metal pollution. Nova Science northern parts. Considering national drink- Publishers, Inc; 2008. ing water standard [34], prolonged [2] Järup L. Hazards of heavy metal consumption of such water with mentio- contamination. Brit Med Bull 2003;68:167-82. ned quality can result adverse effects [3] Naja GM and Volesky B. Toxicity between residents. According to Herris and Sources of Pb, Cd, Hg, Cr, As, City Health Center information, change of and Radionuclides in the Environ-

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