High arsenic and boron concentrations in groundwaters related to mining activity in the Bigadic...

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Applied Geochemistry 23 (2008) 2462–2476

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AppliedGeochemistry

High arsenic and boron concentrations in groundwatersrelated to mining activity in the Bigadic� borate deposits

(Western Turkey)

Unsal Gemici *, Gultekin Tarcan, Cahit Helvacı, A. Melis Somay

Dokuz Eylul University, Department of Geological Engineering, Tınaztepe Campus, Buca, 35160 _Izmir, Turkey

Received 27 September 2007; accepted 21 February 2008Editorial handling by R.B. Wanty

Available online 4 March 2008

Abstract

This study documents the environmental impacts of borate mines in Bigadic� district, which are the largest colemaniteand ulexite deposits in the world. Borate-bearing formations have affected the concentrations of some contaminants ingroundwater. Groundwater quality is directly related to the borate zones in the mines as a result of water–rock interactionprocesses. Calcium is the dominant cation and waters are Ca–SO4 and HCO3 type in the mine (Tulu borate mine) fromwhich colemanite is produced. However in the Simav and Acep Borate Mines, ulexite and colemanite minerals are pro-duced and waters from these open pit mines are Na–HCO3–SO4 types. High SO4 concentrations (reaching 519 mg/L)might be explained by the existence of anhydrite, gypsum and celestite minerals in the borate zone. Groundwater fromtuff and borate strata showed relatively low pH values (7–8) compared to surface and mine waters (>8). EC values rangedfrom 270 to 2850 lS/cm. Boron and As were the two important contaminants determined in the groundwaters around theBigadic� borate mines. Arsenic is the major pollutant and it ranged from 33 to 911 lg/L in the groundwater samples. Theconcentrations of B in the study area ranged from 0.05 to 391 mg/L. The highest B concentrations were detected at themine areas. The extension of the borate zones in the aquifer systems is the essential factor in the enrichment of B andAs, and some major and trace elements in groundwaters are directly related to the leaching of the host rock which aremainly composed of tuffs and limestones. According to drinking water standards, all of the samples exceed the tolerancelimit for As. Copper, Mn, Zn and Li values are enriched but do not exceed the drinking water standards. Sulfate, Al and Feconcentrations are above the drinking water standard for the groundwater samples.� 2008 Elsevier Ltd. All rights reserved.

1. Introduction

Boron is not found as a free element in nature. Itusually occurs as orthoboric acid in some volcanicspring waters and as borate minerals like borax

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* Corresponding author. Fax: +90 232 4531129.E-mail address: [email protected] (U. Gemici).

(Na2B4O7 � 10H2O), colemanite (Ca2B8O11 � 5H2O)and ulexite (NaCaB5O9 � 8H2O). In the earth’s crust,the average B concentration is 10 ppm (Dotsikaet al., 2006). Borates are defined by industry as anycompound that contains or supplies boric oxide. Alarge number of minerals contain boric oxide, butborax, ulexite and colemanite are the most impor-tant commercial minerals. These minerals are

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U. Gemici et al. / Applied Geochemistry 23 (2008) 2462–2476 2463

produced in a limited number of countries domi-nated by the United States and Turkey, whichtogether furnish about 90% of the world’s boratesupplies (Lyday, 1991; Helvacı, 2005). Turkish pro-duction is controlled by the Eti Mine Cooperation,the national mining enterprise, which supplies mostof the commercially traded ulexite, colemanite andborax from mines in the Bigadic�, Emet, Kestelekand Kırka districts (Kistler and Helvacı, 1994; Hel-vacı, 2005).

The Bigadic� borate deposits are among the larg-est colemanite and ulexite deposits in the world. Thehigh-grade colemanite and ulexite ores are adequateto supply the world’s B needs for many years. TheBigadic� deposits formed within Neogene perennialsaline lake sediments located in a NE–SW-trendingbasin (Helvacı, 1995). The Bigadic� borate district islocated in the SW of the known borate deposits ofTurkey. The mine area is drained by the SimavRiver and its small tributaries. The climate in Big-adic� is transitive between the Mediterranean andBlack Sea climate regions. Climate is characterizedby arid, sunny summers and wet, cold winters.Autumn is long and spring is short and rainy. Themean precipitation is around 570 mm. The yearlyaverage temperature is 14.5 �C.

After the discovery of borate deposits aroundBigadic� in 1950, mines were opened in the north-eastern and southern parts of the area (Meixner,1956). The deposits are mined by open pit andunderground mining. Earlier studies in the Bigadic�field have been related mainly to the borate depositsto evaluate their geological, mineralogical and iso-topic properties, their genesis and the reserve andeconomical potential of the borate deposits (Gun-dogdu et al., 1989; Helvacı and Alaca, 1991; Hel-vacı, 1995; Erkul et al., 2006). This study focuseson hydrogeological and environmental studies ofthe ground and surface water in and around Bigadic�borate mining area.

Boron can be found in water systems as a resultof natural or anthropogenic sources. Natural B isderived from geothermal discharges, leaching froma large variety of rocks, or the mixing of groundwa-ter with oil field water or connate or fossil brines.High B concentrations of thermal waters cause envi-ronmental problems in groundwaters and surfacewaters (Gemici and Tarcan, 2002; Vengosh et al.,2002). Anthropogenic B sources include B in wash-ing powders, municipal wastewaters, and industrialresidues, B-pesticides, B-fertilizers, etc. (Col andCol, 2003; Dotsika et al., 2006; Gemici et al.,

2007). Case studies in the Mediterranean regionhave shown that B dissolved in groundwater is gen-erally geogenic and related to hydrothermal or sal-ine water resources, water–rock interactionprocesses and sea water intrusion (Kloppmannet al., 2004; Bianchini et al., 2005; Pennisi et al.,2006).

Arsenic enrichment in groundwater is a globalconcern. High As concentrations are found ingroundwater for various reasons; leaching of Asfrom Tertiary volcano-clastic sediments, release ofsorbed As where redox conditions in groundwatersare reduced (Nimick, 1998; Gemici, 2004; Keimo-witz et al., 2005; Tarcan and Gemici, 2005; Gemiciand Tarcan, 2007). Another source of naturallyoccurring As is from geothermal discharges (Gemiciand Tarcan, 2004). Arsenic is relatively soluble inhot or warm hydrothermal fluids (White, 1981)and commonly causes environmental problemsdownstream of hot spring systems (Axtmann,1975; Craw et al., 1999). Environmental problemsrelated to As toxicity are encountered in variousparts of the world. The most noteworthy occur-rences are in parts of Argentina, Bangladesh, Chile,China, Hungary, India (West Bengal), Mexico,Romania, Taiwan, Vietnam and many parts of theUSA (Smedley and Kinniburgh, 2002). Toxicityrelated to As-rich groundwater in southern WestBengal (India) and in some parts of Bangladesh isan important problem to which large numbers ofpeople are exposed. Although As-rich pyrite orother As minerals are rare or absent in the affectedsediments, As occurs adsorbed on Fe-oxyhydroxidecoated sand grains and clay minerals (Acharyyaet al., 2000). Many areas in Europe also are affectedby elevated As concentrations, such as Hungary,Romania, Greece, Spain, Finland and Germany(Nordstrom, 2002; Smedley and Kinniburgh, 2002;Kouras et al., 2007). High As concentrations ingroundwaters from geothermal sources have beenfound in Northern Greece where drinking waterswith As concentrations up to 120 lg/L are beingconsumed (Mitrakas, 2001; Fytianos and Christof-oridis, 2004; Katsoyiannis et al., 2007). High Ascontents of geothermal origin up to 6900 lg/L havebeen detected in the Campanian Volcanic Provinceof Italy (Aiuppa et al., 2006). Concentrations upto 150 lg/L have been detected in the southern partof the Great Hungarian Plain (Varsanyi et al.,1991). Gurzau and Gurzau (2001) also reportedAs concentrations, up to 176 lg/L, in the associatedaquifers of neighboring Romania (Smedley and

2464 U. Gemici et al. / Applied Geochemistry 23 (2008) 2462–2476

Kinniburgh, 2002). Colak et al. (2003) and Gemiciet al. (2007) discussed the natural As enrichmentin groundwaters and soils related to borate depositsin Emet (Turkey). The purpose of the present inves-tigation is to determine the hydrogeological andhydrogeochemical properties of groundwaters, theirrelationships with borate deposits and environmen-tal impacts of borates in the Bigadic� borate district.Special emphasis is put on the high B and As con-centrations in groundwaters, their origin and theirmobility in the aquifers.

