ISSN 0097 8078, Water Resources, 2016, Vol. 43, No. 1, pp. 184–199. © Pleiades Publishing, Ltd., 2016.
WATER QUALITY AND PROTECTION: ENVIRONMENTAL ASPECTS
Observation of Excess Heavy Metal Concentrations in Water Resources to Infer Surface Water Influences on Shallow Groundwater: a Typical Example of the Porsuk River (Eskisehir Turkey)1 Candan Alptekina and Galip Yuceb aDepartment of Geological Engineering, Istanbul University, Avcιlar 34320 Istanbul, Turkey bDepartment of Geological Engineering, Hacettepe University, Beytepe 06800 Ankara, Turkey E mail: [email protected], [email protected] Received March 22, 2015
Abstract—The Eskisehir province is well known due to its industrial and agricultural activities, which are a threat for the aquatic environment. Hence, monitoring of water quality in the area is of vital importance because of an excess heavy metal contents, especially As. The Porsuk River is heavily polluted by industrial activities from Kutahya city. It discharges into the Porsuk Dam and from there it flows relatively clean to Eskisehir city center, but beyond this point it increasingly deteriorates due to the negative impact of industrial and agricultural activities up to the junction point of Porsuk and Sakarya rivers. Heavy metal concentrations and As contents in surface and ground waters were selected as pollution indicators to examine pollution level and compare an interaction between river and groundwater. For this purpose, water samples taken between 2008 and 2010 from the Porsuk River along the section from the west of Kutahya to the discharge point into the Sakarya River, as well as groundwater samples from the wells located close to or far of the Porsuk River, were evaluated. Based on the obtained results, we found that the Porsuk River, especially at the locations close to the Sakarya River, and groundwater are polluted in terms of heavy metals and As compounds. In conclu sion, the heavy metal and As pollution is also observed in the wells close to the locations in which groundwater is fed by the Porsuk River since it acts as an influent river. Thus, surface water is considered as a polluting source of groundwater.
Keywords: Porsuk River, groundwater, pollution, heavy metal, arsenic DOI: 10.1134/S0097807816120022
1 INTRODUCTION oxygen requirement indicate that pollution is increas ing [11]. The study area is occupied about 500 km2 in the This study aims to investigate the pollution of sur north western part of Middle Anatolia between face water caused by the waste generated by industrial 39°41′00″–39°32′30″ N and 30°22′46″–31°08′00″ E and agricultural activities along the river catchment, as including the city of Eskisehir (Fig. 1) [10]. The total well as the pollution occurred in groundwater because length of the Porsuk River is 436 km with the area of of the river influence, since the river passes through the 11326 km2 [1]. In recent years, the Porsuk River which center of the city and carries the waste water into has been widely used for domestic water supply is groundwater. As a result, the pollution of the ground increasingly polluted in terms of heavy metals, espe water was identified with their possible sources. cially As. In spite of the water treatment plant for the Porsuk River, the increase in urban population, the MATERIALS AND METHODS intense activities of the various branches of industry, uncontrolled discharges of chemical wastes are the major causes of this pollution [3, 10]. Water samples, Study Area and Geology especially taken from the Porsuk River at Eskisehir Triassic metamorphic schist marble and ophiolitic sugar mill and the wastewater treatment plant after melange is the oldest units in the study area [5]. 2001, had the reduction in the value of dissolved oxy Eocene, Early and Middle Miocene age formations gen and an increase in the chemical and biological are unconformably overlain by the Pliocene age series mainly composed of conglomerate and sandstone, 1 The article is published in the original. agglomerate, tuff tuffite, basalt andesite, and marl
184 OBSERVATION OF EXCESS HEAVY METAL CONCENTRATIONS 185
S Bozüyük Mhaliçcik a ka An ry kar a a S R tre iv am Porsuk River er Aplu Sazak Dümrek ESKISEHIR
A HY Bicer Yassihöyük TA Liören KÜ Palatli
Sivrihisar N r e v Ri k Günyüzü u s r 0 5 km o P Sevitgazi
