Evaluation of Shallow Groundwater Quality for Irrigation Purposes in the Koprubasi Uranium Area (, )

Hulya Kacmaz and M. Eran Nakoman Dokuz Eylul University, Faculty of Engineering, Dept. of Geological Engineering, Tinaztepe Campus, 35160, -Izmir / Turkey Abstract Koprubasi is a district of Manisa Province in the of Turkey. Shallow groundwater located in this area is generally used for irrigation purpose by village inhabitants. The main objective of this study is to evaluate the quality of shallow ground water collected from the U mineralization area in Koprubasi. In order to achieve this objective, physicochemical parameters (pH, EC, Ca2+, Mg2+, Na+, - - 2- - 2- HCO3 , Cl ,SO4 , NO3 ,and PO4 ), were analyzed. Based on these analyses, parameters like Sodium adsorption ratio (SAR), % Sodium (Na), Residual sodium carbonate (RSC), Kelley’s ratio (KR) and Magnesium hazard (MH) were calculated. pH, the electrical conductivity (EC) and calcium, magnesium, sodium, bicarbonate, chloride, sulfate, nitrate and phosphate concentrations in the shallow groundwater are usually below the usual range set by the Ayers and Wescot, 1985 for irrigation water. In addition, the calculated values of SAR, RSC, % Na, KR and MH indicate good to permissible use of ground water for irrigation.

Keywords: Groundwater, Irrigation, Koprubasi, Uranium

Introduction Groundwater is the main source of irrigation water supply for many settlements. Hence, it is necessary to evaluate the ground water quality for irrigation. The shallow groundwater in Köprübaşı U area is generally used for irrigation purposes by village inhabitant. Kacmaz and Nakoman (2009) have reported hydrochemical characteristics of shallow groundwater in aquifer containing uranyl phosphate minerals, in the Koprubasi (Manisa) area. However, the knowledge about the quality of shallow ground water for irrigation purposes was not included.

The physicochemical parameters of groundwater play a significant role in classifying and assessing water quality (Tank DK and Chandel CPS 2009). The list of physicochemical routinely measured to determine irrigation water quality follow: pH, Electrical Conductivity (EC), Calcium (Ca), Magnesium (Mg), Sodium (Na), Carbonate (CO3) or Bicarbonate (HCO3), Chloride (Cl), Sulfate (SO4) and Nitrate (NO3). In addition to these parameters, the phosphate concentration of the shallow groundwater was also determined due to uranyl phosphate minerals were found in the study area. Chemical data were used for mathematical calculations (SAR, RSC, % Na, KR and MH) for better understanding the suitability groundwater quality for irrigation purposes. Guidelines for irrigation water quality established by the FAO (1985) were used to interpret water quality for irrigation.

Description of the Study Area Koprubasi is located 120 km northeast far from Manisa, in western Turkey (Fig. 1). The geological formation in the Koprubasi area is the fluviatile sedimentary rocks underlain by high grade metamorphic rocks of the Menderes Massif. Neogene fluvial sedimentary rocks are the main aquifer in the Koprubasi area and consist predominantly of sandstone and conglomerate interlayered with minor siltstone, claystone and mudstone.

The sandstones and conglomerates host the majority of the U ore. The uranium ore grade of the sedimentary rocks varies widely, but is generally low to medium grade (0.01 to 0.4 U3O8 %). Moreover, samples from the iron-rich sedimentary rocks have elevated U3O8 values as much as 1.06 % (Kacmaz 2007).

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Figure 1. Location map of the study area.

The secondary uranium phosphates torbernite [Cu(UO2)2(PO4)2·10H2O], meta-torbernite [Cu(UO2)2(PO4)2·8H2O] and meta-autunite [Ca(UO2)2(PO4)2·6H2O], were the main ore minerals; jarosite and chlorite-kaolinite and Fe-oxides were also present in the mineral association. In addition, quartz, feldspars (plagioclase and potash feldspar) and minor amount of muscovite were main primary minerals identified in the sedimentary rocks (Kacmaz, 2007).

Methods and Materials Shallow groundwater (0.5–6 m) samples from dug wells were collected within uranium mineralized regions of Koprubasi area. The Two samples were collected from each site and stored in 1000 ml polyethylene bottles. One sample was preserved (acidified to pH\2.0) using ultra pure HNO3 immediately after filtering for determination of cations and the other was kept unacidified for anion analyses. Acidified samples were sent to an internationally accredited commercial laboratory (ACME) for analyses by ICP-MS. The remaining non-acidified samples were analyzed for anions using ion chromatography at Dokuz Eylul University. The variable parameters of pH, Eh, EC (electrical conductivity), alkalinity and temperatures were measured in the field.

