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Environ Geochem Health (2007) 29:119–129 DOI 10.1007/s10653-006-9071-z

ORIGINAL PAPER

Arsenic mineralization, source, distribution, and abundance in the Kutahya region of the western Anatolia, Turkey Meral Dogan Æ A. Umran Dogan

Published online: 8 February 2007 Ó Springer Science+Business Media B.V. 2007

Abstract Environmental exposure to arsenic (As) in the Kutahya region of the western Anatolia, Turkey has been reported to cause various types of arsenic-associated skin disorders (Dogan, Dogan, Celebi, & Baris, 2005). A geological and mineralogical study was conducted to find the sources and distribution of the As. Geogenic (background) levels were measured in samples collected from various sources in the Gediz, Simav, Tavsanli, Emet, Yoncali, Yenicekoy, and Muratdagi areas of the Kutahya region. Based on this analysis, we determined that natural sources are a domineering factor affecting the distribution of As, which was found: (1) mainly in evaporitic minerals, including colemanM. Dogan (&) Department of Geological Engineering, Hacettepe University, Ankara, Turkey Present Address: M. Dogan Department of Civil & Environmental Engineering, The University of Iowa, Iowa City, IA 52242, USA e-mail: [email protected] A. U. Dogan Department of Geological Engineering, Ankara University, Ankara, Turkey Present Address: A. U. Dogan Department of Chemical & Biochemical Engineering, The University of Iowa, Iowa City, IA 52242, USA

ite (269–3900 ppm) and gypsum (11–99,999 ppm), but also in alunite (7–10 ppm) and chert (54– 219 ppm); (2) in secondary epithermal gypsum, which has a high concentration of As in the form of realgar and orpiment along fracture zones of Mesozoic and Cenozoic carbonate aquifers; (3) in rocks, including limestone/dolomite (3–699 ppm) and travertine (5–4736 ppm), which are relatively more enriched in As than volcanics (2–14 ppm), probably because of secondary enrichment through hydrological systems; (4) in coal (1.9– 46.5 ppm) in the sedimentary successions of the Tertiary basins; (5) in thermal waters, where As is unevenly distributed at concentrations varying from 0.0–0.9 mg/l. The highest As concentrations in thermal water (Gediz and Simav) correlate to the higher pH (7–9.3) and T (60–83°C) conditions and to the type of water (Na–HCO3–SO4 with high concentration of Ca, Mg, K, SiO2, and Cl in the water). Changes in pH can be related to some redox reactions, such as the cation exchange reactions driving the dissolution of carbonates and silicates. Fe-oxidation, high pH values (7–9.3), presence of other trace metals (Ni, Co, Pb, Zn, Al), increased salinity (Na, Cl), high B, Li, F, and SiO, high Fe, SO4 (magnetite, specularite-hematite, gypsum), and graphite, and the presence of U, Fe, Cu, Pb, Zn, and B, especially in the Emet, Gediz, and Simav areas, are the typical indicators for the geothermally affected water with high As content. A sixth source of As in this

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region is the ground (0.0–10.7 mg/l) and the surface waters (0.0022–0.01 mg/l), which are controlled by water–rock interaction, fracture system, and mixing/dilution of thermal waters. The high As concentration in groundwater corresponds to the areas where pathological changes are greatest in the habitants. Arsenic in ground water also effects ecology. For example, only Juriperus oxycedrus and J. varioxycedrus types of vegetation are observed in locations with the highest concentration of As in the region. Branches and roots of these plants are enriched in As. Keywords Arsenic mineralization
Groundwater
Kutahya
Messinian crisis
Sources of arsenic
Turkey
Western Anatolia