BLACK SEA City Centre ESKISEHIRAnkara Country Centre Town Kütahya Study Area Motorway MEDITERRANEAN SEA AEGEAN SEA Main road Rivers Porsuk River
Fig. 1. Location map of the study area. claystone (Fig. 2). The alluvium composes of two parts formed by the EPA 200.8 method through “ICP_MS” of Pleistocene age (Villafransiyen) and Late Quater device in the local laboratory of the State Hydraulic nary deposits which were cut by all drilled wells in the Works (DSI). By the EPA 200.8, heavy metal contents study area. Alluvium is an essential aquifer mainly in question, including As, were ionized in ICP by composed of the gravel, sand and silt materials [2]. argon before introducing into the MS. Thus, they were The total thickness of old and young alluvium reaches quantified by considering their mass/charge ratio. up to 120 m. However, the thickness of young alluvium Detection limit and uncertainty were 0.20 μg/L varies between 10 and 15 m. The study area is defined (LOD) and 0.07 μg/L, respectively. The analytical as a graben basin formed in the late Neogene with results were given in Tables 2 and 3. The acceptability strike slip faults and thrust faults developed in the of the heavy metal contents of the groundwater and east west direction, due to the pressures in the north surface water samples according to Turkish Drinking south direction started at the end of the Triassic period Water Standards [6] were examined. Obtained results [2]. Figure 3 shows the general groundwater direction were plotted and evaluated in graphs to understand along the Porsuk River from east towards west. possible relations between surface water and ground water interaction. Distribution of As, Zh, Fe, Mn and Ni in water samples was plotted on the maps by Surfer Sample Collection and Extraction Procedures program using Krigging approach. 35 samples of the ground water and 38 samples of the surface water were taken within the scope of this RESULTS AND DISCUSSION study to investigate the relationship between pollution parameters and surface water groundwater interaction The analytical results of the heavy metals, and As on the basis of the Porsuk River. Sampling information were evaluated over the data on all groundwater is given in Table 1. A Garmin brand handheld GPS was (Table 2) and surface water (Table 3) samples collected used to transfer the sampling points to the map. Plastic in this study. All sampling points were plotted onto the bottles of 1 L were used for sample collection. The map to better understand their interactive distances water samples for heavy metal analysis were filtered between surface and groundwater samples (Fig. 4). through 0.45 μm PTFE (polytetrafluoroethylene) The heavy metal, and As correlation tables of the syringe filter. After filtration diluted HNO3 (5% N) groundwater and surface water in 2008–2010, and the was added to ensure the pH ≤ 2 conditions. Metal correlation coefficients of the groundwater and sur compounds were prevented to form complex com face water samples were investigated considering their pounds with oxygen. Heavy metal analysis was per close proximity to each other. Finally the plots of the
WATER RESOURCES Vol. 43 No. 1 2016 186 CANDAN ALPTEKIN, GALIP YUCE
ESKISEHIR
Y R E HOLOCENE N R E Formation boundry T Ollivium, clay, silt, sand, gravel A PLEISTOCENE U Q Bedding, strike and dip direction PLIOCENE Clay, tuff, limestone volcanics r Fault, dip throw pe Up le idd M Conglomerate, sandstone volcanics Probable fault r we NEOGENE Lo Overthrust MIOCENE
CENOZOIC EOCENE Claystone, marl Porsuk River basin boundry TERTIARY
PALEOCENE Conglomerate, sandstone 012.5 25 km PALEOGENE 1/250.000 Upper Ophiolitic gravel, schist, sandstone, claystone, mudstone
Lower CRETACEOUS MESOZOIC r pe Up le Limestone idd r M we Lo JURASSIC per Up le idd Ophiolite, greywacke, sandstone, limeston r M we Lo TRIASSIC
Gneiss, schist, marble PALEOZOIC
Fig. 2. Geology map of the study area.
789 N 795 788 782 Equipotential curves 787 786 785 784 783 Flow direction
781 SW: Surface water sampling location GW: Groundwater sampling location 0 1000 m GW 9 Sugar Fac 781 GW 14 GW 18 782 SW 21SW 23SW 24 780 783 786 Pors 784 GW 12 uk Ri 785 ver 779 786 Sa SW 25 risu 787 GW 20 SW 19 787 GW 7 Landfill Area 788 789 789 790 791 r ve i 790 k R SW 9 su or SW 7 P 789 SW 3
Fig. 3. Groundwater equipotential lines and flow directions (after [10]).
