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Environmental geochemistry of toxic heavy metals in soils around


Environ Earth Sci (2011) 62:449–465 DOI 10.1007/s12665-010-0539-x

ORIGINAL ARTICLE

Environmental geochemistry of toxic heavy metals in soils around Sarcheshmeh porphyry

copper mine smelter plant, Rafsanjan, Kerman, Iran
Mehdi Khorasanipour ? Alijan Aftabi

Received: 26 October 2009 / Accepted: 26 March 2010 / Published online: 14 April 2010 ? Springer-Verlag 2010

Abstract The Sarcheshmeh copper mine smelter plant is one of the biggest copper producers in Iran. Long-time operation of about 25 years of the smelter plant causes release of potentially toxic heavy metals into the environment. In this paper, geochemical distribution of toxic heavy metals in 28 soil samples was evaluated around the Sarcheshmeh smelter plant. Soils developed over the nonmineralized and uncontaminated areas have an average background concentration of 41.25 mg kg-1 Cu, 26.6 mg kg-1 As, 12.7 mg kg-1 Pb, 0.9 mg kg-1 Sb, 1.9 mg kg-1 Mo, 1.7 mg kg-1 Sn, 0.2 mg kg-1 Cd, 0.15 mg kg-1 Bi, 235 mg kg-1 S and 73.4 mg kg-1 Zn, respectively. As a result of smelting process, the upper soil layers (0–5 cm) were polluted by Cu ([1,397 mg kg-1), Cd ([3.42 mg kg-1), S ([821 mg kg-1), Mo ([10.3 mg kg-1), Sb ([11.7 mg kg-1), As ([120.6 mg kg-1), Pb ([83.8 mg kg-1), Zn ([214.9 mg kg-1), and Sn ([3.7 mg kg-1), respectively. These values are much higher than the normal concentration of the elements in the uncontaminated soil layers. The elemental values decrease with distance travelled away of the smelter plant, especially at minimum wind direction. Furthermore, high contaminated values of Cu (8,430 mg kg-1), As (500 mg kg-1), Pb (331 mg kg-1), Mo (61 mg kg-1), Sb (56.2 mg kg-1), Zn (664 mg kg-1), Cd (17.2 mg kg-1), Bi (13.4 mg kg-1), and S (3,780 mg kg-1) were observed in the upper soil layers close to the smelting

waste dumps. Sequential extraction analysis shows that about 270 mg kg-1 Cu, 28 mg kg-1 Pb, 50.33 mg kg-1 Zn, and 47.84 mg kg-1 As were adsorbed by Fe and Mn oxides. The carbonate phases include 151 mg kg-1 Cu, 28 mg kg-1 Pb, 25 mg kg-1 Zn, and 32.99 mg kg-1 As. Organic matter adsorbed 314.6 mg kg-1 Cu and 29.18 mg kg-1 Zn. Keywords Sarcheshmeh porphyry copper smelter plant ? Soil toxic heavy metals ? Sequential extraction analysis ? Contaminated upper soil layers

Introduction Heavy metal contamination of soils around smelter plants and waste sites is a common geoenvironmental problem. Soil as a part of biogeochemical system plays a crucial role in elemental cycling and has important function as storage, buffer, ?lter, transformation compartment, and supporting interrelationship between the biotic and abiotic component (Merain et al. 2004; Soylak and Turkoglu 1999; Tumuklu et al. 2007). Metal mining, smelting, and processing introduce heavy metals in excess of natural soil background concentration (Dudka and Adriano 1997; Selim and Sparks 2001 Callender 2005; Selinus 2005). During the smelting of metalliferous ores, many metals such as Sb, As, Bi, Cd, Cr, Co, Cu, Pb, Hg, Ni, Ta, Se, and Zn and metalloids are released into the soil (Selinus 2005). The environmental impact of potentially above-mentioned toxic heavy metals due to anthropogenic activities has been frequently investigated (Adriano 1986; Chuan et al. 1996; Cambier 1997; Dijkstra 1998; Sheppard et al. 2000; Cezary and Bal Ram 2001; Burt et al. 2003; Soylak and Turkoglu 1999; Saracoglu et al. 2009). Toxic metal pollutions are critical because the soil can purify only

M. Khorasanipour Department of Earth Sciences, Shiraz University, Shiraz, Iran A. Aftabi (&) Department of Geology, Shahid Bahonar University of Kerman, P.O. Box 76135-133, Kerman, Iran e-mail: aftabi@mail.uk.ac.ir

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slowly and partially, so pollutants tend to be accumulated in soil (Lim et al. 2005; Luo et al. 2005; Meers et al. 2005). The geochemistry of potentially toxic heavy metals in soil depends primarily on the type and chemistry of parent material from which the soil derived, but anthropogenic inputs especially as a result of smelting of ores may lead to concentration highly exceeding those from natural sources (Siegel 2004; Callender 2005). Descriptions of notable examples of toxic metal geochemistry in Iran are rare and exciting. The Sarcheshmeh porphyry copper mine is one of the world’s largest Miocene porphyry copper deposits. The

approach in this paper is to study the geochemical aspects of potentially toxic metals in soils around Sarcheshmeh Copper smelter plant, especially around the Sarcheshmeh Township.

Geology, site characteristics and mineralization The Sarcheshmeh porphyry copper mine is situated about 160 km southwest of Kerman city, southern Iran (Fig. 1). Approximately, up to 70% of the geology of this area is composed of Eocene basic to intermediate volcanic rocks

Fig. 1 Central Iranian tectonovolcanic belt and location of the Sarcheshmeh porphyry copper deposit in the Dahaj-Sarduiyeh subdivision belt (modi?ed after Shahabpour and Kramers 1987; Dimitrijevic 1973)