Introduction In the Mediterranean region, the Upper Miocene was a time of convergence and interaction of different geological processes, including tectonics, volcanic, and hydrothermal activities, and desiccation of the Mediterranean Sea. The Messinian salinity crisis was probably the most outstanding geological event of the late Cenozoic in the western Anatolia. Evaporation resulted in unusually high occurrences of some minerals, including arsenic (As) and borate minerals in the Kutahya region of the western Anatolia (Fig. 1). The redistribution of As in response to the geologic processes of the Messinian is reflected in the high content of As in the minerals, rocks, and drinking water of this area. Long-term exposure to these naturally occurring high levels of As may increase the risk of diseases to the inhabitants of the area, as has been manifested by the severe health problems that have been found in various populations drinking As-rich water for long periods of time (Guha et al., 1998; Hopenhayn-Rich, Biggs, & Smith, 1998; Jaafar et al., 1993; NRC, 2001; Plesko, Vlasak, Kramarova, & Obsitnikova, 1993; Smith et al., 1992, 2000; Tondel et al., 1999). Arsenic affects many organ systems, including the respiratory, gastrointestinal, cardiovascular, nervous, and hematopoietic systems. Skin lesions are the most common manifestations of As toxicity. An apparent dose-response relationship between

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the consumption of As-contaminated drinking water and skin disorders was observed in the Kutahya region when 153 individuals were screened from the Igdekoy and Dulkadir villages in the Emet area of the Kutahya region (Dogan et al., 2005). Figure 2 shows As-related skin lesions in the sole of a person from the Igdekoy area. At Igdekoy, 30.9% of the inhabitants had As-related skin disorders compared to 5.35% in Dulkadir, where lower levels of As were found in the drinking water. In the Kutahya region, typical symptoms of chronic As intoxication in terms of individual lesions include palmo-planter keratosis (PPK), basal cell carcinoma (BCC), planter keratodermi, planter hyperkeratosis, pigmented nodular lesion, mycosis fungicides, keratic papules, Bowenoid lesions, hyperhydrosis, verru plantaris, and verru planteris et palmaris (Dogan et al., 2005). Lung and bladder cancers are also observed in some localities of the Kutahya region (Turkish Ministry of Health, Department of Cancer Control data). Little is known about the geological processes that determine both the emplacement and source of the observed As enrichments in the area. A knowledge of the surface geology and mineralogy of the are is important to an understanding of the origins of the observed As distribution. In turn, the determination of the distribution of As in geological materials is critical to determining its effect on surface and ground water. This knowledge is also important for defining geochemical baselines for potentially harmful As so that any future perturbations caused by human influence or natural events may be recognized and measured. Hence, this geological study focused on gaining an understanding of both the relationship of the distribution of high contents of As and the geological controls and mineral–water interactions in the Kutahya area, western Anatolia, Turkey.

Materials and methods In this study, field, mineralogical, and geochemical studies were conducted to determine the source(s) of As. Representative samples of rocks including peridotite, serpentinite, basalt, andesite, trachy andesite, tuff, gabbro, diorite, applite,

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Fig. 1 Upper map location of the Kutahya region, Turkey. Lower map the locations of the study area (Gediz, Simav, Emet, Tavsanli, Yoncali, Yenicekoy, and Muratdagi of the Kutahya region in western Anatolia)

limestone/dolomite, marl, and travertine; minerals, including gypsum, chert, colemanite, alunite, and clinoptilolite; coal; water; and plant material were systematically collected. A total of 105 rock and mineral samples were analyzed for their As contents by inductively coupled plasma-emission spectrometry (ICP-ES)(Table 1) (ACME laboratory, Canada). To establish the regional distribution of As in water, we collected 40 samples directly from water supply wells, geothermal water, cold spring water, and creeks. Each of the water samples was put into two plastic bottles, which were tightly

sealed and immediately analyzed to determine the total As concentration. A portion of each water sample was filtered through a 0.45-lm membrane filter; this filtered sample was either acidified to pH 2 for cation analysis, or not acidified for anion analysis. Concentrations of As were measured by means of graphite-furnace atomic absorption spectrophotometer (AAS) at the Water and Sewer Administration of Ankara (ASKI) and the Hygienic Institutes of Izmir, Turkey. For verification, both sampling and analyses were repeated three times for the samples with the highest concentrations of As in the area.