WATER RESOURCES Vol. 43 No. 1 2016 OBSERVATION OF EXCESS HEAVY METAL CONCENTRATIONS 187
Table 1. The information of groundwater and surface water sampling locations Sample No Location Name Sample No Location Name GW 1 Behind the flour mill Kιzιlinler SW 1 Kutahya before purification GW 2 Yusuflar village SW 2 Kutahya after purification GW 3 Karacasehir Rural Services well (47076) SW 3 Agaçkoy GW 4 Eskisehir entry from Kutahya SW 4 Kutahya before nitrogen factory GW 5 Garbage dump site SW 5 Kutahya after nitrogen factory GW 6 17147 numbered well SW 6 Calca Before joint of Porsuk River and GW 7 31969 numbered Sarar (Sumerbank) well SW 7 Guvez Stream GW 8 Source in garbage dump site estuary SW 8 Bridge of Guvez Stream after joint Porsuk River and Guvez GW 9 43036 numbered State Supply Office well SW 9 Stream GW 10 14768 numbered Anadolu University SW 10 Sabuncupinar Bridge (Academy) well GW 11 DSI well SW 11 Sabuncupinar Stream Kargin GW 12 Suleyman Cakir (Justice Elementary School) well SW 12 Porsuk Dam exit GW 13 A dig well in garbage dump site SW 13 Ulucayir Stream GW 14 38673 numbered Tulomsas well SW 14 Esenkara 1 GW 15 TSK–13 numbered well SW 15 Porsuk River after Kizilinler village GW 16 Sugar factory well SW 16 Forest nursery at city entrance GW 17 Sugar factory well SW 17 Before Porsuk River purification GW 18 Sugar factory wells SW 18 Front of Sümerbank factory GW 19 DSI 3. Region Machine supply well SW 19 Sarisu Channel GW 20 32996 numbered Tusas well SW 20 Adalar entrance (Ataturk street bridge) GW 21 5779/B slaughter house well SW 21 Çukurcarsi GW 22 Elementary school well SW 22 Before Sugar factory GW 23 46169 numbered SSK Maternity Hospital well SW 23 After Sugar factory GW 24 1047 Muttalip well SW 24 After slaughter house GW 25 30177 Numbered Meat and Fish Authority well SW 25 Porsuk River air base GW 26 Organized Industry well (no. 10) SW 26 City exit (Hasan Bey farm bridge) GW 27 A shallow well (10 m depth) SW 27 Irrigation Channel 1 GW 28 South of PC/VIII numbered well SW 28 Irrigation Channel 2 GW 29 39345 numbered Botas well SW 29 Alpu GW 30 50 m depth well in Catma Farm SW 30 Beylikova GW 31 Drilling well at Alpu exit SW 31 Yunusemre GW 32 Shallow well at Beylikova exit SW 32 Bicer village Porsuk River GW 33 Shallow well of Yunusemre Municipality SW 33 Iloren Sazilar GW 34 A well in the Bicer village SW 34 Sakarya River before Porsuk River before joint of Porsuk River and GW 35 A well in the Kiranharmani village SW 35 Sakarya River SW 36 After joint of Porsuk River and Sakarya River SW 37 Ankara Stream SW 38 Before joint of Ankara Stream Sakarya River
WATER RESOURCES Vol. 43 No. 1 2016 188 CANDAN ALPTEKIN, GALIP YUCE SW 37
m a er e iv r R SW 36 t ya S r SW 34 a a ak r S N a Kiranharmani k
n SW 35
A SW 38 GW 35 mpling location 0 5 10 15 20 SW 33 km
Bicer SW 32 GW 34 SW: Surface water sampling location GW: Groundwater sa Settlement Refinement
Sazak
Unusemre SW 31 GW 33 Porsuk River Porsuk GW 32 SW 30 BEYLIKOVA ling locations in the study area. GW 31 SW 29 Left Irrigation Channel GW 26 SW 28 Right Irrigation Channel GW 30 SW 27 SW 26 GW 22 GW 23 Ground water and surface water samp and surface water Ground water GW 29 GW 13 GW 27 SW 24 SW 25 GW 19 Landfill Frea GW 8 GW 18 GW 24 GW 20 GW 21 Fig. 4. SW 23 GW 17 SW 22 GW 12 GW 5 GW 16 GW 7 SW 21 GW 11 GW 4 GW 14 SW 20 SW 17 GW 3 GW 10 GW 25 GW 15 SW 13 GW 9 GW 2 SW 19 SW 18 GW 6 SW 12 SW 11 SW 15 SW 14 SW 16 GW 1 SW 9 SW 8 SW 10 SW 3 SW 5 SW 2 SW 4 SW 1 SW 6 SW 7
WATER RESOURCES Vol. 43 No. 1 2016
OBSERVATION OF EXCESS HEAVY METAL CONCENTRATIONS 189
for As for Error margin Error
1.71 1.98 1.33 1.55 1.00 0.86 0.71 0.78 0.82 2.87 0.76 0.80 2.53 1.51 0.96 2.83
(μg/L) As As
36.1 24.40 40.45 11.41 22.21 14.30 41.01 10.84 28.33 19.01 21.56 12.30 13.77 10.11 11.17 11.68
(μg/L)
Al Al
(μg/L)
Ni Ni
2.96 15.66 3.06 0.21
(μg/L) Cu Cu 5.37 1.22 0.09 o the [4] (GW: Groundwater o the [4] (GW: 3.70 2.583.46 4.19 0.07 15.68 1.32 1.22 0.09 0.09
198.00
(μg/L) Fe Fe
14.17 1.32 16.76 5.67
(μg/L) Mn Mn
21.62 649.30 62.90 338.70 413.00
(μg/L)
Cr Cr 1.654.65 0.00 3.91 0.91 0.06 0.95 0.07
47.92 4.8213.42 1.16 125.90 6.96 0.49
(μg/L) Zn Zn
28.65 29.08 40.7 10.85 0.76 141.50 103.70 101.80 207.50
(μg/L)
Pb Pb 10 100 50 50 200 200 20 200 10 ±
11.92 10.11
Year
No Sample
ITASHY (2005) ITASHY
for As for Error margin Error 2.5 GW 30 2010 D 13.57 8.29 0.58