Result and Discussion The physicochemical analysis of the shallow groundwater samples is presented in Table 1. Groundwater samples from Koprubasi U mineralization area show near neutral pH values (6.2–7.1). All groundwater samples have pH value lower than the Ayers and Wescot (1985) irrigation water guidelines. Electrical conductivity (EC) values of groundwater samples are between 87–329 µS/cm and under the Ayers and Wescot, (1985) irrigation limit.

Calcium and sodium are dominant cations which vary between 0.58 and 1.23 me/l and 0.28 and 1.16 me/l, respectively. Mg concentration is generally low. Minimum and maximum values are 0.26 mg/l and 0.67 me/l. Bicarbonate content ranges between 0.78 and 1.78 me/l. Likewise; they are mostly characterized by mixed cationic Ca dominating bicarbonate types and (Kacmaz and Nakoman 2009). The usual range for bicarbonate in irrigation water is 0-10 me/l (Ayers and Wescot, (1985). All of the groundwater samples fall below this range.

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Concentrations of sulfate vary between 0.06 and 0.81 me/l which are beneath the usual limits according to irrigation water standards. Chloride is another ion commonly found in irrigation waters. In general, waters with chloride values of below 30 me/l are considered to be good quality irrigation waters (Ayers and Westcot, 1985). The chloride concentrations of shallow groundwater from the area are very low, ranging from 0.11 to 0.51 me/l. Only one sample (3) nitrate values reaches to 18 mg/l are above irrigation water standard (10 mg/l). The phosphate concentration varies between 0.34 mg/l and 3.4 mg/l. Table 1 show that only one sample phosphate concentrations (3.4 mg/l) exceeds the usual range of 2 mg/l.

Table 1. The physicochemical analysis of the shallow groundwater samples

1 2 34 5 6 7 *Usual range in irrigation water

Depth (m) 3 2 6 0.5 4 6 6 T (0C) 14.3 14.8 15.914.7 15.3 15.7 16.2 pH 6.5 6.7 6.67.1 6.5 6.3 6.2 6.0-8.5 EC (µS/cm) 87 154 329 191 181 185 138 0-3 ds/m Ca2+ (me/l) 0.58 0.77 1.23 0.85 0.97 0.77 0.66 0-20 Mg2+ (me/l) 0.26 0.45 0.67 0.32 0.39 0.45 0.26 0-5 me/l Na+ (me/l) 0.28 0.41 1.16 0.29 0.50 0.70 0.48 0-40 me/l - HCO3 (me/l) 0.90 1.06 0.78 1.78 1.44 1.36 0.84 0-10 me/l Cl- (me/l) 0.11 0.23 0.51 0.20 0.25 0.39 0.23 0-30 me/l 2- SO4 (me/l) 0.13 0.31 0.81 0.06 0.31 0.44 0.38 0-20 me/l - NO3 (mg/l ) 3.72 6.79 18 2.1 2.67 1 2.5 0-10 mg/l 2- PO4 (mg/l ) 1.29 0.70 0.45 3.40 0.48 0.69 0.34 0-2 mg/l SAR 0.42 0.52 1.190.37 0.60 0.903 0.70 0-15 me/l % Na 29.96 33.70 39.18 44.12 30.20 38.98 36.85 RSC 0.06 -0.16 -1.13 0,610.08 0.15 -0,08 KR 0.33 0.33 0.610.24 0.37 0.58 0.52 MH 31.16 37.17 35.3427.58 28.43 36.97 28.37

*Laboratory determinations needed to evaluate common irrigation water quality problems Ayers and Wescot 1985.

U.S. Salinity (SAR) While a high salt concentration in water leads to formation of saline soil, a high sodium concentration leads to development of an alkaline soil (Singh, AK et al.). The sodium adsorption ratio (SAR) parameter evaluates the sodium hazard in relation to calcium and magnesium concentrations. The United States of Salinity diagram (USLL, 1954) of the water is based on the EC and the sodium adsorption ratio (SAR). SAR can be is calculated by the formula:

SAR= Na+/ [(Ca2+ + Mg2+) /2]0.5

According to the U.S. Salinity diagram classification of irrigation water (USLL, 1954), the shallow ground waters fall in the field of C1S1–C2S1 (Fig. 2), which indicates a low to medium salinity hazard but not an alkalinity hazard due to low Sodium Adsorption Ratio (SAR 0.37 to 1.19).

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Figure 2. US Salinity classification of shallow groundwater for irrigation (USLL, 1954).