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Environ Geochem Health (2007) 29:119–129 Table 1 Average and range of the As concentrations in the mineral and rock samples collected from the study area Rock/sediment/ mineral type

As concentration average and range (ppm)

Peridotite/ serpentinite Basic rocks (basalt) Basic rocks (gabbro/diorite) Intermediate (andesite, trachyandesite) Acidic rocks (aplite) Ignimbirites (tuff) Limestone/ dolomite Travetene Marl Zeolite (clinoptilolite) Chert Gypsum

9.6 (<2–53)

9

14.8 (<2–140)

8

61.6 (<2–129)

6

50.0 (2–150)

8

3.5 (3–4)

3

Allunite Colemanite Coal Plant

Number of analyses (samples)

9.6 (<2–21) 140.44 (3–699)

4 17

4,28 (5–4,736) 23.0 (15–30) 0.6 (<2–2)

6 5 5

110.75 (54–219) 16,677.83 (11– 99,999) 8.01 (7–10) 2,800 (269–3,900) 13.6 (1.9–46.5) 0.425 (0.35–0.50)

5 6 3 5 13 2

Fig. 2 Arsenic-related skin lesions in a palm and sole of an inhabitant of Emet

The pH and temperature data were obtained by the Water Work Department of Turkey. Groundwater samples were collected from aquifers composed of metamorphic rocks, limestone/dolomite, and travertine. Root and branches of some plants (Juriperus oxycedrus and J. varioxycedrus type) present in the area were also analyzed for As content by AAS.

Geological settings Kutahya region is located in the western part of Anatolia within the Izmir-Ankara-Erzincan (IAE) ophiolitic zone representing the northern branch of Neo-Tethys (Brinkmann, 1972) as part of the Alpine-Himalayan orogenic belt. The subduction of the African-Arabian plate beneath the Anatolian plate is widely accepted. Kocak

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(1990) suggested that the melting plumes, emplaced at shallow depths in the crust, supply the heat for the thinning of the rift structure. A high mantle contribution to surface heat flow has also been suggested by Alptekin, Ezen, and Ucer (1990). A generalized stratigraphy of the area was established and is summarized in Fig. 3. The oldest exposed basement rocks are Carboniferous-Permian low-grade metamorphic rocks, including meta-sediments, ophiolitic fragments, gneiss, schists, and marble. Overlying the Carboniferous-Permian rocks are Mesozoic platform sequences representing the Anatolide continental margin, and these include an ophiolitic me´lange, Late Cretaceous Kinik ophiolite, and Tertiary cover units (Ozcan & Cagatay, 1989). Several lacustrine basins developed in the western Turkey during the Tertiary. These basins are generally represented by volcano-sedimentary successions. Evaporitic (i.e., colemanite and gypsum)

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Fig. 3 Generalized stratigraphic section of the study area (modified from Akdeniz and Konak, 1979)

sequences are represented in the stratigraphic record and consist of several episodes of evaporation in these lacustrine basins of the area. Volcanic activity occurred in the area from Early Miocene to Late Miocene (Helvaci, 1984). Volcanic rocks comprise calc-alkaline and alkaline lava suites, including trachyte, basalt, and andesite. Tertiary sedimentary successions are conglomerate, marl, sandstone, limestone, dolomite, and gypsum. These intervals in the Tertiary section are especially important because they preferentially host ore minerals such as Fe,

Cu–Pb–Zn, Sb, S, Cr, Au, Mn, and magnesite (Table 2). The mining of Fe deposits ceased in the area because of the high As, S, and SiO2 content of the ore. Lead and silver mining has taken place in the Kutahya region for thousands of years ago, continuing up to the present time. Kaptan (1981) described metallurgical remnants and old underground mining dating back as early as the beginning of second millennium BC, and an ‘‘ore crushing and grinding tool’’ from the second century AD were found at the entrance of another adit in the western Anatolia. Tertiary

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Table 2 Important mineral deposits in the study area Locations

Ore minerals

Emet Gediz

Borate (colemanite), Fe, Mn, kaolinite Alunite, Hg, gypsum, kaolinite, Mn, Fe, Sb Sb, Cu–Pb–Zn, Fe, S, kaolinite F, Mn, magnesite Au