Central Iranian volcano-plutonic copper belt Sarcheshmeh Porphyry Copper Deposit

Porphyry Copper Mineralization

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Smelter plant

Sarcheshmeh mine

Sampling location

Roads

Fault

Drainage

Dacite

Quaternary

Sandstone and pebbly sandstone

Calcareous terraces

Fresh and alterd quartz diorite, quartz monzonite and granodiorite

Fresh and altered Trachybasalt and Trachyandesite

Wind direction

Fig. 2 Geological map around Sarcheshmeh porphyry copper mine smelter plant (modi?ed after Dimitrijevic 1973)

with composition of trachybasalt, trachyandesite ± andesite (Dimitrijevic 1973; Anonymous 1973) (Fig. 2). The Miocene stockwork-vein porphyry copper mineralization occurs both in granitoid intrusive phases (quartz diorite, quartz monzonite, and granodiorite), trachybasalt and trachyandesite (Bazin and Hubner 1969; Dimitrijevic 1973; Etminan 1977; Ghorashizadeh 1978; Shahabpour 1982; Aftabi and Atapour 1997, 2000; Hezarkhani 2006). The potassic and phyllic mineralized zones are composed of pyrite, chalcopyrite, quartz, bornite, and molybdenite with minor amounts of sphalerite, galena, and magnetite. The Sarcheshmeh copper mine contains about 1,200 million tones ores with an average grade of 1.2% copper, 0.03% molybdenum, 3.9 g/t Ag and 0.11 ppm Au (Waterman and Hamilton 1975; Ellis 1991). Annual temperature of the area ranges between -20 and 32°C with

mean rainfall of 440 mm and annual evaporation of about 1,170 mm (Shirashiyani 2004). As a result of climate condition, development of soil pro?le is restricted, and most of soils are classi?ed as inceptisol or young immature soils (Fig. 3). The Sarcheshmeh copper smelter plant started to work in 1981 (Shirashiyani 2004), and mainly uses up to 90% matte by pyrometallurgical methods to produce copper. As a result of smelting process, 136,000 m3 h-1 gases that contain 2.6% SO2 are released by convertor furnaces. Also, reverberatory furnaces release 136,000 m3 h-1 of gases with 4.8% SO2 into the atmosphere (Ebrahimi and Hakimi 2002). Geochemical data show that many potentially toxic metals such as Cu, As, Sb, Pb, Zn, Mo, Cd, Bi, and Sn are detected in emitted gases (CAQC 2003). Release of these toxic elements into the natural environment around smelter

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Thin A horizon

Bedrock

Fig. 3 A typical immature soil pro?le in the area (depth of soil is approximately 50 cm)

plant can increase natural baseline of these elements considerably and cause disturbances in geochemical and possibly biogeochemical cycles of metals.

Materials and methods Bulk samples Field studies show that soil pro?les depth are mainly between 30 and 50 cm and commonly consist of coarse-grained material from trachybasalt and trachyandesite. Sampling of soil pro?les were done in four levels, including surface soil horizon (0–5 cm), intermediate soil horizon (2–20 cm), deep soil horizon (20–45 cm), and bedrock (mainly[45 cm). For the selection of soil pro?le factors such as vicinity to smelter plant, Sarcheshmeh township and minimum and maximum of local wind directions were considered. Beside soil pro?les, some samples from surface soil (0–5 cm) especially around smelting waste dumps were also collected. Generally, about 28 samples were collected (Fig. 2). Particular caution was taken to avoid metal contamination during sampling of the soil. A normal soil sample showing the background nature of the uncontaminated and/or unminersalized zones was sampled. Selective subsampling and selective chemical extraction In many geochemical studies, a bulk sample is analyzed for its potentially toxic trace metals (Colbourn and Thornton 1978; Hernandez et al. 2003; Horchmans et al. 2005).

However, because of dilution effects on the metal content in the bulk samples, the resulting data may demonstrate that some metal values are evaluated but to the levels that fall within natural limit or geochemical baseline, which could be misleading (Siegel 2004). Therefore, selective subsampling and selective chemical extractions is necessary to clarify bioavailability of metals from a geochemical source. Commonly, the metal concentration in the ?ner fraction is more than other size fractions by natural adsorption onto the charged surface of minerals and associated amorphous solids (Siegel 2004). As a result of particulate pollution near smelting plants, the distribution of metals in various size fractions of soil must be changed considerably. In this study, surface soil samples (0–5 cm) at three locations with respect to smelting plant were separated in three diameters (d [ 2 mm, 0.11 \ d \ 2 mm, and d \ 0.11 mm). In order to prevent the sample contamination, plastic sieves were used for separation of soil sub-samples. Selective chemical extraction of potentially toxic metals from soil or sediments provides insight on how the metals are incorporated in various component phases (Kramer and Allen 1988; Jason et al. 2001; Gleyzes et al. 2002; Peijn¨ enburg and Jager 2002; Forstner et al. 2004; D’ Amore et al. 2005; Sauquillo et al. 2003). This approach also was used in environmental evaluation of toxic heavy metals around several smelter plants (Burt et al. 2003; Cezary and Bal Ram 2001). In this study, the Tessier et al. (1979) procedure was selected for selective chemical extraction. Analytical method For total metal determination, only ?ne fractions (\2 mm) of the representative samples from the air-dried soils were chosen to be analyzed after crushed with tungsten grinder. To avoid the possible contamination, the grinder capsule was washed with distilled water after each sample preparation. Total concentration of potentially toxic metals was measured with inductively coupled plasma optical emission spectrometry (ICP-OES) method in Amdel laboratory, Perth City, Western Australia. Also check samples were submitted to Als Chemex laboratory, Canada. The precision, accuracy, and limit of detection for analyzed samples were calculated according to Quevauviller (1995) (Table 1). The accuracy and precision of analysis are higher than 90%, except for Ag which is 73 and 71%, respectively. In fact, the differences between data for check samples are below 10%. Following the sequential extraction procedure of Tessier et al. (1979), chemical partitioning allow to distinguish ?ve fractions representing the following chemical phases; exchangeable metals, carbonate minerals, Fe–Mn oxides, sul?des, organic matters, and residential fraction. The

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Immature soil layers (≈ 50 cm)

Environ Earth Sci (2011) 62:449–465 Table 1 Limit of detection, accuracy, and precision for heavy metals Element Method of Detection limit Data of analysis for repeated sample in different laboratories (mg kg-1) analysis (mg kg-1) Laboratory Aa Cu Cd Fe Zn Ni Mn Pb Cr As Co S Al Bi Sb Sn Ag
a b

453

Accuracy (%) Data of analysis for repeated sample (mg kg-1) Laboratory Aa 99.0 88.1 96.2 90.8 92.4 96.7 93.4 62.6 96.3 85.0 91.4 98.4 93.3 95.9 99.5 73.6 9,170 3.6 71,900 943 44 902 170 50 144 38.8 27,800 70,400 1.7 36.4 2.6 0.87 8,810 4.3 70,400 930 42 871 184 42 123 36.9 27,650 68,800 1.8 41.1 2.7 1.56