2. Geological and hydrogeological settings

Geological units are divided into two mainsgroups in the study area. Paleozoic and Mesozoicrocks form the basement. Paleozoic metamorphicrocks consist of marble and mica schists, and aMesozoic ophiolite complex, which includes theophiolite itself, together with radiolarite, limestoneand greywacke. A Neogene sequence in the regionrests unconformably on the Paleozoic and Mesozoicbasement complex (Ozpeker, 1969).

The Neogene basins in western Turkey containimportant borate deposits, mostly in western Ana-tolia, within an area 300 km east–west and 150 kmnorth–south (Helvacı and Orti, 1998; Helvacı andAlonso, 2000). Approximately 80% of the totalworld borate reserves occur in these basins (Helvacı,2005). The main borate districts are Bigadic�, Kes-telek, Sultanc�ayırı, Emet and Kırka. These boratedeposits formed in lacustrine environments duringperiods of nearby volcanic activity which com-menced in early Tertiary times and continued atleast until the beginning of the Quaternary (Helvacıand Yagmurlu, 1995). The Bigadic� borates formedin two different zones separated by a thick tuff unit,elongated in a NE–SW direction (Helvacı, 1995;Fig. 1).

Neogene units begin with the basement (basal)volcanics (Fig. 1). This unit is more than 250 mthick, and comprises of rhyodacite, dacite, trachy-cite, trachyandesite, basalt, agglomerate and tuff(Erkul et al., 2006). The basement rocks are overlainby the basal volcanic unit, which is also overlainuncomfortably by the lower limestone unit. Thelower tuff unit is dominantly rhyolitic and rhyoda-citic and is agglomeratic in the lower part and over-lies the limestone unit (Helvacı, 1995). The boratebeds alternate with limestone, clayey limestone,marl, claystone, mudstone, and tuff and they arelocated in the lower parts. The lower borate zone

can be observed at the Tulu open pit and the Yeni-koy underground mine (Fig. 2). Borate mineralsoccur predominantly as nodules, thin beds andlenses within the borate zone. The current produc-tion from the lower borate unit comes from the Tuluopen pit mine, the borate unit being 0.2–65 m thick(Helvacı and Orti, 1998). Borate minerals are dom-inantly colemanite and ulexite. Howlite (Ca2B5-

SiO9(OH)5, probertite (NaCaB5O9 � 5H2O) andhydroboracite (CaMgB6O11 � 6H2O) are the otherborate minerals in the lower borate zone (Helvacı,1995). Calcite, dolomite, anhydrite, and gypsumalso occur within this zone, along with montmoril-lonite and illite. Laminated brown claystone andgray-white limestone overlie the borates. Gypsumis found particularly in deep boreholes of the lowerborate zone, as bands between ore beds. Anhydritealso occurs with colemanite in the lower borate-bearing unit. The upper borate zone is composedof alternating beds of limestone, claystone clayeylimestone, marl, and tuff and includes lenses ofborate beds at intermediate levels with thicknessesbetween 0 and 30 m. Economically exploited borateminerals are colemanite and ulexite. Inyoite, meyer-hofferite, priceite, terschite, hydroboracite, howlite,tunellite and rivadavite are also found in the upperborate zone (Helvaci, 1995). Calcite, aragonite,dolomite, anhydrite, gypsum, celestine, heulandite,clinoptilolite, analcime, K-feldspar, quartz, opal-CT, montmorillonite, chlorite and illite are all asso-ciated with the clay, tuff, marl, and limestone bedsof both the borate zones. Anhydrite, celestite, anal-cime and B-bearing K-feldspar are more rarelyobserved within the borate deposits (Helvacı et al.,1993; Helvacı, 1995).

Paleozoic and Mesozoic rocks (marble, schist,ophiolites, limestones) are the fractured aquifers ofthe basement rocks in the study area. These rocksoutcrop in the SW of the study area. Neogene rocksconsist of alternating terrestrial sediments and vol-canic rocks. Groundwater is located in the fracturesof these rocks. Springs generally are found along thecontact of the alternating beds of permeable andimpermeable (clayey levels) units; these springs sat-isfy part of the water demand for drinking and agri-cultural purposes for the people in the villagesaround the study area.

Groundwater from most of the springs is in con-tact with the borate mineral bearing rocks of thelower and upper borate zones. The dominant Band As in the groundwaters are related to the geo-logical setting of the study area (Fig. 1). Lower

Fig. 1. Geological map (after Helvacı 1995), sampling locations and the geological section of the study area.


Fig. 2. (a) The view of the Simav borate mine and (b) the waste pool.


and upper borate zones consist of dominantly cole-manite and ulexite. The anticipated groundwaterflow direction in the Neogene rock aquifers is fromnorth to south. Springs are fed from the northernparts of the study area mainly by the fractures.Groundwater moves along the permeable levels ofborate zones, limestones and tuffs and emerges assprings. Tuffs are widespread in the study area.Although there are many springs derived from tuffs,their permeability and discharge rates are quite low.

Waters derived from the basement rocks are ofgood quality for drinking and irrigation. They arenot enriched in As and B to the extent of the watersfrom Neogene rock aquifers. Therefore, detailedstudies for B, As and other contaminants that mightbe derived from borate mines were focused on thewaters from the Neogene rock aquifer.

3. Material and methods

Sampling of surface and groundwaters was per-formed in 2004 in the Bigadic� district. A total of

25 water samples were sampled for analysis fromriver, open pit mines, springs and a waste pool.The pH, temperature, EC and Eh were measuredin the field with portable devices. After makingthese measurements, the samples were filteredthrough 0.45 lm filter papers and preserved foranalysis. Each sample was stored in two polyethyl-ene bottles. One of them was acidified with 10 mLHCl for cation analysis. The other was kept unacidi-fied for Cl, SO4 and HCO3 analyses. Samples werestored at 4 �C for no more than 1 week prior to lab-oratory analyses, which were carried out by ACMElaboratory (Canada). Chloride, SO4 and HCO3

analyses were done in the Geochemistry Laboratoryof Geological Engineering Department, DokuzEylul University. The computer program PHRE-EQCi (Parkhurst and Appelo, 1999) using databasellnl was used to calculate the distribution of aqueousspecies. The program is designed to perform a widevariety of aqueous geochemical calculations, basedon an ion-association aqueous model. This com-puter program also has been used to evaluate which


solids might be precipitating by means of saturationindex (SI). The Aquachem (Calmbach, 1997) com-puter code was also used to classify water typesand for correlation analysis of water samples.