0.81 GW 18 2008 D 0.200.711.06 GW 18 2010 W0.94 GW 18 2010 D0.89 GW 21 9.78 2009 W0.77 GW 21 0.00 2009 D0.87 GW 21 6.98 W 2010 14.57 0.00 GW 21 7.60 13.28 2010 D 1.07 136.90 11.06 2.84 8.22 7.71 0.00 3.211.922.71 GW 30 3.79 2008 W GW 30 0.27 0.00 5.55 2008 D 0.39 0.30 7.49 14.57 3.02 3.16 4.40 174.70 0.22 122.00 0.000.80 0.49 2.15 2.33 GW 33 0.15 18.70 W 2010 6.92 9.80 0.48 0.69 0.92 GW 35 2010 W 6.51 91.82 39.79 14 3.37 95.59 8.08 0.57 0.85 GW 18 2009 W 0.67 0.00 5.08 0.00 2.35 GW 30 2009 W 0.16 0.00 9.92 0.00 8.32 0.58
2008 and 2010, the bold values indicate over limit according t indicate over 2008 and 2010, the bold values
(μg/L) As As
2.09 0.15 GW 30 2009 D 24.89 1.95 27.44 13.48 12.40 11.41 11.57 12.12 10.17 15.12 12.73 10.98 38.74 13.17 33.53 35.77
(μg/L)
Al Al
0.13
(μg/L) Ni Ni
22.67
(μg/L) Cu Cu
0.00 5.333.49 5.47 0.00 26.84 1.60 1.12 0.11 0.08 GW 22 GW 22 2010 W 2010 D 23.80 9.61 6.77 2.48 0.17 12.31
(μg/L) Fe Fe
28.94 0.22 8.00 0.00 356.70 200.00
(μg/L) Mn Mn
99.26
466.80 523.60
(μg/L)
Cr Cr 8.13 5.48 1.47 0.10 GW 26 2009 D 32.37 2.59 2.23 6.37 2.94 2.22 2.52 0.18 GW 30 2010 W 16.48 16.35 3.62
13.81 4.64 11.82 10.65
(μg/L) Zn Zn
15.01
142.70 641.10 517.00 721.70 181.20 505.70
(μg/L)
Pb Pb 10 100 50 50 200 200 20 200 10 ±
10.35 Year
Heavy metal analyses results which belong to groundwater between between Heavy metal analyses results which belong to groundwater
No (2005)
ITASHY Sample Sample GW 14 2010 W 10.14 6.91 9.97 0.70 GW 34 2010 D 0.52 23.05 9.78 7.86 GW 9 2010 W 60.98 10.00 1.14 0.08 GW 26 2009 W 1.14 0.00 3.03 0.00 GW 14 2008 D 0.17 12.01 GW 9 2008 W 0.00 11.41 1.24 GW 14 W 2009 0.00 0.00 8.41 0.00 9.48 0.66 GW 33 2010 D 0.44 20.39 8.32 7.03 GW 8 2009 W 0.00 0.00 21.54 0.00 1.55 0.11 GW 22 2008 W 1.74 1.13 GW 7 2008 D 0.26 18.09 2.39 145.80 1.42 0.73 3.76 GW 13 2008 W 0.00 20.23 0.00 26.10 0.00 0.88 0.13 1.23 0.09 GW 31 2010 W 5.44 2.79 GW 7 2009 DGW 7 2010 W 0.78 GW 7 2010 D 17.28 11.06 GW 12 D 2008 GW 12 W 2009 0.96 0.79 32.01 8.01 12.19 3.03 117.00 1.60 9.46 2.80 0.00 GW 1 2010 DGW 2 2008 D 3.49 2.23 7.22 6.74 182.50 0.00 5.07 5.92 1.12 0.08 GW 18 2009 D 5.29 3.23 GW 9 2009 WGW 9 2009 D 0.00 0.00 1.15 82.48 2.98 0.00 3.80 0.27 GW 26 2008 W 1.34 0.00 0.09 GW 26 2008 D 8.47 0.29 50.04 0.00 0.29 0.05 2.15 0.15 GW 10 2008 DGW 12 2008 W 0.36 0.00 19.26 0.87 4.55 16.71 1.94 2.51 97.68 5.73 0.08 2.33 16.53 4.31 0.37 0.30 GW 26 2010 D 10.48 15.73 9.75 0.68 GW 12 D 2009 GW 1 2010 W 95.35 6.92 GW 7 2008 W 0.00GW 7 2009 W 0.09 0.00 8.06 8.85 0.00 17.98 0.00 0.00 0.00 0.00 GW 9 2010 DGW 10 2008 W 0.60 0.00 14.64GW 12 0.00 2010 W GW 12 43.99 2010 D 0.00 1.93 GW 13 4.21 D 2008 0.24GW 13 0.59 2010 D 3.08GW 14 2008 W 0.22 0.00 GW 26 2010 W 24.80GW 14 2009 D 0.68GW 18 6.76 16.74 W 2008 0.99 0.83 0.13 1.73 108.40 7.39 14.61 0.00 1.64 8.14 4.07 0.11 0.00 0.59 9.59 GW 31 2010 D 0.67 GW 32 2010 D 9.41 6.63 8.35 0.58 GW 34 GW 32 2010 W 2010 W 0.95 27.58 4.67 4.62 25.17 33.79 5.17 9.86 0.69 GW 8 2009 DGW 8 2010 W 6.37 27.65 17.16 15.16 2.29 0.16 1.78 GW 22 2009 W 0.12 0.25 GW 22 2008 D 0.20 8.17 GW 8 2010 DGW 9 2008 D 2.31 26.79 7.24 7.39 2.08 0.15 GW 22 2009 D Table 2. Table sample, W: Wet period, D: Dry period) Wet sample, W:
WATER RESOURCES Vol. 43 No. 1 2016
190 CANDAN ALPTEKIN, GALIP YUCE
for As for Error margin Error
1.14 0.61 0.83 0.68 0.78 0.84 0.48 0.73 0.68 0.94 0.76 0.93 0.34
(μg/L) As As
13.45 11.92 16.25 10.43 11.18 13.28
(μg/L) Al Al
347.90 9.75
(μg/L) Ni Ni
23.56 502.10 10.92 53.33 219.20 12.06
to [4] (GW: Groundwater to [4] (GW:
(μg/L) Cu Cu 0.00 8.01 0.00 9.17 82.02 2.26
10.19
100.20 9.78
(μg/L)
Fe Fe
(μg/L) Mn Mn
56.15 215.90 85.06 137.00
134.10 421.10 177.30 3084.00
(μg/L) Cr Cr
10.5510.63 0.00 6.91
(μg/L) Zn Zn
243.60 329.00
(μg/L)
Pb Pb
Year
No Sample
SW 23 2010 D 12.60 5.47 5.28 SW 24 2010 W 3.86 36.72SW 24 8.36 2010 D SW 25 W 2008 13.43 2.03 5.57 34.39 6.02 SW 25 W 2009 3.22 4.81
for As for Error margin Error
0.61 1.00 0.91 1.08 0.13 0.79 0.26 0.38 0.23 0.97 0.29 0.72 0.38 n 2008 and 2010, the bold values indicate over limit according indicate over n 2008 and 2010, the bold values
(μg/L) As As
14.24 13.92 13.01 10.25
(μg/L) Al Al
221.3 11.35
(μg/L)
Ni Ni
(μg/L) Cu Cu
8.31 2.61 69.6 1.85 SW 23W 2010 4.90 6.24
(μg/L) Fe Fe
107.2
(μg/L)
Mn Mn
(μg/L) Cr Cr
1.05 0 3.76 SW 24 2008 W 1.55 4.50 5.44
(μg/L) Zn Zn
53.99 8.5284.07 7.34 18.03 21.80 151.3