Precision (%)

Laboratory Bb 8,590 13.55 47,900 552 32.6 919 385 46 538 24.6 3,180 82,300 11.7 60.9 10.3 3.52

IC3M IC3M IC3E IC3M IC3E IC3E IC3E IC3E IC3M IC3M IC3E IC3M IC3M IC3M IC3M IC3M

0.2 0.05 100 0.2 2 2 2 2 0.5 0.2 50 10 0.1 0.1 0.2 0.01

8,430 17.20 44,400 664 28 865 330 21 500 18.2 3,780 79,800 13.4 56.2 10.2 2.05

97.9 91.2 98.8 99.3 97.6 98.2 96.0 91.3 92.1 97.4 99.7 98.8 97.1 93.9 98.1 71.63

Amdel laboratory, Perth City, Western Australia Check sample submitted to Als Chemex, Canada

procedure was carried out with an initial weigh of 1 g of the sieved dry soil samples. The sequential extraction procedure is described as the following (Tessier et al. 1979). Fraction 1 includes exchangeable phases, in which the samples were extracted at room temperature for 2 h with 25 ml of 1 M NaOAc (pH 8) with continuous stirring. Fraction 2 contains the carbonate phases that formed by washing residue of fraction 1 at room temperature with 20 ml NaOAc (adjusted to pH 5 with HOAc) for 3 h with continuous stirring and the pH was controlled during stirring and adjusted to pH 5 with HOAc. Fraction 3 contains oxide phases extracted from the residue of fraction 2 with 20 ml of 0.04 NH2OH?HCl in 25% HOAc (v/v) for 6 h at 80°C and at pH 2 in a water bath with occasional stirring. Fraction 4 comprises of organic phases, which was extracted by residue of fraction 3 and was added 8 ml of 0.02 M HNO3 and 12 ml of H2O2 30% (adjusted to pH 2 with HNO3). The mixture was heated to 80°C and occasionally stirred. Fraction 5 consists of residual phase that formed by the residue of fraction 4 and was digested with 6 ml of HF (40%) and 6 ml HClO4 for 5 h. Reagents used for sequential extraction were of high purity and quality and include NaOAc HOAc, H2O2, HClO4, and HNO3 (Merck, Darmstadt, Germany), HF (Fluka, AG, CH-9470 packed in Switzerland), and NH2OH?HCl (Fluka, A Sigma-Aldrich Company, USA).

Results Physical and chemical properties of soil horizons The soil texture mainly ranges from coarse-grained loamy sand to sandy loam with maximum 14% clay, 90% sand, and 35% silt that are characteristics of the immature soils. In arid and semiarid regions, as a result of formation of Ca carbonate and other evapotranspiration salts, pH values of soil commonly ranges between 7 and 9. The pH values of soil samples are in the range 5.2–7.8. The low pH values of soil occur around smelter plant and might be due to SO2 emitted by the smelting process and acidic particulates. Most samples had organic matter between 0.08 and 1.4% and cation exchange capacity values are varied between maximum 20 meq/100 g to minimum 5.8 meq/100 g. Total concentration of metals in the studied soil samples re?ects both natural differences in soil genesis, properties, and degree of contamination from anthropogenic sources. Table 2 indicates elemental values in soil samples and Fig. 4 shows trend of variation of these elements in soil pro?les. The distribution of heavy metals within the depth of soil could indicate the relative mobility of metals originated from surface-deposited contamination (Selim and Sparks 2001). The soil pro?les that developed over gossan have high natural concentration of As (162.5 mg kg-1), Sb (32.8 mg kg-1), Pb (105 mg kg-1), Cu (184 mg kg-1),

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454 Table 2 Distribution of heavy metals in soil pro?les and sur?cial soil samples (mg kg-1) Sample Sample no location 1 North of smelter plant Distance from Sample smelter plant depth (km) 5 0–5 cm 5–20 cm 20–40 cm Bedrock 2 Township 5.35 0–5 cm 5–20 cm 20–40 cm Bedrock 3 West of smelter plant 2.55 0–5 cm 5–20 cm 20–40 cm Bedrock 4 North west of smelter plant 15 0–5 cm 5–20 cm 20–40 cm Bedrock 5 Pro?le over gossan 4.43 0–5 cm 5–20 cm 20–40 cm Bedrock 6 Township 4.94 0–5 cm 5–20 cm 20–40 cm Bedrock 5 Township 4.34 0–5 cm 5–20 cm 20–40 cm Bedrock 8 9 10 11 12 13 14 15 16 17
a b

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Element concentration (mg kg-1) Pb 113 26.7 21.5 35.1 49.5 23.4 27.5 12.2 60 15.2 12.9 8.8 22.1 17.8 15.5 10.2 129 As 116 10.7 8.4 9.7 53.6 22.4 14.6 4.4 121 32.4 26.2 12.9 17.3 16.7 14.1 9.1 136 Cu 1,220 104 111 53.7 311 97.5 148 225 479 55.6 46.3 90.5 124 120 143 216 300 125 117 142 232 44.6 36.2 32.5 813 73.2 71.7 46.2 146 188 1,760 376 1,320 1,500 8,430 41.25 34 28 Mo Sb Zn 240 98.9 87.8 89.8 134 98.9 101 91.3 169 94 93 86 98 105 124 69.5 263 199 342 461 118 62.7 53.8 68.8 99.8 83.8 75.9 106 117 246 194 202 256 664 73.4 36 67 Sn Cd Bi 2.3 bdl bdl 0.1 0.6 0.1 bdl bdl 1.3 0.2 0.2 bdl 0.2 0.1 bdl 1 0.2 0.2 0.2 0.6 0.1 0.1 bdl 0.1 bdl bdl 0.2 0.3 0.7 0.8 1.3 2.7 S 710 50 60 160 320 250 100 bdl 400 160 150 bdl 100 60 bdl 150 130 180 70 390 280 320 bdl 180 60 310 150 280 2,090 260 990 910

7.9 13.9 1.1 1.1 1 2.7 1.9 1.8 1.2 3.7 1.9 1.8 1.4 3 1 0.7 0.6 0.7 0.5 0.6 4.1 1 0.8 0.5 7.6 1.2 0.9 0.3 0.75 1 0.6 0.4