4. Results and discussion

4.1. Hydrogeochemistry

Water samples from the study area could bedivided into two main groups, with 4 samples ofsurface water and 20 samples of springs. Physico-chemical data for water samples are summarizedin Table 1. In addition to these water samples, thepond in the mining area was also sampled (sample7). During the mining, waste waters are depositedin the ponds (Fig. 3). Sample 7 reflects these typesof the waters from the borate mining area. Alkalinepond waters with a pH of 8.3 have electricalconductivity values of around 985 lS/cm. Na–Ca–HCO3 and SO4-type pond waters have As concen-trations of about 16 lg/L, which is lower than theexpected values for a pond water in a borate miningarea.

The Simav River passes through the mining area,and is the most important surface water in the studyarea. Some water samples were collected from differ-ent parts of the Simav River and its tributaries(samples 16, 17, 22, 25). The chemical compositionof surface waters is similar to the groundwaters.They are also Ca–Mg–HCO3 type but the concen-trations of the dissolved solids are lower. The aver-age EC value is 375 lS/cm. Sample 22, which wastaken upstream of the open pit mine, had low As(9.9 lg/L) and B (119 lg/L) values. However sam-ple 25, which is located downstream of the Acepand Simav open pit mines was enriched in As(20.3 lg/L) and especially B (2080 lg/L). Thisremarkable increase in B concentrations is due tothe contamination by leaching of borate mineralsin the mine tailings when the stream passes down-stream through the open pit mines, although mostof the Simav River has been artificially channelized.

Groundwater that comes from tuff and boratezones have lower pH values (7–8) than those ofthe surface and mine waters (pH > 8). EC valuesrange from 270 to 2850 lS/cm. The sampled watersare classified into two different types according toIAH (1979); Na–HCO3(SO4) and Mg–Ca(Ca–Mg)–HCO3. The Piper triangular diagram is usefulfor evaluating the geochemical evolution of thegroundwater that not only shows the chemical char-

acter of each water sample, but also the relationshipto other samples (Fig. 3). Groundwaters in theregion are significantly dominated by Ca, Mg andHCO3.

Springs in the open pit mines (samples 1, 2 and 4)have different water types depending on the domi-nant borate minerals in the mine. Groundwaterquality is directly related to the borate zones inthe mines as a result of the water–rock interactionprocesses. Springs issue from the contacts of inter-bedded limestones and clayey levels of the borateunit. Colemanite is produced in the Tulu open pitmine, Ca is the dominant cation and waters areCa–SO4–HCO3 type. However, in the Simav (sam-ple 1) and Acep (sample 4) open pit mines, ulexiteand colemanite minerals are produced. Ulexite is aNa–Ca borate and causes increased Na contentsof the groundwaters. Waters from these open pitmines are Na–HCO3–SO4 types. High HCO3 andSO4 contents are derived from the carbonate andgypsum contents in the lower parts of the boratezones. Dissolved solids for mine spring waters arehigher than those of the water samples from surfaceand other spring waters around the study area. ECvalues reach 2850 lS/cm with pH of 8.5. Arsenicand especially B have remarkable high values of0.9 mg/L and 391 mg/L, respectively.

Sodium concentrations vary between 4.5 and301 mg/L in the study area. Especially in the minesprings and the waste waters in the pool, the domi-nant cation is Na except in the Tulu mine. Sodiumcan be derived from ulexite. Calcium and Mg aremajor cations in the groundwater that dischargesfrom the borate zone and tuff. The origin of Ca isprobably from colemanite, calcite and aragonite.Mg concentration is approximately 44 mg/L. Mag-nesium is found in hydroboracite in the Guneviand Kireclik mines (Helvacı, 1995).

Sulfate concentrations are between 6 and519 mg/L. In samples 1, 2, 5 and 7, SO4 values aremore than 20% (in meq/L). This can be explainedby the existence of anhydrite, gypsum and celestitethat are present in the borate zone.

Boron, As, Li, Sr and Si are more abundant ele-ments than other minor ions in the study area. Lith-ium has been detected in large amounts in theborate deposits of Turkey (Helvacı et al., 2004), par-ticularly the Bigadic� deposits which have a high con-centration (Li2O = 0.71%), this reflects the presenceof Hectorite (Na0.4Mg2.7Li0.3Si4O10(OH)2). Lithiumconcentrations of the borate deposits are positivelycorrelated with the amounts and types of clay.

Table 1Chemical properties of the water samples

Samples T

(�C)

pH Eh

(mV)

EC

(mS/

cm)

Na

(mg/

L)

K

(mg/

L)

Ca

(mg/

L)

Mg

(mg/

L)

Cl

(mg/

L)

HCO3

(mg/

L)

SO4

(mg/

L)

Al

(lg/

L)

As

(lg/

L)

B

(mg/

L)

Cu

(lg/

L)

Fe

(lg/

L)

Li

(mg/

L)

Mn

(lg/

L)

Pb

(lg/

L)

Sb

(lg/

L)

Si

(mg/

L)

Sr

(mg/

L)

Zn

(lg/

L)

1 (Spring in

Simav

borate mine)

10.0 8.80 �107 1.20 224 4.90 53.7 16.9 10.0 580 222 168 911 161 2.50 84.0 0.77 6.10 – 9.20 12.6 8.00 3.20

2 (Spring in Tulu

borate mine)

8.00 8.30 �82.0 1.43 21.6 2.60 306 22.8 7.00 400 519 42.0 280 227 1.50 307 0.46 3.20 – 21.7 8.81 13.7 4.50

3 (Spring in

tuff unit)

13.0 7.10 �15.0 0.86 4.50 0.30 59.7 69.8 15.0 425 54.0 11.0 24.6 0.13 1.10 29.0 0.30 0.60 – 0.50 17.9 1.81 1.60

4 (Spring in Acep

borate mine)

10.0 8.80 �109 2.85 351 4.00 60.7 11.4 7.00 800 126 77.0 752 391 3.40 17.0 0.73 2.70 – 17.20 6.4 4.97 3.70

5 (Spring) 15.0 7.50 �40.0 1.20 26.0 0.60 107 81.8 16.0 450 282 20.0 96.3 86.5 1.70 99.0 0.74 1.00 – 1.20 28.2 8.80 3.50

6 (Spring in

tuff unit)

13.0 7.60 �44.0 0.82 12.2 0.30 74.2 55.8 13.0 430 72.0 7.00 73.2 21.4 0.90 74.0 0.57 0.40 – 1.30 25.6 2.55 3.70

7 (Pond water) 8.00 8.70 �102.0 0.99 135 3.60 40.1 21.2 12.0 340 171 24.0 167 148 0.90 <10 0.28 0.30 – 5.70 8.5 5.41 0.60

8 (Spring) 15.0 7.90 �60.0 0.74 10.4 0.30 65.2 52.6 10.0 455 33.0 12.0 91.6 3.74 3.80 66.0 0.52 0.40 – 1.50 26.8 1.93 3.20

9 (Spring) 13.0 7.70 �50.0 0.75 11.6 4.60 51.4 58.5 9.00 395 30.0 53.0 142 23.9 2.80 76.0 0.28 1.20 0.10 1.90 16.4 1.36 2.90

10 (Spring) 12.0 8.30 �80.0 0.78 40.7 3.50 82.3 29.9 20.0 350 69.0 19.0 34.1 0.78 2.80 119 0.07 1.70 0.30 0.70 15.4 0.47 8.30