Simav Tavsanlı Kapıo¨renAktepe Ku¨tahya Ilıca

Graphite, calcite, Cr Magnesite

volcanic units are either intercalated with borates or constitute a major component of bedded epiclastic material in the basin; these units contain, in some regions, important resources of fossil fuels and industrial minerals, including lignite, bituminous shale, clays, and zeolites (clinoptilolite). Helvaci (1995) suggested that the borate deposits formed by evaporation in shallow playa lakes. There are two colemanite lenses recognized in these successions. Gypsum and celestine are also present. Quaternary units are composed of sand, gravel, clay, and travertine. Metamorphic rocks of Paleozoic and carbonates of Mesozoic and Cenozoic rocks host the majority of the thermal waters and ground water in the study area. To the southwest, in Gediz graben, alluvium, and Quaternary travertine are also host to the ground water. The area is seismically very active with a number of earthquakes with a magnitude of over six being recorded in the past. Seismic events directly affect the surface expression of the hydrology of the area. Springs have been observed to stop flowing and new springs have been found to appear in response to earthquakes.

Results and discussion Source and initial enrichment of arsenic and its distribution in minerals and rocks Serpentinized peridotite, basalt, gabbro, diorite, andesite, trachy andesite, applite, tuff, marl, limestone/dolomite, travertine rock samples; and gypsum, alunite, clinoptilolite, colemanite mineral samples were analyzed for their As content.

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Table 1 shows the average and range of the As content of these samples. Gypsum is interbedded in the mixed sequences of volcano-sedimentary rocks of Tertiary deposits and was formed by evaporation in a playa environment. It also occurs as veins along the fracture zones of the Cenozoic limestone-dolomite aquifer located to the north of the area. The gypsum in the veins was formed following calcite and dolomite precipitation, possibly as hydrothermal fluids moved through the karstic rocks of these younger aquifers in the area. The high concentrations of As detected in the gypsum veins in the Emet region are attributed to the accumulation of As from dissolution, with evaporation of the bedded sulfate, and hydrothermal activity in the area. Arsenic in the veins is present as realgar and orpiment, which appear as epithermal deposits occurring at the temperature of 50–200°C, low pressure, and shallow depth. The gypsum crystals are largely grown as open space filling in cavities and vugs. The veins commonly show a crustiform ‘‘banded’’ structure, sometimes called a ‘‘comb’’ structure. The gypsum crystals making up the vein fill grew perpendicular to the fracture walls, suggesting that opening and filling of the fractures was contemporary and that the fractures are extensional. Arsenic is particularly enriched in the following minerals and rocks in these sequences: colemanite (269–3900 ppm), evaporitic gypsum (11–99,999 ppm), and travertine (5–4736 ppm). It is also relatively enriched in alunite (7–10 ppm), limestone/dolomite (3–699 ppm), and chert (54–219 ppm). Western Turkey possesses two thirds of the boron (B) resources in the world. Colemanite mined in the Emet district of Kutahya, and hydrothermally generated B-rich springs associated with volcanic rocks supply B to form colemanite (Helvaci, 1995; Inan, Dunham, & Esson, 1973). Gundogdu, Yalcin, Temel, and Clauer (1996) suggested that the most important chemical changes occurred during the diagenetic transformation of silicic volcanic glasses that enriched in B. However, Floyd, Helvaci, and Mittwede (1998) suggested four stages of transportation for B: (1) initial concentration in subduction-derived fluids; (2) incorporation into continental crust via arc