4.6 4.7 1.4 0.4 1.6 0.1 1.4 0.2 2.8 1.2 2.1 0.3 2.4 0.1 2.4 bdl 3.5 2.5 1.9 0.1 1.9 0.2 1.6 bdl 1.8 0.3 1.5 0.1 1.4 0.1 2.4 1.6 2 0.7 1.9 1.3 1.2 0.4 2.6 1.2 1.6 0.2 1.5 0.2 2.5 bdl 2.5 0.2 2.3 bdl 1.6 0.2 2.1 0.5 2.9 0.6 3.1 1.7 2.8 1.7 2.9 3.3 4.5 5.6 1.7 0.2 2 0.5

1.7 0.21 0.18 100

9.6 30.2 2.3 21.2 4.3 47 1.6 50.1 2 1.1 2 2.6 3 2.3 2.7 2.6 2.9 2.6 3.9 0.9 0.9 0.9 1.3 1 1 2 3

88.5 94.7 97.7 197 21.1 38.4 15.5 12.5 19.7 56.1 34.8 26 25.9 23.1 36.5 73.5 53.7 105 338 12.7 47 17 98.7 53.9 17.8 15 6.4 51.9 24.6 21 5.6 51.8 43.3 67.2 67.4 151 500 20.6 13.75 4.8

4.09 133

2.8 0.84 0.52 300

West of township Township Around smelting waste (vicinity of township) West of smelter plant Vicinity of smelter plant Northeast of smelter plant Around smelting waste Background soil township Average worldwide soila Crustal abundanceb

6.90 5.87 6.7 5.87 0.5 2.8 2.1 – – –

0–5 cm 0–5 cm 0–5 cm 0–5 cm 0–5 cm 0–5 cm 0–5 cm – – –

14.4 14.3 2.1 9.6 5.7 8.8

57.4 171

12.4 17.1 61.1 56.2 1.9 2 1.1 0.9 2 0.4

10.2 17.2 13.4 3,780 0.15 235 0.2 300

2.1 0.09 0.16 621

bdl below detection limits McBride (1994) Rudnick and Gao (2003)

Mo (5.4 mg kg-1), and Zn (268 mg kg-1) with respect to other soil pro?les. The process of gossan formation especially around porphyry copper deposits started with oxidation of pyrite

and other sul?des to form Fe oxyhydroxides plus sulfuric acid. Amorphous ferric hydroxide and associated minerals with Fe oxides such as jarosite, gypsum, clay minerals, and silica are important products from weathering of gossan.

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During gossan formation, trace metals are strongly adsorbed by initial amorphous to very ?ne-grained precipitates and the amount of adsorbed elements decreases in strongly acidic solutions (Rose et al. 1979; Thornber 1985). At mildly acid to neutral pH values, trace metals are sorbed or coprecipitate with Fe oxides. Generally, Pb, Cu, and Ag are strongly adsorbed by iron oxide and elements occurring as anion complexes such as Mo, As, and Se are strongly sorbed to Fe oxide under acidic condition (Atapour and Aftabi 2007). The immature gossans around Sarcheshmeh porphyry deposit contain high values of Cu (160.3 mg kg-1), Zn (826.7 mg kg-1), and Pb (88.6 mg kg-1) (Atapour and Aftabi 2007). These values are similar to those in soil pro?les that we investigated. Therefore, soils over gossan are immature and have natural concentration of some potentially toxic trace metals. In soil pro?les that are situated in maximum direction of wind and at the vicinity of smelter plant, the contents of Cu, As, Cd, Pb, Bi, Zn, Mo, Sb, Sn, and S (Fig. 4) in surface soil layers (0–5 cm) are considerably higher than deeper soil layers and bedrock. The surface enrichments of metals in the soils are related to wind-transported pollutants. This anomalous distribution of metals is similar to the soil values around smelting plants reported by Schroeder and Lane (1988) and Rasmussen (1998). Also, some studies (McBride et al. 1997; Dijkstra 1998) show that trace toxic metals have been found to be accumulated in surface organic layer by plants accumulation from lower horizon or chemical complexing of metals by organic compounds. As a result of the weakly developed soil pro?les in this region and low organic matter in surface soil samples (maximum 1.4%), the role of plants or organic compounds in surface enrichment of the metals are less important. Scocart et al. (1983) presented soil pro?le distribution of Cd, Pb, Zn, and Cu in two soil types (e.g., sandy acidic and loamy neutral soils) that were taken directly adjacent to Zn smelter plant. For both soil types, the total metal concentration was greater in soil samples closer to the smelter site. However, for loamy soils at neutral pH, the majority of the heavy metals remained in the upper soil layers. Other trace metals such as Cr, Co, and Ni appear to have a more uniform surface and subsurface distribution, suggesting either more limited or no deposition from smelter. Soil pro?les that are situated in Sarcheshmeh Township also show some enrichments for Cu, S, Pb, As, and Mo in sur?cial soil layers, but because of increases of distance from smelter plant the amount of pollution is decreased. Soil pro?les that are located in minimum wind direction and maximum distance from the smelter plant have more uniform distribution of all toxic metals. The distribution of elements in these soil pro?les and soil pro?les that developed over gossan shows that the concentration of trace metals in virgin soil depends mainly