11 (Spring) 12.0 7.30 �32.0 0.62 13.8 0.90 88.6 22.4 19.0 295 63.0 18.0 307 0.17 1.80 187 0.07 1.30 0.10 1.70 18.7 0.58 4.60

12 (Spring

in tuff unit)

13.0 7.20 �25.0 0.76 22.0 0.90 116 22.7 17.0 420 42.0 19.0 273 0.10 1.30 253 0.07 7.40 0.20 1.30 14.1 0.96 3.20

13 (Spring in

tuff unit)

13.0 7.70 �52.0 0.80 51.7 0.80 51.0 56.2 10.0 500 24.0 23.0 186 58.1 2.60 66.0 0.83 0.60 0.10 2.20 34.7 5.62 3.60

14 (Spring) 13.0 7.60 �46.0 0.70 58.0 1.60 51.6 35.3 7.00 435 21.0 70.0 326 0.40 5.20 196 0.62 4.90 12.0 2.70 29.2 1.20 16.0

15 (Spring in

contact of the

borate zone)

11.0 7.90 �60.0 0.59 30.4 0.60 51.9 36.5 2.00 375 24.0 54.0 30.7 331 1.80 25.0 0.54 1.50 1.50 2.60 27.1 4.77 5.80

16 (River water) 9.00 8.40 �83.0 0.27 12.7 2.30 26.1 15.0 6.00 170 9.00 130 14.9 0.13 1.90 117 0.02 23.8 0.80 0.90 9.54 0.14 5.50

17 (River water) 9.00 8.20 �73.0 0.29 13.5 2.40 27.4 16.3 7.00 180 12.0 109 18.1 0.24 7.40 116 0.03 24.6 3.50 1.10 10.1 0.16 9.90

18 (Spring) 14.0 7.30 �31.0 0.94 12.7 0.40 81.6 78.1 12.0 440 21.0 18.0 95.3 1.69 29.3 138 0.98 1.10 2.10 1.60 37.8 2.69 22.1

19 (Spring) 10.0 8.00 �63.0 0.87 12.4 0.30 65.9 75.6 10.0 520 6.00 21.0 65.7 0.49 3.80 109 1.04 1.40 1.60 1.20 40.9 2.45 6.30

20 (Spring from

the contact

of borate zone

and upper

tuff unit)

12.0 8.20 �75.0 0.75 8.90 0.30 74.0 55.8 11.0 460 18.0 22.0 32.4 8.33 3.50 226 1.25 1.70 1.40 1.40 39.4 3.82 6.20

21 (Spring) 9.00 7.50 �48.0 0.68 26.2 0.60 88.8 25.6 12.0 380 27.0 26.0 337 0.21 4.30 209 0.19 17.1 1.70 2.10 16.6 0.95 7.50

22 (River water) 7.00 8.40 �82.0 0.40 16.5 2.80 51.0 17.1 8.00 210 33.0 231 9.90 0.12 4.90 353 0.02 22.0 1.50 0.90 10.7 0.24 7.60

23 (Spring

in tuff unit)

13.0 7.60 �38.0 0.58 14.9 2.40 81.5 20.9 8.00 355 21.0 6.00 30.5 0.05 1.10 188 0.07 0.40 � 0.10 15.1 0.51 2.10

24 (Spring in

lower

limestone)

11.0 7.60 �49.0 0.76 12.2 0.70 91.1 50.0 10.0 540 21.0 6.00 33.3 0.20 0.90 277 0.06 0.30 – 0.10 11.1 0.44 2.30

25 (River water) 8.00 8.30 �82.0 0.42 19.1 3.10 56.3 18.3 10.0 250 39.0 275 20.3 2.08 4.40 441 0.03 28.7 0.80 0.80 10.8 0.32 9.30

2468U

.G

emici

eta

l./Ap

plied

Geo

chem

istry2

3(

20

08

)2

46

2–

24

76

Fig. 3. Distribution of the water samples in the Piper triangular diagram.


The whole-rock mineralogy of the Bigadic� claysconsists of dominant smectite, K-feldspar, ulexiteand calcite. Lithium concentrations of the watersamples in the study area range from 21.3 lg/L(Simav River) and 1250 lg/L (Upper borate-tuffcontact), with an average value of 421 lg/L.

Silicon concentrations range between 6.35 and40.9 mg/L in the study area. Although all of thewaters are ‘‘cold water”, Si values have high valuessimilar to some of thermal waters. Especially in thewaters from borate zone (samples: 5, 6, 8, 13, 15, 18,19 and 20) Si values are as great as 41 mg/L. Due tothe existence of howlite [Ca2B5SiO9 � (OH)5] inborate deposits and the tuffs, Si can be transferredto the water as a result of water rock interactionprocesses.

The chemistry of Sr is similar to that of Ca andcommonly replaces Ca in igneous rock minerals(Hem, 1985). Strontium contents of waters fromvolcanic rocks and tuffs are between 43 and1440 mg/L in the Bigadic� Basin (Helvaci, 1995).On the other hand, tunellite [SrB6O10 � 4H2O] andcelestite are present in the study area and Sr concen-trations of the waters range from 144 to 13,700 lg/L. The maximum Sr values were detected in ground-water from an open pit mine, the borate zone andwaste water pool. Due to both the exchange of Sr

and Ca; and existence of tunellite and celestite, theamount of Sr can be as high as 14 mg/L in thewaters.

Correlation analyses were carried out for As, Band some selected major and trace elements. Thesalinity of the waters (EC values) is derived fromNa, HCO3 and B ions which can be seen from thecorrelation matrix. Calcium and SO4 ions show agood positive correlation (r2 = 0.77) that indicatesthe dissolution of gypsum in the study area. In addi-tion to Ca, Sr has a near-perfect correlation(r2 = 0.89) with SO4, derived from celestite. Sodiumis correlated with HCO3, Al, As and B in thegroundwater samples (r2 = 0.81, 0.71, 0.85 and0.68, respectively). Arsenic has a positive correlationwith B (r2 = 0.23), Al (r2 = 0.25) and Sb (r2 = 0.54).A weak positive correlation is also seen between Asand SO4 (r2 = 0.11). Boron has positive correlationswith Na (r2 =0.48), Cl (r2 = 0.30) and Li(r2 = 0.033). The relationships between As, B andother elements suggest possible rock leaching fromthe host rocks containing borate minerals.

4.2. Saturation and species

An equilibrium mass-balance model has beenused to calculate the elemental aqueous speciation


and the stability of solid phases with respect to thedissolved constituents. The chemical equilibriummodeling of the waters was carried out using thePhreeqCi computer code (Parkhurst and Appelo,1999). The potential for mineral precipitation or dis-solution may be assessed using the saturation index(SI). Oversaturation is indicated when the solubilityproduct (Q) is higher than the solubility constant(K) values (Q > K) at a particular temperature andprecipitation may be expected. When Q < K, thesolution is theoretically undersaturated and dissolu-tion might be possible.

Surface and groundwaters from the study areahave similar characteristics according to their satu-ration index states. Most of the water samples wereoversaturated with calcite, dolomite, Al-silicates,quartz, strontianite and clay minerals such assmectite, montmorillonite, kaolinite and illite. Incontrast, saturation index values were negative forAs minerals, gypsum, barite and B minerals (Table2).