(μg/L) Pb Pb 10 100 50 20 50 100 20 200 10 ± (2005) ITASHY 10 100 50 20 50 100 20 200 10 ±
61.22 153.20 23.05 113.50 Year
Heavy metal analyses results which belong to surface water betwee Heavy metal analyses results which belong to surface water
No (2005)
ITASHY ITASHY Sample Sample A1 2008 D 0.45A1 2009 W 1.05 5.51 2.2 41.99 1.61 6.14 SW 7 2010 W SW 8 2009 DSW 8 2010 W 3.71 44.34 22.25 4.66 31.02 4.11 SW 25D 2008 5.19 14.16 A1 2009 DA1 2010 W 60.83A1 D 2010 68.09 2.94 20.94 4.37 4.4 5.39 3.29 SW 24 8.69D 2008 1.61 SW 24W 2009 0.70 SW 24 0.00D 2009 5.81 6.27 0.00 8.74 SW 8 2010 D 0.73 31.46 11.25 6.74 5.47 SW 25D 2009 7.37 SW 7 2009 D SW 7 2010 D A1 2008 W 0.73 0.97 3.03 Table 3. Table sample, W: Wet period, D: Dry period) Wet sample, W:
WATER RESOURCES Vol. 43 No. 1 2016
OBSERVATION OF EXCESS HEAVY METAL CONCENTRATIONS 191
for As for Error margin Error
0.61 1.13 0.88 0.73 0.57 0.20 0.67 0.81 2.14 0.47 1.45 0.99 1.56
(μg/L) As As
14.13 22.24 10.47 12.55 16.21 11.51 20.66
(μg/L)
Al Al
(μg/L)
Ni Ni
(μg/L)
Cu Cu
(μg/L)
Fe Fe
(μg/L)
Mn Mn
(μg/L) Cr Cr
14.6918.27 19.78 13.65 4.86 ± 2.83 14.20 17.30
(μg/L) Zn Zn
184.90 207.80 231.80
(μg/L)
Pb Pb Year
2009 D2009 3.87
No Sample
SW 31 W 2010 1.57 11.49 7.04 16.13 SW 35 SW 25 2010 D 2.69 SW 29 W 2010 6.20 SW 29 D 2010 2.82 35.36SW 30 9.97 W 2010 2.27 41.30 10.23 9.92 13.04 8.13 6.65
for As for Error margin Error D1.20 SW 31 2010 32.25 10.53W SW 32 2010 D1.61 SW 32 2010 32.70 13.34W1.43 7.70 SW 34 8.34 2010 19.81 5.61 SW 8.87 9.59 3.83 21.39
± SW 25 2010 W 7.71
1.16 1.00 0.90 0.87 0.93 0.90 0.88 0.60 0.85 0.58 0.82 0.44 0.74
(μg/L) As As
12.84 14.29 15.39 12.85 13.32 12.37 12.13 16.62 12.60 11.70 10.62
(μg/L)
Al Al
(μg/L)
Ni Ni
(μg/L)
Cu Cu
0.00 3.87 71.46 8.271.95 6.70 25.91 SW 30 2010 D 4.37 90.01 15.56 12.380.00 8.82 170.10 6.350.36D0.71 9.60 8.68 SW 34 193.00 2010 14.09 7.68 7.10
(μg/L)
Fe Fe
(μg/L) Mn Mn
41.91 149.40 24.82 229.50 31.87 79.99 58.15 198.40
(μg/L) Cr Cr
10.54 15.16
(μg/L) Zn Zn
43.00 4.75 55.07 5.88 6.73
(μg/L) Pb Pb
13.04 96.71 224.90 58.08 Year
(Contd.)
No Sample Sample SW 9 2010 W SW 9 2010 D SW 9 2009 D SW 17 D 2008 0.93 4.92 SW 15 2010 W 1.24 10.30 3.84 19.24 SW 17 W 2009 0.69 0.00 2.92SW 17 2010 W 1.58 10.89 3.83 0.00 20.42 SW 17 W 2008 0.37 0.70 SW 15 D 2010 9.09 4.71 4.17 SW 17 2010 DSW 19 W 2008 9.43 0.00 4.69SW 19 D 2008 0.82 1.51 8.08 3.55 SW 17 D 2009 1.75 32.95 116.00 Table 3. Table
WATER RESOURCES Vol. 43 No. 1 2016
192 CANDAN ALPTEKIN, GALIP YUCE for As for Error margin Error
±
1.09 1.19 1.71 1.30 0.87 1.05 1.50 0.96 0.93 1.28
(μg/L) As As
21.44 24.47 30.64 14.98 15.62 13.71 18.55 13.25 12.38 18.25 17.02
(μg/L)
Al Al
(μg/L)
Ni Ni
(μg/L)
Cu Cu
(μg/L)
Fe Fe
(μg/L)
Mn Mn
(μg/L) Cr Cr
23.5 45.42 20.17 22.87 21.2421.23 7.10 43.21
(μg/L) Zn Zn
131.8
116.40 130.40 106.70
(μg/L)
Pb Pb
Year
No Sample
SW 38 2010 D 2.77 42.41 12.15 21.12
for As for Error margin Error D8.49 SW 37 2009 D1.15 SW 38 2009 12.87 7.89
1.17 1.18 0.61 0.60 0.44 0.53 0.58 0.58 0.48 0.77 0.78
(μg/L) As As
8.61 SW 38 2010 W 8.14 8.25D0.59 SW 36 2010 18.33 6.42 8.87
11.18 16.66 10.97 16.86
(μg/L) Al Al
238.10 281.80
(μg/L)
Ni Ni
(μg/L) Cu Cu
0.18 6.62 170.30 0.00 3.75 0.00 3.16
(μg/L)
Fe Fe
(μg/L) Mn Mn
26.23 59.60 26.76 131.70 28.92 60.05
(μg/L) Cr Cr
3.73 3.70 8.76 SW 37 2010 D 4.07
(μg/L) Zn Zn
600.20
(μg/L)
Pb Pb Year
(Contd.)
No Sample Sample SW 19 W 2010 16.63 5.36 7.64 SW 36 D 2009 3.77 SW 19 W 2009 0.00 0.00 3.32 0.00 8.55 ± SW 35 2010 W 3.57 15.26 5.81 50.88 SW 19 D 2009 6.29 SW 35 2010 K 1.21 24.52 10.97 11.68 SW 19 D 2010 9.23 4.82 3.79 8.31 SW 36 2010 W 7.60 6.54 8.86 SW 23 2008 DSW 23 2008 0.25 6.01 17.71 41.62 0.00 6.41 129.30 SW 21 D 2008 0.64 7.16 SW 23 W 2009 0.06 0.00 4.84 0.00 SW 21 W 2010 2.96 SW 23 W 2008 0.00 2.05 SW 21 W 2008 0.00 7.22 SW 21 W 2009 1.02 5.53 5.43SW 21 D 2010 0.85 27.76 0.00 6.28 6.90 5.63 SW 37 2010 W 6.91 Table 3. Table
WATER RESOURCES Vol. 43 No. 1 2016 OBSERVATION OF EXCESS HEAVY METAL CONCENTRATIONS 193
GW 9 N µg/L 4408000 GW 10 Sugar Factory GW 30 38 36 GW 14 0 GW 18 2 0 4406000 SW 21 1 34 GW 7 GW 12 SW 24 32
0 30 3 GW 26 4404000 Landfill Area 28 26 24 4 402000 22 20 20 18 4400000 0 GW 13 16 1 14 12 4398000 0 10 8 6 4396000 4 2 0 4394000 Porsuk River 4392000 Irrigation channels 284000 286000 288000 290000 292000 294000 296000
Fig. 5. As distribution map of the sampling locations in the dry period of 2008.