upon the bedrock type from which the soil parent materials were derived. High level of contamination in soils around smelting waste dumps by As, Cu, Cd, Pb, and Mo is a remarkable issue that demonstrates and these materials contribute to the soil pollution (Siegel 2004). Schroeder and Lane (1988) and Rasmussen (1998) showed that As is a volatile element and was least likely to be deposited at vicinity of the source of pollution as trended to remain in the atmosphere, where it was subjected to a long-range transport. Therefore, it is obvious that the source of such elements conforms to the smelted waste and dust rather than stack and fugitive gases (Farago 1980; Verner and Ramsey 1996). The correlation coef?cient matrix is listed in Table 3. In general, the correlation between contaminated elements is signi?cantly obvious. In contrast, the association of Cr, Ni, Co, and other elements are generally weak, so these elements in soil may come from different sources of natural origin. By considering the association of contaminated toxic metals in different soil horizons, the scatter plots give signi?cant relationships. The scatter plots between As and Cd, As and Sb, Cd and Zn, Zn and Sb, and As and Zn (Fig. 5) show that these elements in soil are well correlated and do not give remarkable differences between soil layers and bedrock. In contrast, the positively and signi?cant association of As–Cu, Bi–Cd, Cd–Sn, Cu–Zn, Cu–Mo, Cu–Pb, Cu–S, Cu–Sb, Cu–Zn, Mo–S, Pb–Mo, Pb–S, Sb–Mo–S, S–Bi, Sb–S, and Zn–S in surface soil layer is considerably different from subsoil layers and bedrock that are less signi?cant (Fig. 6). As showed by Tumuklu et al. (2007) heavy metals that have high and medium level of positive correlation are released from the same source. Accordingly, the positive correlation among the heavy metals in sur?cial soil samples is consistent with contaminated source of the Sarcheshmeh smelter plant. Sequential extraction for Cu, As, Pb, Mo, Zn, and Cr has been done in surface soil samples at three sites similar to the selective physical sub-samples. The changes of metals in various component phases (F1–F5) are different for soil at these sites (Fig. 7). The results show that the pedological compartment especially Fe and Mn oxyhydroxides, carbonate phases, and organic matter effectively adsorb heavy metals. These factors are effective in delaying metal translocation in the soil and likely decreasing its toxicity ? ¨ (Keller and Vedy 1994; Forstner 1991). Enrichment factor and index of geoaccumulation The enrichment factor represents the amount of the excess of particular element that expected from a natural rock or soil source. It is often assumed that the content of elements

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b Fig. 4 Evolution of toxic heavy metal concentration in soil pro?les (mg kg-1) (?lled diamond north of smelter, ?lled triangle soil pro?le developed over gossan, ?lled square west of smelter, open triangle, open square, open circle soil pro?le in Sarcheshmeh township, ?lled circle soil pro?le that situated 15 km far from smelter in minimum wind direction)

Table 3 Correlation matrix between heavy metals in soil samples Pb Ag 0.9 Bi S Sn As 0.9 Sb Cu Mo Zn Cd Sn S Bi Ag

0.72 0.93 0.94 0.86 0.92 0.89 0.3 0.7 0.82 0.78 0.73 0.71 1 0.93 0.85 0.97 1 1

0.93 1

0.92 0.9

0.94 0.97 0.35 0.98 0.95 0.13 1

0.82 0.75 0.71 0.9 0.91 0.88 0.66 0.9

Cd 0.93 0.93 0.72 0.93 0.96 0.84 1 Zn 0.96 0.96 0.93 0.89 0.9 Mo 0.92 0.91 0.74 0.97 1 Cu 0.94 0.89 0.75 1 Sb As Pb 0.88 0.88 1 0.95 1 1

where [M]Total and [M] are the concentration of trace metals in soil sample and references respectively and [Al] is total concentration of Al (mg kg 1-1). The results of these calculations are summarized in Table 4. These results show that Cu, Mo, Cd, Sb, As, and S have the maximum enrichment caused by anthropogenic source. Also Pb, Zn, Bi, and Sn have some enrichment in surface soil samples but in lesser order than previous elements. An important point is that in soil pro?les that developed over the gossan, the enrichment factor and anthropogenic sources are in the range of normal values similar to those pro?les that are situated faraway from the smelter plant. ¨ The geoaccumulation index (Muller 1979) can be used to assess the degree of contamination. This index is calculated as follows: Igeo ? log2 ?Cn =1:5Bn ? where Igeo is the geoaccumulation index, log2 is log base 2, Cn the concentration in the soil or sediments, and Bn the background or references concentration. After the geoaccumulation index has been calculated, it can be used to classify the soil in terms of quality (Table 5). In calculation of Igeo, the background value (Bn) is the concentration of toxic elements in deeper soil layers. The Igeo, for Cu, Mo, Cd, As, Sb, Pb, Zn, Sn, Cr, Co, Mn, and S in studied soils are indicated in Fig. 8. According to the index of geoaccumulation (Igeo), the degree of contamination from the most to the least in studied soils are Cu [ Cd [ S [ Mo [ Sb [ As [ Pb [ Zn [ Sn [ Cr & Co & Mn. These results indicate that some soil samples are very highly to highly polluted by Cu and Cd. Elements such as S, Mo, As, Sb, and Zn are highly to moderately polluted in soil samples, but Cr, Ni, Co, Mn, and other elements were considered to be uncontaminated. General discussion The distribution of toxic heavy metals at three investigated sites shows that trend and variations of these elements are considerably various in separated surface soil sub-samples (Fig. 9). The values for Cu, As, Zn, Cd, Mo, S, Pb, Sb, Sn, and Bi near smelter plant are higher than the other sites. In contaminated soils, the values of these elements in separated sub-samples decrease in this order: ?ner traction [ medium fraction [ bulk sample [ coarse fraction. It seems that in the vicinity of pollution sources such as smelter plant, the concentration of metals in ?ner fraction is increased due to natural sorption. In two other sites with increasing distance from the smelter plant, the concentration of metals decrease considerably and the difference between concentrations of metals in separated sub-samples

Correlation is signi?cant at the 0.01 level (two-tailed)

such as Al, Y, Sc, Ti, and Zr in natural medium (e.g., soil) is due solely to crust or geogenic source. In order to evaluate if the present-day heavy metal content in soil derives from natural or anthropogenic sources, an enrichment factor for soil samples was calculated using Al as an immobile reference element (Eby 2004). The reference values were taken on one hand from bedrock values (Eq. 1) and on the other hand, for all the considered metals from the concentrations in each deepest soil horizon (Eq. 2) proposed by Hernandez et al. (2003) ?  ? EF1 ? ??M ?=?Al??soil ??M ?=?Al?? Bedrock ?1? EF2 ? ??M ?=?Al??soil =??M ?=?Al??Deeper soil horizon ?2?

where [M] = total heavy metal concentration in soil samples (mg kg 1-1) and [Al] total concentration of Al (mg kg-1). In this calculation, EF near 0.5 and 2 can be considered in the range of natural variability, whereas ratios greater than 2 or 3 indicate some enrichment corresponding mainly to anthropogenic inputs. Also the percentage contribution of anthropogenic source is calculated from Eq. 3, proposed by Hernandez et al. (2003) and Eby (2004). n % Anthro ? ?M ?Total  0 ? ?Al?Sample ?M ?=?Al?Reference material o ?M ?Total ? 100 ?3?