Water samples from the study area are typicallyundersaturated with respect to the main relevantAs-bearing minerals such as arsenolite, orpiment,and realgar. They would be predicted to dissolve.Although B content of the water samples is very high(up to 331 mg/L), water samples are undersaturatedwith respect to B-bearing minerals such as coleman-ite, hydroboracite and B2O3, according to the Phre-eqCi results (Table 2). This undersaturatedcondition means that B minerals will tend to dissolvealong the circulation path of the groundwaters.

The behavior of B in most groundwaters is con-trolled by the borate ion-boric acid equilibrium.The distribution of these species is controlled bypH, salinity and specific cation concentrations(Dotsika et al., 2006). The dominant aqueous speciesof B are undissociated boric acid, B(OH)3 (trigonalspecies), and the borate anion, B(OH)4� (tetrahedralspecies), whose relative abundances are a sensitivefunction of pH. At pH less than about 8.8 at25 �C, B(OH)3 is the dominant species and B in solu-tion generally behaves conservatively (Larsen et al.,2001). In the pH range between about 7 and 10 Badsorption reactions with some minerals, such assome of the clays, become increasingly importantas B(OH)4� becomes the dominant B species in solu-tion (Larsen et al., 2001). Boron3+ is the dominant Bspecies for the water samples; more than 93.7% is inthe form of B(OH)3. The rest is mainly in the form ofBO2� and Ca(or Mg)B(OH)4+, with about 5.4% and0.6%, respectively. In samples 1, 4 and 7 the B(OH)3

molality was less and BO2� was the dominant Bspecies.

Using the llnl database, speciation and saturationstate was calculated for the As system. In alkalineoxidizing environments, As(V) is commonly presentin the form of HAsO2�

4 and is thermodynamically sta-ble at the Eh–pH conditions encountered (Fig. 4). Inthe neutral and slightly alkaline waters, As(III) spe-cies are dominant and the major species are HAsO2

and As(OH)3. Depending on the Eh–pH characteris-tics, As(III) is the dominant As species for watersfrom the study area. Arsenic(III) species are moremobile than As(V) in the groundwater systembecause As(III) is less likely to become stronglysorbed to a mineral surface than a negatively chargedAs(V) complex (Ongley et al., 2001; Sracek et al.,2004). Due to the greater toxicity of As3+, nearly 60times that of As5+, samples 3, 5, 6, 11, 12, 13, 14,18, 21 and 24 are considered to be more dangerousfor living organisms in and around the study area.

The plotted data in Fig. 4 are located near theboundary of H3AsO3 and HAsO�2

4 . For samples 3,5, 6, 11, 12, 13, 14, 18, 21 and 24, As(III) is domi-nant. These results coincide with the data obtainedby species calculations with PhreeqC. The As(III)/As(V) ratio of 11 water samples (samples 3, 5, 6,9, 11, 12, 13, 14, 18, 21 and 24) have values greaterthan 1.00 and as high as 37 in sample 3. This situa-tion indicates the toxicological risk at this site. Themajor species of As(III) are HAsO2 and As(OH)3

with mean values of 50% and 45%, respectively.H2AsO�3 and AsO�2 are the minor species (2.9%).For As(V), the dominant species are HAsO�4(92%) and H2AsO�4 (8.4%).

The species and SI calculations with the PhreeqCicomputer code show that the dominant species of Liis Li2+ and the samples are saturated with Li–Alsilicates, petalite (LiAlSi4O10), spodumene (LiAl-Si2O6); and also smectite (Ca � 025Na � 1K � 2Fe �5Fe � 2Mg1 � 15A11 � 25Si3 � 5H2O12), K-feldspar(KAlSi3O8) and calcite (CaCO3). This situationshows the similarity with whole rock mineralogyof the Bigadic� clays. Lithium values are relativelyhigh in water samples that give rise to the saturationfor Li minerals mentioned above. However Helvacıet al. (2004) stated that no Li minerals were detectedby XRD and Li was bound in the smectites which isprobably hectorite in Bigadic�.

In addition, Sr found in the carbonate mineralsand the reaction is as follows:

SrðHCO3Þ2 ¼ SrCO3 þ CO2 þH2O

Table 2Saturation indices of some selected minerals and the speciation of arsenic and boron

1 2 4 5 7 8 9 10 11 12 13 14 15 17 18 19 21 22 24 25

Albite 3.0 1.2 1.9 1.8 1.7 1.2 1.4 1.4 1.2 0.9 2.6 2.9 2.7 1.5 1.8 2.4 1.6 2.2 0.1 2.2Analcime 2.3 0.5 1.4 0.8 1.1 0.3 0.6 0.7 0.3 0.2 1.5 1.9 1.6 0.9 0.7 1.2 0.7 1.4 �0.5 1.4Anhydrite �2.0 �1.0 �2.2 �1.5 �2.1 �2.5 �2.7 �2.1 �2.1 �2.2 �2.8 �2.8 �2.8 �3.2 �2.6 �3.4 �2.5 �2.6 �2.6 �2.5Barite 0.8 1.0 1.0 1.4 0.7 0.2 0.3 0.5 0.2 0.5 0.4 �0.3 0.4 �0.4 0.5 �0.1 �0.2 0.3 0.1 0.2Calcite 1.2 1.2 1.1 0.4 0.7 0.7 0.3 1.1 0 0.2 0.5 0.3 0.4 0.2 0.1 0.7 0.3 0.6 0.6 0.7Celestine �1.6 �1.1 �2 �1.5 �1.8 �2.9 �3.1 �3.2 �3.1 �3.1 �2.6 �3.3 �2.6 �4.3 �2.9 �3.6 �3.3 �3.7 �3.8 �3.6Dolomite 3.1 2.6 2.7 2.1 2.4 2.6 2.1 3.0 0.8 1.1 2.3 1.7 2.0 1.5 1.6 2.9 1.3 2.1 2.2 2.2Gypsum �1.6 �0.6 �1.9 �1.2 �1.8 �2.2 �2.4 �1.8 �1.8 �1.9 �2.5 �2.5 �2.4 �2.9 �2.3 �3 �2.2 �2.2 �2.3 �2.1K-Felds 4.4 3.3 3.1 3.1 3.2 2.6 4.0 3.4 3.0 2.5 3.8 4.4 4.0 3.9 3.4 3.9 3.0 4.5 1.9 4.5Petalite 4.4 3.2 2.8 4.3 2.7 3.9 3.6 2.5 2.9 2.2 5.0 5.5 5.0 2.6 5.0 5.7 3.4 3.1 1.5 3.2Quartz 0.7 0.6 0.4 0.9 0.5 0.9 0.7 0.7 0.8 0.7 1.1 1.0 1.0 0.6 1.1 1.2 0.8 0.7 0.6 0.7Arsenolite �13 �11 �13 �11 �14 �12 �11 �14 �10 �10 �11 �10 �13 �14 �11 �12 �9.7 �15 �12 �14Arsenopyrite �51 �48 �51 �49 �49 �50 �50 �52 �48 �48 �50 �49 �52 �51 �49.5 �51.3 �46.5 �51.2 �49 �50Orpiment �73 �64 �72 �64 �72 �69 �67 �74 �60 �61 �68 �65 �70 �72 �64.6 �71 �57.9 �72.8 �65 �70Realgar �30 �27 �30 �26 �30 �28 �27 �30 �25 �25 �28 �27 �29 �30 �26.5 �29.3 �24.4 �30.6 �27 �30Borax �5.6 �7.7 �3.9 �11 �6.2 �17 �13 �17 �23 �23 �11 �19 �7.5 �20 �18.9 �19.7 �21.2 �20.8 �22 �16Boric acid �1.6 �1.4 �1.2 �1.8 �1.6 �3.2 �2.4 �3.9 �4.5 �4.7 �2 �4.1 �1.2 �4.3 �3.5 �4.0 �4.4 �4.6 �4.4 �3.4Colemanite �4.5 �3.7 �2.3 �9.9 �5 �17 �13 �19 �27 �28 �11 �24 �5.3 �24 �21 �22 �26 �24 �25 �17Hidroboracite �3.6 �3.5 �1.6 �8.6 �3.9 �16 �12 �18 �26 �28 �9.1 �23 �4.1 �23 �20 �21 �25 �23 �24 �16