GW 18 GW 30 µg/L N 4405000 GW 7 GW 26 GW 31 SW 32 40 4400000 GW 1 GW 33 SW 31 GW 34 35 280000 290000 300000 310000 320000 330000 340000 350000 360000 370000 380000 30
Porsuk River 25 Irrigation channels 20
15 10
5 0
Fig. 6. As distribution map of the sampling locations in the dry period of 2010. heavy metals contained in the groundwater samples tion canals have higher concentrations of heavy metals were drawn according to the standards set by the and As. It could be related to old fashion agricultural TDWS [6], and the sampling points that exceed the activities that used arsenical pesticides or surface water limit values were identified. influence. Most possibly, high As content in ground water in some parts of the study area is sourced from The As, Fe, Ni, Mn and Zn distribution maps of the remnants of arsenic based pesticides which accu the groundwater samples were plotted to assess if there mulated at the top of soil and infiltrates into ground was any interaction between groundwater and surface water through irrigation waters. water (Figs. 5–13). Furthermore, similar interaction was searched by the evaluation of Tables 2 and 3. The Indeed, As content in all samples was less than evaluation of these maps revealed that the groundwa 50 µg/L, which was the previous Maximum Contam ter samples located close to the Porsuk River or irriga inant Level (MCL). However, the Joint FAO/WHO
WATER RESOURCES Vol. 43 No. 1 2016 194 CANDAN ALPTEKIN, GALIP YUCE
GW 18 GW 7 GW 12 µg/L N 4405000 GW 31 4400000 GW 33 GW 34 SW 21 GW 32 40 GW 1 280000 290000 300000 310000 320000 330000 340000 350000 360000 370000 380000 35
Porsuk River 30 Irrigation channels 25
20
15
10
5
0
Fig. 7. As distribution map of the sampling locations in the dry period of 2010.
GW 9 N µg/L 4408 000 GW 30 700 GW 18 0 650 4406 000 SW 21 GW 7 600 GW 12 550 4404000 500
2 450 50 4402000 400 350 GW 8 300 4 400000 GW 1 250 280 000 282000 284000 286000 288000 290000 292000 294000 296000 200 Porsuk River 150 Irrigation channels 100 50 0
Fig. 8. Zn distribution map of the sampling locations in the dry period of 2010.
Expert Committee on Food Additives (JECFA) reas the National Academy of Sciences (NAS) to review sessed the effects of As on human health, taking into the Agency’s interpretation and application of As account the new data. Moreover, EPA requested from research, worked with its National Drinking Water
WATER RESOURCES Vol. 43 No. 1 2016 OBSERVATION OF EXCESS HEAVY METAL CONCENTRATIONS 195
GW 9 µg/L 4408000 N Previous Landfill Area GW 10 520 Sugar Factory GW 30 480 SW 19 00 0 GW 14 GW 18 4 20 4406000 GW 17 SW 24 440 GW 12 400 GW 7 360 200 4404000 320 GW 26 280 240 4402000 200 160 120 440000 GW 13 80 284000 286000 288000 290000 292000 294000 296000 40 Porsuk River 0 Irrigation channels
Fig. 9. Fe distribution map of the sampling locations in the dry period of 2008.
Advisory Council (NDWAC). Finally, the MCL was 34 (40.45 µg/L) that are above the standard during the decreased to 10 µg/L after all these scientific research wet period of 2010 (Fig. 6). As concentration in GW and discussions. In spite of the unfavorable conse 12 (35.77 µg/L) may also influenced by SW 21 quences that may come from moderately high levels of (10.97 µg/L) during the dry period of 2010 (Fig. 7). As in water (10–50 µg/L), the Committee stated that However, relatively higher As contents in groundwater such intervals could be considered as tolerable [8]. In showed reverse migration, i.e., groundwater contami conclusion, EPA announced that 10 ppb (0.010 mg/L) nates the Porsuk River. High As content in the ground standard for As would remain as an achievable limit for water samples relatively increase during dry period due public health to protect probable unsatisfactory to the lack of fresh water recharge, such as rainfall. results. On the other hand, higher As concentrations in the As can be seen from the distribution of As in the dry samples taken in the vicinity of the confluence of period of 2008 (Fig. 5), As concentrations in SW 21 Sakarya and Ankara streams (SW 35, SW 36, SW 37, and GW 12 are 16.66 and 38.74 µg/L, respectively. and SW 38) (Fig. 4) are thought to be closely related Groundwater might be contaminated from Landfill to the geological units they are located on, their prox Area (Fig. 3). On the other hand the As contamination imity to the intense industrial and agricultural areas, of the groundwater from the Porsuk River is rejected and returning irrigation water to the river. for these couple (GW 12, SW 21) because the The same influence can be found between GW 12 groundwater is discharged to the surface water where and SW 21 based on the Zn concentration for the wet these samples are located (Fig. 3). Both values are period of 2010 (Fig. 8), since the Zn concentration is clearly higher than the allowable limit for drinking above the allowable limit of TDWS (100 µg/L) by water (10 µg/L) according to [6]. Since the position of 600.20 µg/L in SW 21 and 721.70 µg/L in GW 12 SW 21 is very close to the GW 12, high As content in which are located close to each other. GW 12 most probably occurs due to surface water The distribution of Fe during the wet period of 2008 groundwater influence between SW 21 and GW 12. A is shown in Fig. 9. The Fe concentration in GW 9 and similar interaction can be expected between GW 18 SW 19 are 356.70 and 198.40 µg/L, respectively that and SW 24, which is nearby the GW 18 with a higher µ µ are above the allowable limit (50 g/L) for drinking As concentration (16.25 g/L). purpose. Hence, a probable groundwater surface The possible interaction can also be observed water interaction between GW 9 and SW 19 can be between SW 31 (12.55 µg/L), SW 32 (16.21 µg/L) implied. Furthermore, Fe concentration in SW 21 and, GW 31 (11.68 µg/L), GW 33 (36.1 µg/L), GW (131.70 µg/L) is comparable with GW 12
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N µ GW 9 g/L 4408000 Previous Landfill Area 210 GW 10 GW 21 GW 30 200 1 6 190 1 0 GW 14 GW 18 SW 19 0 SW 25 0 180 4406000 6 Air Base 170 GW 7 GW 12 160 150
1 140 1 0 GW 26 4404000 0 130 1 0 1 6 120 110 100 4402000 90 80 6 0 70 60 GW 8 50 4400000 GW 13 40 30 284000 286000 288000 290000 292000 294000 296000 20 Porsuk River 10 Irrigation channels
Fig. 10. Fe distribution map of the sampling locations in the dry period of 2008.