123

458

Environ Earth Sci (2011) 62:449–465

Fig. 5 Scatter plots between As and Cd, As and Sb, Cd and Zn, Zn and Sb, and As and Zn in investigated soil pro?les (mg kg-1)

are less important and caused by natural geology and soil formation process. The metal values from sequential analysis are low in exchangeable fraction at three sites (F1). This smaller proportion of more soluble fraction may be due to high soil pH ([7) accompanied with large amounts of carbonates. The high pH and carbonate content provide buffering against acidi?cation that result in a less soluble and therefore, less mobile fraction of trace metals (Burt et al. 2003). Also, elements attributed by smelter contamination may initially exist in more reactive forms and could be transformed to less reactive forms over time (Ma and Uren 1995). Cr does not seem to have an anthropogenic pollution source in studied soils, thus mostly occurs as F5 fraction (Residual, up to 87%) in soil samples. This partitioning also shows that most of the Cr is relatively immobile. Copper in soil sample near smelting plant is mainly distributed by F4 (organic matter 39.5%), F3 (Fe and Mn oxides 33.9%), and F2 (carbonate phases 18.9%) phases. The greater proportion of Cu in these speci?c fractions is associated with smelter emissions (Kabala and Singh 2001; Karzewska 1996). The result from the sequential extraction studies indicates that in the contaminated soils; copper was adsorbed by organic matter and Fe, Al, and Mn oxides (Levesque and Mathur 1996; Grazebisz et al. 1997; Nyamangara 1998). The Distribution of Pb in soil samples near the smelter plant is associated with Fe and Mn oxides (F2) and carbonate phases (F2) about 36.76 and 30.35%, respectively. In contrast, in two other samples up to 68% of

Pb is present in residual fraction. Zinc shows similar distribution pattern as Pb in different phases. These natural sorbents decrease the bioavailability in the contaminated soils near smelting plant. Arsenic and Mo have higher values in exchangeable fraction, about 12.9 and 12.2%, respectively. Molybdenum has maximum values in residual fraction of the soil. Although arsenic has the same distribution as Mo, but it seems that this element is partially adsorbed by carbonate phases (F2 14.8%) and Fe and Mn oxides (F3 21.5%) in the soil samples around smelting plant. On the basis of the distribution of metals in various soil phases, the relative index of metal mobility was calculated as ‘‘mobility factor’’ (MF: Salbu et al. 1998; Narwal and Singh 1999) by following equation: MF ? f?F1 ? F2 ? F3?=?F1 ? F2 ? F3 ? F4 ? F5?g ? 100 Metal forms extracted in F3 are relatively less mobile than metal extracted in F1 and F2, which are strongly bound to the soil component and the above-mentioned index described their potential mobility (Salbu et al. 1998). The relative mobility of metals increases in soil near the smelting plant (Table 6) except of Cr that has approximately the same MF in all samples (\7%). Among the investigated metals, Pb and Cu with 67.9% and 53.6% have the maximum MF close to the smelting plant. As a result of smelting process, the contents of toxic metals are increased in soils. Part of this pollution is adsorbed

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459

Fig. 6 Scatter plots between As and Cu, Bi and Cd, Cu and Sb, Sn and Cd, Cu and Zn, Cu and S, Pb and Cu, Mo and Cu, Mo and S, Mo and Zn, Pb and S, Pb and Mo, Sn and Bi, Zn and S, and Sb and S in investigated soil pro?les (mg kg-1)

123

460 Fig. 7 Distribution of Cu, As, Pb, Mo, Zn, and Cr in chemical sequential extraction phases (mg kg-1) (F1 the exchangeable phases, F2 the carbonate phases, F3 the oxide phases, F4 the organic phases, and F5 residual fraction)

Environ Earth Sci (2011) 62:449–465

350 300

120 100

Cu (mg kg-1)

As (mg kg )

-1

250 200 150 100 50 0 F1 F2 F3 F4 F5 Near Factory Townshipe Background

80 60 40 20 0 F1 F2 F3 F4 F5 Near Factory Townshipe Background

35 30

6 5

Pb (mg kg )

Mo (mg kg )

-1

20 15 10 5 0 F1 F2 F3 F4 F5 Near Factory Townshipe Background

-1

25

4 3 2 1 0 F1 F2 F3 F4 F5 Near Factory Townshipe Background

90 80 70 60 50 40 30 20 10 0 F1 F2 F3 F4 F5

60 50

Zn (mg kg )

Cr (mg kg )

-1

40 30 20 10 0 F1 F2 F3 F4 F5 Near Factory Townshipe Background

Near Factory Townshipe Background

and neutralized by carbonate phases, Fe and Mn oxides and organic matter, which may be available for translocation through food chain and biogeochemical cycles. Also, it is notable that any decrease in pH of soils by acidic deposition may decrease the retention of metals by the oxide fractions (e.g., aluminum, iron, and Mn oxides). This is reported to be effective in the pH values below the zero point of charge (Wilkens and Loach 1997). It is obvious that most of toxic metals are also convey in biological cycle through sur?cial pollution of plants. The Sagebrush plant in the area was chosen as an index of sur?cial pollution of plants. The plant grows in temperate climates of the northern hemisphere and southern hemisphere, usually in dry or semi-dry habitats (Watson 2002). The results show that Cu, Zn, Pb, As, Sn, Sb, Mo, Cd, Co, Bi, Ag, and Tl in Sagebrush in the vicinity of smelting plant are higher than other plants (Fig. 10). The relation between most of these metals such as Cu and Mo are synergistic (Siegel 2004) and the simultaneously uptake of high metal values by plant roots are impossible, so it is well demonstrated that most of high elemental values result from deposition of toxic metals that were emitted from the smelter and anthropogenic sources. Conclusion The environmental geochemistry of toxic metals in soils around smelter plants is an important subject of natural

environment. Investigation on environmental geochemistry of the heavy metals in soils around the Sarcheshmeh porphyry copper smelter plant has the following results: 1. The soil pro?les developed around the Sarcheshmeh porphyry copper mine are young and of inceptisol horizons. Gossans as natural phenomena form around porphyry copper deposits and serve as high concentrations of As, Cu, Sb, Zn, Pb, and Mo. During weathering and soil formation in arid and semiarid regions, these natural geochemical signatures are preserved and equilibrated between soil layers and bedrock, especially in immature gossans and are used as exploration guides. As a result of smelting process, the upper soil layers are mainly polluted by Cu, As, Cd, Pb, Bi, Zn, Mo, Sn, and S. The concentration of these metals in soil samples decreases as distance increased from the smelter plant and the role of natural geology in trace metal content of soil becomes dominant. Also, very high concentrations of toxic metals were observed in soil samples around smelter waste dumps. These data reveal that dumping of the waste material in an environmental-accepted manner is very important. The soil contamination around the waste sites and at the vicinity of Sarcheshmeh township is caused by Pb (78 mg kg-1), Cu (1,760 mg kg-1), As (67.2 mg kg-1), Mo (14.4 mg kg-1), Sb (14.2 mg kg-1), Zn (246 mg

2.