As(III) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)HAsO2 43 50 44 52 45 52 52 49 53 53 52 52 51 50 53 51 52 49 52 50As(OH)3 39 44 39 46 41 46 46 44 47 47 46 46 46 45 47 46 47 44 46 45H2AsO�3 8.9 3.0 8.4 0.7 7.0 1.5 1.0 3.7 0.4 0.3 1.1 0.7 1.4 2.2 0.5 1.6 0.5 3.2 0.7 2.9AsO�2 8.9 3.0 8.4 0.7 7.0 1.5 1.0 3.6 0.4 0.3 1.1 0.7 1.4 2.2 0.4 1.6 0.5 3.2 0.7 2.9

As(V) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)HAsO�2

4 99 98 99 88 99 94 92 98 81 78 92 90 94 96 83 95 86 98 90 97H2AsO�4 0.7 2.1 0.8 11.7 0.9 6.0 8.5 2.3 19 22 7.6 11 5.6 3.6 17 4.8 14 2.3 10 2.5

B(3) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)B(OH)3 78 90 79 98 82 96 97 90 99 99 97 97 96 94 99 95 99 91 98 92BO�2 20 7.2 19.2 1.5 16.5 3.2 2.2 8.20 0.9 0.7 2.4 2.4 3.4 5.3 1.0 3.7 1.2 7.8 1.7 7.1CaBðOHÞþ4 1.2 2.5 1.1 0.3 0.9 0.5 0.4 0.90 0.1 0.1 0.4 0.4 0.4 0.3 0.2 0.8 0.2 0.7 0.2 0.7

U.

Gem

iciet

al./A

pp

liedG

eoch

emistry

23

(2

00

8)

24

62

–2

47

62471

Fig. 4. Distribution of water samples in Eh–pH diagram (modified form Vink 1996).


According to this reaction, all of the waters areoversaturated with respect to SrCO3 in the studyarea except samples 11 and 23. Most of the watersare oversaturated with respect to different types ofsilicates containing Al, K, Mg, Fe, Ca, U, Zn andSiO2.

4.3. The distribution of contaminants

Enrichment of B, As and some major and traceelements in groundwaters is directly related to theleaching of the tuff and limestone aquifer rocks.The groundwaters emerge as springs along fracturezones and contacts of the limestones and tuffs.Along their flowpaths, groundwaters dissolve cole-manite and ulexite, leading to a strong increase inthe B concentrations, and affecting the overall waterchemistry as well. Arsenic minerals or As-bearingpyrite are absent in the Neogene sequence of theBigadic� borate deposits. However results of thechemical analyses for colemanite and ulexite miner-als showed that As was around 70 mg/kg (Helvacıand Alaca, 1991), coinciding with the high As con-centrations in groundwaters.

Trace element analyses show the distribution ofpollutants in the water samples. These analysesshow that some ions such as SO4, and those of Asand B are enriched due to mining activity especiallyat the Gunevi and Acep mines. Their distributionsare given in Fig. 5.

The concentrations of B in the study area rangefrom 54 to 391,000 lg/L. The average B concentra-tion is around 640 mg/L and 35 mg/L for surfaceand groundwater samples, respectively. The greatestB concentrations were detected at the mine areas.

Springs in open pit mines have higher values, aver-aging 260 mg/L. These values exceed recommendedlimits for drinking and especially irrigation.

The mean value of 77 mg/L SO4 is exceeded atseveral sampling points near the borate mines,where the maximum value was 519 mg/L. HighSO4 concentrations have been associated with thedissolution of gypsum. Sulfate concentrationexceeds the tolerance limits (250 mg/L for bothEPA (2003) and TS (1997) in the samples of 1, 2,5 and 7 (Fig. 5e). Total dissolved solids (TDS)increase towards the north especially in and aroundmines. This is supported by the EC distribution map(Fig. 5a). Copper, Mn, Zn and Li values areenriched but do not exceed the drinking water stan-dards of TSE 266 (TS, 1997). In general Al contentsare lower with the maximum value of Al, 220 lg/L,found in sample 25, which exceeds the drinkingwater standards of 200 lg/L for the EPA (2003)and TS (1997) (Fig. 5b). One of the highly concen-trated metals in the waters is Fe, which exceededthe drinking water standard (TS, 1997; 0.2 mg/L)in samples 2, 12, 20, 21, 22, 24 and 25. The greatestvalues, up to 440 lg/L, are seen in and around theTulu and Gunevi mines (Fig. 5d).

One of the major pollutants is As, found at con-centrations between 33 and 911 lg/L in the ground-water samples. Arsenic is a common constituent ingroundwater that affects human health adverselyat levels as low as 10 lg/L (WHO, 1993; Bhattach-arya et al., 2002). A wide variety of adverse healtheffects, including skin and internal cancers and car-diovascular and neurological effects, has beenattributed to chronic As exposure, primarily fromdrinking water (NRC, 1999). The distribution of

Fig. 5. Distribution of some selected elements in groundwaters (all sample numbers are same as in Fig. 1).



As concentration is shown in Fig. 5f. Arsenic con-centrations increased systematically near the Simavand Gunevi mines. Although the As concentrationsdecreased in the south of the study area, concentra-tions in all of the waters exceed the tolerance limits.Antimony is a Group V element that is similar to Asin many aspects of chemical behavior and toxicity toanimals (Gurnani et al., 1994; WHO, 1993; Filellaet al., 2002). The observed Sb concentrations werelower than those of As (Fig. 5h).

5. Conclusions

Groundwater samples from the Bigadic� B miningarea were analysed to evaluate the B and As distri-butions. High B, As, Li and Sr anomalies wererecorded within the aquifer of the Bigadic� area.Laboratory data and field investigations showedthat high B and As concentrations in groundwatersare in part natural and related to leaching of theborate-bearing rocks of Neogene saline lake sedi-ments. Groundwaters were classified as mainlyNa–HCO3(SO4) and Mg–Ca(Ca–Mg)–HCO3 whichreflects the lithologies of the aquifer rocks andwater–rock interaction processes. High Na and Caconcentrations could be derived from dissolutionof ulexite [NaCaB5O9.8H2O] and colemanite[Ca2B8O11 � 5H2O], or calcite. The presence of gyp-sum in the lower parts of the borate zones causesthe enrichment of the SO4.

Arsenic is one of the major pollutants in the area,and showed high spatial variation ranged from 33 to911 lg/L in the groundwater samples. Arsenic val-ues increased close to the Simav and Gunevi mines,reaching 305 lg/L and decreased to the south of thestudy area. Arsenic concentrations of all the watersamples exceeded the limit of 10 lg/L proposedfor human consumption. Speciation calculationsperformed with the PhreeqCi computer codeshowed that As(III) is the dominant As species forgroundwaters in the study area. Because As(III) ismore mobile and toxic than As(V), drinking thesegroundwaters could pose a threat to human health.