% Na (Sodium Percentage) EC and sodium concentration are very important in classifying irrigation water. The salts, besides affecting the growth of the plants directly, also affect soil structure, permeability and aeration, which indirectly affect plant growth (Singh, AK et al. 2008).

Wilcox (1955 diagram) uses sodium percentage (% Na) and EC values for classifying irrigation water quality. Na % is calculated by using following formula:

% Na= [(Na+ + K+)*100]/(Ca2++Mg2+ + Na+ + K+)

The sodium percentage (% Na) in the area ranges between 29.96 and 44.12 % in shallow ground water of the study area. The plot of analytical data on the Wilcox (1955) diagram related to EC and sodium percent indicates (Fig. 3) that the shallow ground waters are excellent to good quality.

Residual sodium carbonate (RSC) Another way to examine the irrigation water is to estimate the residual sodium carbonate (RSC) as suggested by Eaton, 1950. The RSC has the following equation

- - 2+ 2+ RSC= (CO3 +HCO3 )-(Ca +Mg )

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Figure 3. Evaluation of shallow groundwater for irrigation in Wilcox (1955) diagram

Kelley’s Ratio (KR) The level of Na+ measured against Ca2+ and Mg2+ is known as Kelley’s ratio, based on which irrigation water can be rated (Kelley, 1940 and Paliwal 1967). Waters with Kelley’s ratio less than one are suitable for irrigation.

All of the groundwater samples have KR value <1, indicating the good quality of the groundwater for irrigation purpose.

Magnesium Hazard (MH) Szabolcs and Darab (1964) proposed magnesium hazard (MH) value for irrigation water as given below

MH= Mg2+/(Ca2+ + Mg2+) *100

MH > 50 is considered harmful and unsuitable for irrigation use. In the analyzed ground waters have MH < 50. The MH indicates that the groundwater is not harmful for irrigation.

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5 Conclusion Physicochemical parameters of shallow groundwater in Köprübaşı U area, Manisa, Turkey was used to evaluate the quality of groundwater for determining its suitability for irrigation purposes. Although phosphate and nitrate concentrations in a one ground water sample are slightly high, the shallow groundwater in the study area seems to be suitable with compared with FAO quality criteria for irrigation. In addition, the calculated values of SAR, % Na, RSC, Kelley’s ratio and Magnesium hazard indicate good to permissible use of ground water for this aim. On the other hand, there is no stated limit for uranium in FAO irrigation standard and the use of this groundwater for irrigation may be dangerous because of possible effects of uranium on human health. Hence, to protect the human health, these shallow ground water located in uranium mineralization area are not recommended for irrigation.

Acknowledgements This study was supported by Scientific Research Project Division of Dokuz Eylul University, Turkey (Project Number: 03.KB.FEN.019).

References Ayers R.S, Westcot D.W., 1985: Water quality for agriculture, FAO Irrigation and Drainage Paper No. 29, Rev. 1, U.N. Food and Agriculture Organization, Rome.

Eaton, F.M., 1950: Significance of carbonates in irrigation waters. Soil Sci 39:123–133.

Kacmaz, H., 2007: Manisa--Köprübaşı Uranyum zuhurunun incelenmesi, PhD, Dokuz Eylul Universitesi, Fen Bilimleri Enstitüsü, Izmir [in Turkish].

Kacmaz, H, Nakoman ME., 2009: Hydrochemical characteristics of shallow groundwater in aquifer containing uranyl phosphate minerals, in the Köprübaşı (Manisa) area, Turkey", Environmental Earth Sciences, 59,449-457.

Kelley, W. P., 1940: Permissible composition and concentration of irrigation water. Proc. Amer. Soc. Civ. Engin. 66: 607-613.

Paliwal, K.V., 1967: Effect of gypsum application on the quality of irrigation waters. The Madras Agricultural Journal, 59, 646–647.

Singh, A.K., Mondal, G.C. Kumar, S.Singh, T. B., Tewary, B. K., Sinha, A., 2008: Major ion chemistry, weathering processes and water quality assessment in upper catchment of Damodar River basin, India. Environ Geol, 54:745–758.

Szabolcs I, Darab C., 1964: The influence of irrigation water of high sodium carbonate content of soils. In: Proceedings of 8th International Congress of Isss, Trans, vol II, pp 803–812.

Tank, D.K., Chandel C.P.S., 2009: A hydrochemical elucidation of the groundwater composition under domestic and irrigated land in Jaipur City Environ Monit Assess , DOI 10.1007/s10661-009- 0985-7

USSL 1954: Diagnosis and improvement of saline and alkali soils. USDA Agr. Handbook No. 60, Washington DC

Wilcox IV 1955: Classification and use of irrigation water. USDA Circ. 696, Washington DC

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