(229.50 µg/L) for the dry period of 2008 (Fig. 10). Finally, surface water influence can be mentioned Both values are higher than allowable limit for drink for Ni content between SW 25 and GW 18 with con ing purpose. centrations of 23.56 and 22.67 µg/L, respectively The distributions of Mn for the wet and dry period (Fig. 13). of 2008 are shown in Figs. 11 and 12. The Mn concen tration in SW 24 (85.06 and 56.15 µg/L), which is By the examination of the parallel changes in heavy located close to GW 18 that has higher concentrations metal and As concentrations in surface water and (466.80 and 413.00 µg/L) than allowable limit groundwater, pair of water samples was obtained (50 µg/L). Thus, this can invoke a possible influence (Table 4). The most prominent changes can be seen in of surface water on the groundwater quality. As. Fe and Mn contents (Table 4). Variation in the
Table 4. Changes of parameters in the pairs of surface water groundwater (parameters in bold exceed allowable limits in the water pairs) Water Pairs Surface Water Groundwater Similarity in terms of parameters sample no. sample no. dry and wet period SW 15 GW 1 As, Cr SW 19 GW 9 Fe, Pb, Cr, Cu, Ni, Zn, Al SW 21 GW 12 As, Zn, Cr, Mn, Fe, Cu SW 24 GW 8–GW 19–GW 21 Fe, As, Mn, Pb, Zn SW 29 GW 31 As SW 30 GW 32 As, Zn, Cr SW 31 GW 33 As SW 32 GW 34 As, Cr
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N GW 9 µg/L 4408000 GW 10 460 440 GW 30 420 Sugar Factory 0 GW 14 0 0 0 400 0 0 1 GW 18 3 2 380 4406000 GW 12 360 GW 7 SW 24 340 320 1 0 300 0 2 GW 26 280 4404000 00 260 240 220 200 4 402000 100 180 160
0 0 140 120 100 4400000 80 GW 13 60 284000 286000 288000 290000 292000 294000 296000 40 20 Porsuk River 0 Irrigation channels
Fig. 11. Mn distribution map of the sampling locations in the dry period of 2008.
N GW 9 µg/L 4408000 GW 10 420 GW 30 400 Sugar Factory 380 GW 14 0 0 GW 18 0 0 2 1 360 4406000 340 1 30 0 0 SW 24 320 GW 12 0 GW 7 2 0 300 0 280 4404000 GW 26 260 240 220 200 100 180 4402000 160 140 0 120 100 4400000 80 GW 13 60 40 284000 286000 288000 290000 292000 294000 296000 20 Porsuk River 0 Irrigation channels
Fig. 12. Mn distribution map of the sampling locations in the dry period of 2008.
WATER RESOURCES Vol. 43 No. 1 2016 198 CANDAN ALPTEKIN, GALIP YUCE
µ GW 9 N g/L 4408000 GW 10 GW 30 22 Sugar Factory GW 14 0 1 20
2 GW 18 4406000 0 SW 25 GW 12 AirBase 18 GW 7 16 1
0 4404000 GW 26 14 Landfill Area 12
10 10 4402000 8 6
4400000 GW 13 4
284000 286000 288000 290000 292000 294000 296000 2 Porsuk River 0 Irrigation channels
Fig. 13. Ni distribution map of the sampling locations in the dry period of 2008.
As 2008 wet period As 2008 dry period As 2009 wet period As 2009 dry period 30 45 40 20 25 40 35 18 35 30 16 20 30 14 25 12
25 G/l G/l 15 G/l 20 10 µ µ G/l 20 µ 8 µ 10 15 15 10 6 5 10 4 5 5 2 0 0 0 0 GW 7 GW 8 GW 9 GW 2 GW 7 GW 7 GW 8 GW 7 GW 9 GW 9 GW 9 GW 12 GW 14 GW 18 GW 21 GW 22 GW 26 GW 30 GW 10 GW 12 GW 13 GW 14 GW 18 GW 22 GW 26 GW 30 GW1 2 GW 14 GW 18 GW 21 GW 22 GW 30 GW 26 GW 10 GW 12 GW 13 GW 14 GW 18 GW 22 GW 26 GW 30
45 As 2008 wet period 45 As 2010 dry period 700 Fe 2008 wet period 400 Fe 2008 dry period 40 40 600 350 35 35 300 30 500 30 250 25 25 100 G/l
G/l 200 G/l 20 20 µ 300 µ 15 µ 15 200 150 10 10 100 5 5 100 50 0 0 0 0 GW 1 GW 7 GW 8 GW 9 GW 1 GW 9 GW 8 GW 7 GW 7 GW 9 GW 9 GW 7 GW 2 GW 18 GW 14 GW 21 GW 31 GW 26 GW 30 GW 12 GW 32 GW 33 GW 34 GW 34 GW 22 GW 21 GW 31 GW 12 GW 18 GW 32 GW 33 GW 34 GW 22 GW 26 GW 30 GW 10 GW 12 GW 13 GW 14 GW 18 GW 22 GW 26 GW 30 GW 10 GW 12 GW 13 GW 14 GW 18 GW 26 GW 22 GW 30 Mn 2008 wet period Mn 2008 dry period Zn 2009 wet period Zn 2009 dry period 500 450 120 600 450 400 400 350 100 500 350 300 80 400 300 250 G/l 250 G/l 60
µ 300 G/l 200 200 µ 150 µ 150 40 200 100 10 5 50 20 100 0 0 0 0 GW 7 GW 9 GW 7 GW 9 GW 2 GW 7 GW 9 GW 7 GW 8 GW 9 GW 12 GW 18 GW 21 GW 26 GW 22 GW 30 GW 10 GW 12 GW 13 GW 14 GW 18 GW 22 GW 26 GW 30 GW 10 GW 12 GW 13 GW 14 GW 18 GW 12 GW 14 GW 18 GW 21 GW 22 GW 26 GW 30 GW 22 GW 26 GW 30 Zn 2010 wet period Zn 2010 dry period 800 700 ITASHY (2005) 700 600 WHO (2006) 600 500 500 400 USERA (2000) 400 G/l 300 µ G/l300 G/l G/l 200 200 100 100 0 0 GW 1 GW 7 GW 9 GW 1 GW 8 GW 7 GW 9 GW 18 GW 26 GW 31 GW 12 GW 21 GW 32 GW 33 GW 34 GW 22 GW 18 GW 12 GW 30 GW 32 GW 22 GW 34 GW 35
Fig. 14. Graphs of heavy metal contents of groundwater samples based on [4, 7, 9].