The average B concentration is around 640 mg/Land 35 mg/L for surface and groundwater samples,respectively, with the greatest B concentrationsdetected at the open pit mines (average 260 mg/L).These values are greater than the safe levels fordrinking and irrigation. The dominant aqueous spe-cies of B are undissociated boric acid, B(OH)3 (aver-age 94%), and the borate anion, B(OH)4�, whoserelative abundances are a sensitive function of pH.

Minor dissolved species of B include BO2� andCa(or Mg)B(OH)4+.

Sulfate, Al and Fe concentrations are also abovethe drinking water standard for some groundwatersamples. Lithium, Sr and Si also are abundant ele-ments in the water samples. Silicon can be trans-ferred to the water as a result of the dissolution ofthe howlite mineral. Due to the both exchangemechanisms of Sr and Ca and the existence of tun-ellite and celestite, Sr concentrations reached 14 mg/L in the waters.

Arsenic-bearing minerals such as arsenolite, orpi-ment, realgar and B-bearing minerals have negativesaturation index values indicating that groundwa-ters will tend to dissolve these minerals, if present,despite their high concentrations. Enrichment ofB, As and some major and trace elements in ground-waters are directly related to the leaching of the hostrock. Groundwaters dissolve colemanite and ulexitecausing an increase in the B concentrations. Arsenicminerals or As-bearing pyrite are absent in the Neo-gene sequence of the Bigadic� borate deposits. How-ever the high contents of As in waters are related tothe existence of As in the rocks. The extension of theborate zones in the aquifer systems for the studyarea is the essential factor for B and As enrichment.

Acknowledgements

The authors acknowledge the financial supportof Dokuz Eylul University Research Fund(03.KB.FEN.085) and Turkish Academy of Sci-ences (TUBA). Field work was supported by Eti-bank State Company. The authors would like tothank anonymous reviewers and Dr. Richard Wan-ty for their critical comment and suggestions in ear-lier version of the manuscript.

References

Acharyya, S.K., Lahiri, S., Raymahasbay, B.C., Guha, S.,

Bhowmik, A., 2000. Arsenic toxicity of groundwater in parts

of the Bengal basin in India and Bangladesh: the role of

Quaternary stratigraphy and Holocene sea-level fluctuation.

Environ. Geol. 39, 1127–1137.

Aiuppa, A., Avino, R., Brusca, L., Caliro, S., Chiodini, G.,

Alessandro, WD., Favara, R., Federico, C., Ginerva, W.,

Inguaggiato, S., Longo, M., Pecoraino, G., Valenza, M.,

2006. Mineral control of arsenic content in thermal waters

from volcano-hosted hydrothermal systems: insights from

island of Ischia and Phlegrean fields (Campanian Volcanic

Province, Italy). Chem. Geol. 229, 313–330.

Axtmann, R.C., 1975. Environmental impact of a geothermal

power plant. Science 187, 795–797.


Bhattacharya, P., Jacks, G., Ahmed, K.M., Routh, J., Khan,

A.A., 2002. Arsenic in groundwater of the Bengal Delta Plain

Aquifers in Bangladesh. Bull. Environ. Contam. Toxicol. 69,

538–545.

Bianchini, G., Pennisi, M., Cioni, R., Muti, A., Cerbai, N.,

Kloppmann, W., 2005. Hydrochemistry of the high-boron

groundwaters of the Cornia aquifer (Tuscany, Italy). Geo-

thermics 34, 297–319.

Calmbach, L., 1997. AquaChem Computer Code Version 3.7.42.

Waterloo Hydrogeologic. Waterloo, ON.

Col, M., Col, C., 2003. Environmental boron contamination in

waters of Hisarcık area in the Kutahya Province of Turkey.

Food Chem. Toxicol. 41, 1417–1420.

Colak, M., Gemici, U., Tarcan, G., 2003. The effects of

colemanite deposits on the arsenic concentrations of soil,

and groundwater in _Igdekoy–Emet–Kutahya–Turkey. Water

Air Soil Pollut. 149, 127–143.

Craw, D., Chappel, D., Reay, A., 1999. Environmental mercury

and arsenic sources in fossil hydrothermal systems, North-

land, New Zealand. Environ. Geol. 39, 875–887.

Dotsika, E., Poutoukıs, D., Michelot, J.L., Kloppmann, W.,

2006. Stable isotope and chloride, boron study for tracing

sources of boron contamination in groundwater: boron

contents in fresh and thermal water in different areas in

Greece. Water Air Soil Pollut. 174, 19–32.

EPA, 2003. Standard Methods for the Examination of Water and

Wastewater. American Public Health Assoc., US.

Erkul, F., Helvacı, C., Sozbilir, H., 2006. Olivine basalt and

trachyandesite peperites formed at the subsurface/surface

interface of a semi-arid lake: an example from the Early

Miocene Bigadic� basin, western Turkey. J. Volcanol. Geo-

therm. Res. 149, 240–262.

Filella, M., Belzile, N., Chen, Y.W., 2002. Antimony in the

environment: a review focused on natural waters: I. Occur-

rence. Earth-Sci. Rev. 57, 125–176.

Fytianos, K., Christoforidis, C., 2004. Nitrate, arsenic and

chloride pollution of drinking water in Northern Greece.

Elaboration by applying GIS. Environ. Monit. Assess. 93, 55–

67.

Gemici, U., 2004. Impact of acid mine drainage from the

abandoned Halıkoy mercury mine (western Turkey) on

surface and groundwaters. Bull. Environ. Contam. Toxicol.

72, 482–489.

Gemici, U., Tarcan, G., 2002. Distribution of boron in thermal

waters of Western Anatolia, Turkey, and examples on their

environmental impacts. Environ. Geol. 43, 87–98.

Gemici, U., Tarcan, G., 2004. Hydrogeological and hydrogeo-

chemical features of the Heybeli Spa, Afyon, Turkey: arsenic

and the other contaminants in the thermal waters. Bull.

Environ. Contam. Toxicol. 72, 1104–1114.

Gemici, U., Tarcan, G., 2007. Assessment of the pollutants in

farming soils and waters around untreated abandoned

Turkonu mercury mine (Turkey). Bull. Environ. Contam.

Toxicol. 79, 20–24.

Gemici, U., Tarcan, G., Helvacı, C., Colak, M., 2007. Distribu-

tion of As, B and other elements in Kocac�ay River catchment

(Emet–Turkey). Water–Rock Interaction 12, 1047–1051.

Gundogdu, M.N., Bonnot-Courtois, C., Clauer, N., 1989.

Isotopic and chemical signatures of sedimentary smectite

and diagenetic clinoptilolite of a lacustrine Neogene basin

near Bigadic�, western Turkey. Appl. Geochem. 4,

635–644.

Gurnani, N., Sharma, A., Tulukder, G., 1994. Effects of

antimony on cellular systems in animals: a review. Nucleus

37, 71–96.

Gurzau, E.S., Gurzau, A.E., 2001. Arsenic in drinking water

from groundwater in Transylvania, Romania. In: Chapell,

W.R., Abernathy, C.O., Calderon, R.L. (Eds.), Arsenic

Exposure and Health Effects IV. Elsevier, Amsterdam, pp.

181–184.

Helvacı, C., 1995. Stratigraphy, mineralogy and genesis of the

Bigadic� borate deposits, Western Turkey. Econ. Geol. 90,

1237–1260.

Helvacı, C., 2005. Borates. In: Selley, R.C., Cocks, L.R.M.,

Plimer, I.R. (Eds.), Encyclopedia of Geology, vol. 3. Elsevier,

pp. 510–522.