3.

123

-1

Environ Earth Sci (2011) 62:449–465

461

Table 4 Enrichment factor and anthropogenic contributions (%) for Pb, Zn, As, Sb, Cd, Cu, Mo, Sn, Bi, and S in the selected soil pro?les
Station Depth Pb Zn As (cm) EF1 EF2 Anthro (%) EF1 EF2 Anthro (%) EF1 EF2 BR N of smelter 0–5 5–20 Township 0–5 5–20 W of smelter 0–5 5–20 NW of smelter 0–5 5–20 Gossan 0–5 5–20 Township 0–5 5–20 Township 0–5 5–20 Station 3.1 0.7 3.9 1.9 9.2 2.2 2.1 1.7 6 3.7 2.4 1.1 2.3 1.4 5.4 1.2 1.8 0.9 4.6 1.1 1.3 1.1 0.1 0.8 2.4 1.1 2.2 1.3 35.6 – 48.8 – 78.3 11 7.8 – 21 17.1 – 16.2 – DSH 63 – – – 56.9 – 5.3 – – 10.7 – – – 2.5 1 1.4 1.1 2.6 1.4 1.4 1.5 0.5 0.3 2.1 1.3 1.9 1.3 3 1.1 1.3 1 1.8 0.9 0.7 0.8 0.5 0.5 1.5 1 1.6 1.4 Mo BR 22.2 – – 1.7 24.7 – – – – – – – – – DSH 28.9 – – – – – – – – – – – – – 11.5 14.2 1 1.2 11.7 3.7 5.1 1.6 12.6 4.6 3.2 1.8 1.9 1.1 1.8 1.4 1.3 0.07 0.8 0.4 10.4 2.6 4.2 1 10.2 2 4.6 1.1 Sn Sb Anthro (%) EF1 EF2 %Anthro BR 86.6 – 82.9 79 56.6 38.6 – – – – 5.6 52 – 56 DSH 85.9 – 46.8 – 84.2 – – – – – – – – – 22.2 1.1 5.3 1.5 0.5 0.5 1.8 2.5 1.8 1.5 14.2 5.2 4.5 1.3 Bi 28.6 1.4 5.2 1.3 8.4 1.2 1.1 1.6 0.06 0.4 3.1 0.8 4.3 1.3 BR 91 – 91.9 46 94.1 61.4 – 20.9 – 62.6 – 55.6 – DSH 93 – 76.6 – 76.2 – – – – 36.7 – 53 – 22.2 1.9 – – – – 2.1 2.6 3.9 1.5 – – 6.6 1 S 48.4 4 12.3 3.2 12.4 0.4 2 2.7 0.1 0.5 4.3 0.8 – – Cd EF1 EF2 %Anthro BR 91.5 – 72.7 50 83.9 – – 4.2 49.1 – 73 – 56.8 – DSH 95.7 50 83.7 38 88.1 – 0.7 – – – 53.2 – 54.8 –

Depth (cm) Cu EF1 EF2

Anthro (%) EF1 EF2 Anthro (%) EF1 EF2 Anthro (%) EF1 EF2 Anthro (%) EF1 EF2 Anthro (%) BR DSH 82.3 – – – 80.6 – – – 24 – 35.5 – 58.1 – 7.6 1 2.1 1.6 3.5 1.7 2.5 1.6 5.8 1.2 0.9 0.6 1.2 0.9 7.3 1 1.5 1.1 2 1 2 1.3 0.2 0.5 0.7 0.4 1.1 0.8 BR 73.6 – 7.1 32 44 – 13.3 17.8 8.8 – – – – – DSH 72.9 – – – 2.5 – – – – – – – – – 3.1 0.9 1.1 0.8 3 1.5 1.2 1.3 1.9 1.5 1.2 0.9 1.9 1.6 3 0.8 1.1 0.9 1.8 0.9 1 1.1 0.3 1 1.2 0.9 1.2 1 BR 36.3 – – – – – 32.3 10.1 – – – – – – DSH 32.4 – – – – – – – – – – – – – 22.1 – – – – – – – 4.9 0.9 – – – – – – – – 6.4 0.9 1.7 1.9 0.5 0.9 4.3 0.8 – – BR 90.6 – – – 69.1 – – – – – – – – – DSH – – – – – – – – – – – – – – 4.2 0.3 – – – – – – 7 1.6 – – 1 0.6 12.8 0.8 3.2 2.7 2.6 1 1.5 1.6 0.2 0.6 0.8 0.7 5.2 3 BR 53.1 – 40 57 24.9 – – 4.2 30.2 – – – 62 – DSH 83.1 – 35.1 26 44.5 – – – 71.4 – 33.6 – – 33.6

N of smelter

0–5 5–20 Township 0–5 5–20 W of smelter 0–5 5–20 NW of smelter 0–5 5–20 Gossan 0–5 5–20 Township 0–5 5–20 Township 0–5 5–20

21.8 11.3 1.8 0.9 1.3 2.15 0.4 0.7 7.1 10.3 0.8 1.1 0.5 0.8 0.5 0.8 3 0.26 0.7 1 3.1 4.6 0.7 1 4.7 3 1.6 –

90.8 – – – 72 – – – 3.6 – 57.2 – 31.9 –

EF1 calculated against the bedrock value, EF2 calculated against the deeper soil layer value, % anthropogenic is calculated against the bedrock and deeper soil layer values, N north, W west, NW northwest

¨ Table 5 Igeo classes and sediment or soil quality (Muller 1979) Igeo class 1 2 3 4 5 6 7 Sediments quality Unpolluted Unpolluted to moderately polluted Moderately polluted Moderately to highly polluted Highly polluted Highly to very highly polluted Very highly polluted Fig. 8 Box-plot of index of geoaccumulation (Igeo) for studied soil samples