WATER RESOURCES Vol. 43 No. 1 2016 OBSERVATION OF EXCESS HEAVY METAL CONCENTRATIONS 199 concentrations of As, Fe, Mn, and Zn in groundwater ACKNOWLEDGMENTS over time is given in Fig. 14 [4, 7, 9]. The authors would like to express their deep grati tude to Dr. Didem Yasin for her valuable supports. We CONCLUSIONS wish to extend our thanks to the Regional Directorate of State Hydraulic Works (DSI), especially to the The groundwater in the study area is drawn from members of Geotechnical Survey and Groundwater the alluvium and the Neogene limestone. Aquifer is Division of DSI Eskisehir. The authors are also open to contaminations. The industrial and agricul indebted to the anonymous reviewer for his valuable tural contaminations in particularly lead to worsening contribution by reviewing the manuscript. of the groundwater, drinking and irrigation water qual ity. It is thought that the pollution is caused by the con REFERENCES tamination of the groundwater through the agricul tural and industrial activities directly, or by the dis 1. Albek, E., Estimation of Point and diffuse contaminant charge of the waste water from these activities to the loads to streams by non parametric regression analysis Porsuk River without any treatment or with insuffi of monitoring data, Water, Air, and Soil Pollution, 2003, cient treatment. According to data on the heavy metal vol. 147, pp. 229–243, doi:10.1023/A:1024592815576. contents, the surface water is prone to contaminate 2. Gozler, Z., Cevher, F., Ergul, E., and Asutay, J., Geol groundwater due to recharge shallow groundwater ogy of southern and middle part of Sakarya, MTA Pub along the some sections of the Porsuk River, especially lications, 1996, no. 9973, p. 97 [in Turkish]. after the treatment plant. Among the heavy metals that 3. Guney, Y., Porsuk River water and sediment’s geotech exceed the limit value, As is the most remarkable and nical, chemical and biological characteristic’s seasonal has been observed in almost all water samples. variation and improving of the sediment wastes, Anad olu Univ. Publications, 2002, Eskisehir. The ten groundwater surface water pairs were determined in close proximity to each other. The tem 4. ITASHY, Regulation on waters for human consumption 2005, Official Gazette dated 17/02/2005, no. 25730 [in poral changes of these pairs show similarity in time. Turkish]. The similar changes in some heavy metal contents in the groundwater and surface water sample pairs which 5. Olmez, E. and Yucel, B., Geothermal Energy Facilities were collected in the same period of the time and have of Eskisehir Region, MTA Publications, 1985, MTA Department of Energy Raw Materials Research and close locations to each other. Higher concentrations of Exploration, pp. 1–18. heavy metals in the wells which are far from the river indicate a local contamination. The correlation coef 6. TDWS, Turkish Drinking Water Standards, Ankara: The ficients of the heavy metals of the groundwater surface Health Ministry, 2005. water pairs in close proximity to each other that were 7. USEPA, The United States Environ. Protection Agency, collected to evaluate surface water groundwater inter Drinking Water Standards and Health Advisories, Wash actions were found higher at each year and at each ington DC: Office of Water U.S. EPA, 2000. period. The increase in concentrations of heavy metals 8. WHO, World Health Organization, Guidelines for Drink in the samples taken especially in recent years and in ing water Quality, http://www.who.int/mediacen the dry periods may be due to the increase in the activ tre/factsheets/fs372/en/, 2012. ities during summer, in addition to the waters given 9. WHO, World Health Organization, Guidelines for Drink from the Porsuk River to the irrigation channels. ing water Quality, First Addendum to 3rd Edition, vol. 1, Recommendations, 2006. The waste water of the sugar mill should not be dis charged to the Porsuk River unless a sufficient treat 10. Yuce, G., Pinarbasi, A., Ozcelik, S., and ment to prevent the contamination parameters in the Ugurluoglu, D., Soil and water pollution derived from groundwater and surface water samples are imple anthropogenic activities in the Porsuk River Basin, Tur key, Environ. Geol., 2006, vol. 49, pp. 359–375, doi: mented. 10.1007/s00254 005 0072 5. High heavy metal concentrations were found espe 11. Yuce, G., Spatial distribution of groundwater pollution cially in the areas of intensive agricultural and indus in the Porsuk River Basin (PRB), Turkey, In. J. Environ. trial activities. Pol., 2007, vol. 30, pp. 539–547.
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