Helvacı, C., Alaca, O., 1991. Geology and mineralogy of the

Bigadic� borate deposits and vicinity. Min. Res. Explor. Bull.

113, 31–63.

Helvacı, C., Alonso, R.N., 2000. Borate deposits of Turkey and

Argentina; a summary and geological comparison. Turkish J.

Earth Sci. 24, 1–27.

Helvacı, C., Orti, F., 1998. Sedimentology and diagenesis of

Miocene colemanite–ulexite deposits (Western Anatolia,

Turkey). J. Sediment. Res. 68, 1021–1033.

Helvacı, C., Yagmurlu, F., 1995. Geological setting and eco-

nomic potential of the lignite and evaporite-bearing Neogene

basins of Western Anatolia, Turkey. Israel J. Earth Sci. 44,

91–105.

Helvacı, C., Mordogan, H., Colak, M., Gundogan, _I., 2004.

Presence and distribution of lithium in borate deposits and

some recent lake waters of west-central Turkey. Int. Geol.

Rev. 46, 177–190.

Helvacı, C., Stamatakis, M., Zagouroglou, C., Kamaris, J., 1993.

Borate minerals and related authigenic silicates in northeast-

ern Mediterranean Late Miocene continental basins. Explor.

Min. Geol. 2, 171–178.

Hem, J.D., 1985. Study and interpretation of the chemical

characteristics of natural waters. US Geol. Surv. Water-

Supply Pap. 2254, third ed.

IAH, 1979. Map of Mineral and Thermal Water of Europe. Scale

1:500.000. International Association of Hydrogeologists,

United Kingdom.

Katsoyiannis, I.A., Hug, S.J., Amman, A., Zikoudi, A., Hatzi-

liontos, C., 2007. Arsenic speciation and uranium concentra-

tions in drinking water supply wells in Northern Greece:

correlations with redox indicative parameters and implica-

tions for groundwater treatment. Sci. Total Environ. 383,

128–140.

Kouras, A., Katsoyiannis, I., Voutsa, D., 2007. Distribution of

arsenic in the area of Chalkidiki, Northern Greece. J. Hazard.

Mater. 147, 890–899.

Keimowitz, A.R., Simpson, H.J., Stute, M., Datta, S., Chillrud,

S.N., Ross, J., Tsang, M., 2005. Naturally occurring arsenic:

mobilization at a landfill in Maine and implications for

remediation. Appl. Geochem. 20, 1985–2002.

Kistler, R.B., Helvacı, C., 1994. Boron and borates. In: Carr,

D.D. (Ed.), Industrial Minerals and Rocks, sixth ed. Society

of Mining, Metallurgy and Exploration, Inc., Littleton,

Colorado, pp. 171–178.

Kloppmann, W., Bianchini, G., Charalambides, A., Casanova, J.,

Cerbai, N., Cioni, R., Dotsika, E., Negrel, P., Guerrot, C.,

Gutierrez, A., Klose, P., Kouimtzis, T., Marei, A., Muti, A.,

Pankratov, I., Pennisi, M., Shathas, A., Vengosh, A., Voutsa,


D., 2004. Boron contamination of water resources in the

Mediterranean region: distribution, social impact and reme-

diation. Final Report Section 6 of Project ‘‘Boremed’’,

Contract EVKI-CT-2000-00046 (European Union).

Larsen, D., Swihart, G.H., Xiao, Y., 2001. Hydrochemistry and

isotope composition of springs in the Tecopa basin, south-

eastern California, USA. Chem. Geol. 179, 17–35.

Lyday, P.D., 1991. Boron-1990. Mineral Commodity Summaries,

US Bureau of Mines, pp. 133–142.

Meixner, H., 1956. Die neue turkische boratprovinz un _Iskelekoy

bei Bigadic� im Vilayet Balıkesir. Sonderabdruck aus Kali und

Steinsals, part, 2. Essen, Verlag, 43–37.

Mitrakas, M., 2001. A survey of arsenic levels in tap, under-

ground and thermal mineral waters of Greece. Fresen.

Environ. Bull. 10, 717–721.

Nimick, A.D., 1998. Arsenic hydrogeochemistry in an irrigated

river valley – A re-evaluation. Ground Water 36, 743–753.

Nordstrom, D.K., 2002. Worldwide occurrences of arsenic in

groundwater. Science 296, 2143–2145.

NRC, 1999. Arsenic in Drinking Waters: Subcommittee on

Arsenic in Drinking Water. National Research Council.

Ongley, L.K., Armienta, M.A., Heggeman, K., Lathrop, A.S.,

Mango, H., Miller, W., Pickelner, S., 2001. Arsenic removal

from contaminated water by the soyatal formation, Zimapan

mining district, Mexico – A potential low-cost low-tech

remediation system. Geochem. Explor. Environ. Anal. 1, 23–

31.

Ozpeker, I., 1969. Batı Anadolu Borat Yataklarının Mukayeseli

Jenetik Etudu (Geological investigation of the borate minings

in the western Anatolia). Ph.D. Thesis, Istanbul Technical

Univ.

Parkhurst, D.L., Appelo, C.A.J., 1999. User’s Guide to PHRE-

EQC (Version 2)-A Computer Program for Speciation, Batch-

Reaction, One-Dimensional Transport, and Inverse Geo-

chemical Calculations. US Geol. Surv. Water-Resour. In-

vest.Rep. 99-4259.

Pennisi, M., Gonfiantini, R., Grassi, S., Squarci, P., 2006. The

utilization of boron and strontium isotopes for the assessment

of boron contamination of the Cecina River alluvial aquifer

(central-western Tuscany, Italy). Appl. Geochem. 21, 643–

655.

Smedley, P.L., Kinniburgh, D.G., 2002. A review of the source

behaviour and distribution of arsenic in natural waters. Appl.

Geochem. 17, 517–568.

Sracek, C., Bhattacharya, P., Jacks, G., Gustafsson, J.P.,

Bromssen, M., 2004. Behavior of arsenic and geochemical

modeling of arsenic enrichment in aqueous environments.

Appl. Geochem. 19, 169–180.

Tarcan, G., Gemici, U., 2005. Effects of the contaminants from

Turgutlu-Urganli thermomineral waters on cold ground and

surface waters. Bull. Environ. Contam. Toxicol. 74, 485–492.

TS (Turkish Standards), 1997. Sular-_Ic�me ve Kullanma Suları

(Waters: for drinking and other purposes). Turk Standartları

Enstitusu, Ankara.

Varsanyi, I., Fodre, Z., Bartha, A., 1991. Arsenic in drinking

water and mortality in the southern Great Plain, Hungary.

Environ. Geochem. Health 13, 14–23.

Vengosh, A., Helvacı, C., Karamanderesi, _I.H., 2002. Geochem-

ical constraints for the origin of thermal waters from western

Turkey. Appl. Geochem. 17, 163–183.

Vink, B.W., 1996. Stability relations of antimony and arsenic

compounds in the light of revised and extended Eh–pH

diagrams. Chem. Geol. 130, 21–30.

White, D.E., 1981. Active geothermal systems and hydrothermal

ore deposits. Econ. Geol., 392–405, 75th Anniv. vol.

WHO (World Health Organization), 1993. WHO Guidelines for

Drinking Water Quality. Health Criteria and Other Support-

ing Information, vol. 2. WHO, Geneva.

High arsenic and boron concentrations in groundwaters related to mining activity in the Bigadic...

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