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magmatism; (3) melting of the B-enriched continental crust to produce ignimbrites; and (4) selective mobilization of B from ignimbrites by local hydrothermal activity. We suggest that the observed enrichment of As and B are the result of hydrothermal and evaporitic conditions, with some redistribution of both elements during diagenesis. The reaction of the primary and secondary phases with circulating water has produced high levels of As in some geothermal water and ground water used for drinking water supplies in the area. Arsenic content of water The presence of As in the ground water has been commonly related to the dissolution of sulfide minerals (Chowdhury et al., 2001), the dissolution or desorption from iron oxyhydroxides (Bhattacharya, Chatterjee, & Jacks, 1997; Nickson et al., 1998), or the up flow of geothermal water (Welch, Helsel, Focazio, & Watkins, 1999). Arsenic concentrations in surface water, thermal wells, ground, and spring waters of the study area vary greatly with location, as does the chemical composition of the thermal waters. The origin of thermal waters from western Anatolia was studied by Gulec (1988) and Ercan, Matsuda, Nagao, and Kita (1994) using 3He/4He data. Their results indicated that helium (He) is partly derived from the mantle in the thermal waters. Giggenbach (1991) used lithium (Li) as a tracer alkali metal for the initial deep rock dissolution processes to evaluate the possible origin of the chloride (Cl) and B constituents of thermal waters. Boron isotopic data in the thermal waters of the area indicated either the leaching of B from the rocks, or a B(OH)3 degassing flux from the deep sources in the area (Vengosh, Helvaci, & Karamanderesi, 2002). The circulation of these thermal waters in the western Anatolia is related to major faults and fracture zones, and discharge along these structures. In this study, As concentrations of the thermal waters of the Kutahya region, which include those from Emet, Tavsanli, Yenicekoy, Simav, Gediz, Yoncali, and Muratdagi were analyzed, and the types of water identified. Figure 4 shows the type, temperature, pH, and As contents of the

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geothermal water. Total As content of the thermal waters was found to vary with temperature and pH, ranging from 0.05 mg/l to 0.95 mg/l. Although the expected type of thermal waters in the aquifers is initially Na–HCO3 in the western Anatolia (Gemici, Tarcan, Colak, & Helvaci, 2004), mixing during up flow and the re-equilibration process cause Na–HCO3-type waters to change into various other types. This conditions that prevail in the formation of Na–HCO3-type waters contribute to the B enrichment in thermal fluids. Na–HCO3-type thermal waters with increasing Na and HCO3 concentrations can be used as an indicator of the degree to which the water–rock interaction take place. Based on their chemical composition, the thermal waters can be divided into two main groups that are largely based on the function of their host rock. To the east of the area (Yoncali, Tavsanli, and Muratdagi), the main water type is either Ca–SO4–HCO3 or Ca–HCO3 with high Mg content. Mesozoic and Cenozoic carbonate rocks are the main reservoir rocks in this region. Yoncali geothermal water in the northeast corner of the study area had the lowest temperatures (30°C) and lower As (0.0 mg/l) and pH (6.52) values, with high concentration of dissolved Mg. Lower temperatures indicate the influence of meteoric and/or ground waters on the geothermal water, while high Mg content indicates the water– rock interactions at low temperatures and/or mixing with cold ground waters. To the west of the area (Yenicekoy, Simav, and Gediz), the water type is Na–SO4–HCO3 or Na–Ca–SO4– HCO3 , with high K, SiO2, and Cl contents. Simav geothermal water, with a temperature of 83°C and a pH of 9.3, had a very high concentration of As (0.9 mg/l). The Na–Ca–HCO3-type of thermal water in Emet had a higher As content (0.17– 0.213 mg/l) and a high Cl content, with a slightly lower temperature than the Ca–SO4–HCO3 type water. The dissolution of Ca–SO4 and Na–Ca– SO4 are important processes in the water–rock interaction to the west of the area. Based on these observations, increasing Na and Ca concentrations can be used as an indicator of the degree to which the water–rock interaction takes place. The relatively high Cl contents of the second group of thermal waters indicate that the waters are fed

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Fig. 4 Location of geothermal water sample sites and types of water. Temperature ( T), pH, and As concentrations (see text for explanation)

from deeper reservoirs at high temperatures with less groundwater mixing. The level of SO4 in this group of thermal waters is likely to be controlled by dissolution and/or oxidation of S and SO4 to form minerals such as epithermal and evaporitic gypsum and pyrite in Emet, evaporitic gypsum in Gediz, and S in Simav. In the Emet area, both main types of water are present due to heavy fracturing and different reservoirs. The As content of the second type of thermal water in Emet is 0.067–0.106 mg/l. High As concentrations in the ground water correspond to areas where pathological changes and a dose-response relationship between the amount of As exposure and frequency of various skin lesions has been observed (Dogan et al., 2005). Large variations in the pH and temperature were also found in the waters of drilled wells and springs (Fig. 5). The temperatures of the groundwater ranged from 12° to14°C, with the exception