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462 Fig. 9 Distribution of trace toxic metals in physical selective sub-samples (mg kg-1) [?ner traction (d \ 0.11 mm); medium fraction (0.11 \ d \ 2 mm); coarse fraction (d [ 2 mm) and bulk sample]

Environ Earth Sci (2011) 62:449–465

350 300

6 5

As (mg kg-1)

Bi (mg kg )

250 200 150 100 50 0 Coarse Medium Fine Bulk Near of smelter Township 15 km NW of smelter

-1

4 3 2 1 0 Coarse Medium Fine Bulk Near of smelter Township 15 km NW of smelter

12 10
-1

8 6 4 2 0 Coarse Medium Fine Bulk Near of smelter Township 15 km NW of smelter

5000 4500 4000 3500 3000 2500 2000 1500 1000 500 0 Coarse Medium Fine Bulk

Cu (mg kg -1)

Cd (mg kg )

Near of smelter Township 15 km NW of smelter

30 25

300 250

Mo (mg kg )

Pb (mg kg-1)

20 15 10 5 0 Coarse Medium Fine Bulk Near of smelter Township 15 km NW of smelter

200 150 100 50 0 Coarse Medium Fine Bulk Near of smelter Township 15 km NW of smelter

-1

35

2500

30

S (mg kg-1)

Sb (mg kg )

2000 1500 1000 500 0 Coarse Medium Fine Bulk Near of smelter Township 15 km NW of smelter

-1

25 20 15 10 5 0 Coarse Medium Fine Bulk Near of smelter Township 15 km NW of smelter

9 8 7 6 5 4 3 2 1 0 Coarse Medium Fine Bulk

600 500

Sn (mg kg )

Zn (mg kg-1)

400 300 200 100 0
Coarse Medium Near of smelter Township 15 km NW of smelter

-1

Near of smelter Township 15 km NW of smelter

Fine

Table 6 The relative mobility factor for the selected heavy metals (%) Location Element As Near smelter Township 15 km NW of smelter 48.6 7.22 14.1 Cu 53.6 33.6 17.9 Mo 6.1 5.7 17.8 Pb 67.9 25.8 11.5 Zn 39.3 23.2 15.9 Cr 4.7 6.9 4.9

4.

kg-1), and S (2,090 mg kg-1), thus stressing this issue. The toxic heavy metals are well correlated in soil samples and the relationship between these metals is more understandable for each soil layer and bedrock through scatter plots. In many cases, the correlations between toxic metals in surface soil layers are more signi?cantly positive than the deeper soil samples.

123

Bulk

Environ Earth Sci (2011) 62:449–465

463

40 35

30 25 20 15 10 5 0 Near Factory Townshipe

7.

Cd

Background

Mo

Sb

Sn

1600 1400 1200 1000 800 600 400 200 0

As

Near Factory Townshipe Background Pb Zn Cu

8.

7 6

Value (mg kg -1)

5 4 3 2 1 0 Near Factory Townshipe Background

9.
Tl

Ag

Bi

Co

Te

Fig. 10 Toxic heavy metal values in Sagebrush plant in some selected sites (mg kg-1)

the natural sorption by ?ne charged soil particles such as clay minerals and Fe–Mn oxyhydroxides in ?ner fraction and low values of metals in coarser fraction of soils, this part of soil in geoenvironmental evaluation has an important role in particular for elemental cycling through plants. In uncontaminated soils, heavy metals are mainly bound to silicate and primary minerals (residual fraction), whereas in contaminated ones they are generally more mobile and bound to other soil phases. The Mn–Fe oxyhydroxides and carbonate phases have an active role in adsorption of Cu, Pb, and Zn. Cu has a good association with organic matter. These factors as a part of natural attenuation are effective in delaying the translocation of metals through the soil and likely decreasing its toxicity. As a means of geochemical and biogeochemical cycles, Cu, Cd, Mo, As, Sb, Pb, Zn, S, Sn, and Bi have a potential for transformation through food chain. An important part of these metals enter into these cycles through sur?cial pollution of plants around the smelter plant and uncontrolled sources such as smelting waste dumps. Analysis of Sagebrush plant has demonstrated high values of heavy metals in plants near the smelter plant. Consumption of such plants by herbivore animals especially sheeps and goats around the smelter plant may have a serious environmental concern, which merits further investigation.

Value (mg kg -1)

Value (mg kg-1)

5.

6.

Copper, Mo, Cd, Sb, As, and S have the maximum enrichment and anthropogenic sources. Also, Pb, Bi, and Sn have some enrichment in sur?cial soil samples but in lesser order than previous metals. The degree of heavy metal contamination decreases as Cu [ Cd [ S [ Mo [ Sb [ As [ Pb [ Zn [ Sn [ Cr & Co & Mn, but in some samples is highly contaminated by Cu, Cd, and highly to moderately polluted by S, Mo, Sb, As, and Zn. Although high concentration of metals were observed in soils samples over the gossans, the enrichment factor for these toxic metals is close to normal ranges. As a special condition of sampling, the segregation of bulk sample in three sub-samples result in different values of heavy metals in contaminated samples. Concentration of metals in ?ner fraction of soil samples is higher than other parts and decreases as the diameter of sample increases. In uncontaminated soil samples and for metals that have no anthropogenic sources, the concentrations of the metals are related to the natural geology and the differences between separated sub-samples are less important. Because of

Acknowledgments This study is a part of the ?rst author’s M.Sc. thesis carried out under the supervision of Dr. A. Aftabi at Shahid Bahonar University of Kerman, Iran. The authors appreciate the cooperation of Research and Development Division of Sarcheshmeh Copper Complex for ?nancial supports and access to sampling and analysis. We also thank the industrial advisors of the project, E. Esmaelzadeh and M. R. Nikoie, who made valuable suggestions during sampling and analysis. We appreciate the cooperation of an anonymous English-speaking geologist for editing the ?rst draft of the manuscript. The comprehensive reviews of an earlier version of the manuscript by Dr. G. Dorhofer and two anonymous reviewers from the Journal of Environmental Geology are greatly appreciated. Finally, Dr. H. Atapour of Geological Survey of Kerman, Iran is thanked for her constructive suggestions.

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