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of Yoncali (40–42°C). The higher temperature of the well and spring water from Yoncali, which is higher than that of the geothermal water in this location, indicates the effects of deeper sources along the fracture systems. Groundwater in Emet showed the highest total As concentration, varying from 8.9 to 107 mg/l. Thus, As is not controlled by either temperature or pH in the groundwater of the cold water (drilled well and cold-spring water) in the area. The proposed source of As is believed the result of a reaction between circulating water and the As-containing components of the rocks. The contribution of thermal waters to cold groundwater aquifers and surface water also causes some degree of contamination. The concentrations of As in the surface water varied from 0.0022 mg/l to 0.01 mg/l, while As content in the groundwater (drilled wells and spring water) was found to vary among locations and with time at the same

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Fig. 5 Location of representative groundwater sample sites and types of water, pH, and As concentrations (see text for explanation)

location (Figs. 4, 5). Groundwater in some parts of the area were found to have higher concentrations of As than the thermal water, surface water, and surface soil. The supply of As to ground water is attributed to the dissolution of As-rich phases. Arsenic in groundwater can reach up to 10.7 mg/l (Igdekoy, Emet) and exceed provisional guideline concentrations for drinking water set by the World Health Organization (WHO) (10 lg/l). However, the reduction of As to 10 ppb will require remediation or, as an alternative, the closure of wells and cessation of water usage in the area. Arsenic content of plants In the study area, vegetation is poor in the locations with high As contents. Locations with very high concentrations of As (i.e., Igdekoy, 9.3–10.7 mg/l) in the ground water have only Juriperus oxycedrus and J. varioxycedrus types of

trees. Roots and branches of these plants were found to be enriched in As (Table 1). Because these plants are commonly used for cooking, drying food, and heating, inhabitants may be exposed to greater amounts of As.

Conclusion Arsenic is a naturally occurring element in minerals, including evaporitic minerals such as colemanite and gypsum, as well as alunite and chert in Tertiary deposits, in secondary epithermal gypsum in the form of realgar and orpiment along the fracture zones in the carbonates rocks, in limestone/dolomite and travertine, volcanic rocks and coal of the Tertiary age volcanosedimentary sequences, and in the thermal, ground and surface waters in the Kutahya region, western Anatolia, Turkey. This contaminant has been found to occur at concentrations

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that exceed the provisional guidelines set by the WHO for As concentrations in drinking water. The release and transfer of As from the local rocks and minerals to plants and humans via water is one of the important mechanisms for the As contamination. We suggest that the observed enrichment of As in the study area is the result of both hydrothermal and evaporitic conditions, with some redistribution of both elements during diagenesis, and rock/mineral– water interaction. The reaction of the primary and secondary phases with circulating water has produced high levels of As in some geothermal and ground waters. The occurrence, origin, and mobility of As in groundwater are primarily influenced by the local geology, hydrogeology, and geochemistry of the sediments. The underlying factors attributing to the observed variations are mineral/rock–water interaction, hydrological network, meteorological factors, and seismicity of the region. As a consequence of earthquakes in the area, some springs have been found to cease flowing, and new ones have been found to appear. The level of Asin the ground water in the area is related to the dissolution of sulfide minerals, the dissolution or desorption from iron oxyhydroxides and/or up flow of geothermal water. High As concentrations in the ground water correspond to the areas where pathological changes are the most prevalent among the habitants. Arsenic in ground water also effects ecology. For example, only the Juriperus oxycedrus and J. varioxycedrus type of vegetation was observed at locations with the highest concentrations of As. The branches and roots of these plants were also found to be enriched in As. Acknowledgements Financial support for this work was partially provided by the Department of Cancer Control, the Ministry of Health of Turkey. We also extend our appreciation to DSI (Water Work Department), and MTA (General Directory of Mineral Research and Exploration) of the Ministry of Energy, Turkey.

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