Hydrochemical Assessment of Groundwater and Some Springs in Qazaniyah Area, Diyala province, East of Iraq

The Qazaniyah study included the analysis of 18 wells and 2 springs for the dry period in October 2018 and the wet period in April 2019, including the analysis of physical and chemical properties and the study of heavy elements (Fe, Zn, Cd, Pb, Ni and Cu).The results showed that the water wells and springs for the two periods are highly mineralized and characterized by low alkalinity and very high hardness. Water was fresh in some wells and salty in the others, whereas it was fresh in the springs. Most of the wells had sodium sulphates type, except the wells 12, 7, 6, and 5 which were of Calcium sulphate type. The springs for both seasons had calcium sulphate type. Based on the World Health Organization criteria , all the wells for both periods are not suitable for human drinking, whereas the springs are suitable only for drinking of livestock and poultry. Sodium adsorption rate (SAR) was excellent for groundwater and springs for both seasons. The percentage of sodium (Na%) in both seasons showed that the wells 18,17,15,11,4,3 as well as the springs are within the permissible limits for irrigation purposes, while the remaining of the wells was not.


Figure 2-
The location of the wells and some springs in the study area.

MATERIALS AND METHODS
The laboratory work involved physical and chemical analyses of water samples, which included the determination of the concentrations of cations (Ca 2 +, Mg 2 +, Na + , K + ), anions (HCO 3 -, SO 4 2 -, Cl -), minor ions (NO 3 --, PO 4 3-), and trace elements (Fe, Ni, Cu, Zn, Cd, Cr and Pb), in addition to the parameters of pH, TDS and EC. Levels of major and minor ions and trace elements were studied in the Ministry of Science and Technology's laboratories. A= 100 -U ……………………… (2) where U is uncertainty or reaction error, A is accuracy or certainty, and r is concentration of ions in epm units.
Using the above equation, the tests of U% and A for all samples over two periods showed values within acceptable limits (less than 5%) which indicates that the test can be used for hydrochemical analysis. with an average of 7.34, whereas that for the wet period ranged between 7.1-7.32 with an average of 7.21 . The values in two spring (S1 and S2) for the dry period were 7.4 and 7.4 and for the wet period 7.27 and 7.38, respectively.

Electrical conductivity (EC)
EC values in the groundwater samples ranged between 2040 and 7100 µS/cm with an average of 3695 µS/cm in the dry period, while it ranged between 2010 and 7000 µS/cm with an average of 3593.72 µS/cm in the wet period. The values in S1 and S2 were 1030 and 1030 µS/cm, in the dry period and 1020 and 1020 µS/cm for the wet period, respectively. According to a previously described relationship between EC and mineralization degree of water [3], we found that the type of all water samples in the present study area is excessively mineralized water for the two periods (Table-4). T.H quality in groundwater samples range from (445-1943.83) ppm with an average of (1088.048) ppm in dry period, whereas in springs (S1,S2) they range from (263.34 to 272.35) ppm with an average of (1028.2) ppm in wet period, whereas in springs (S1,S2) they range from (415.46-1963.9) ppm to (240.63 and 242.22) respectively [4].and [5]. Due to the high concentrations of calcium and magnesium in the water samples, groundwater and springs in the study area are graded as having very hard water for the two periods.

Total dissolved solid (TDS)
TDS values in the groundwater samples ranges between (1043-3841) ppm with an average of (2292.4) ppm in the dry period, while it ranges between ( 1001-3640) ppm with an average of (2156.5) ppm in the wet period. For S1and S2, the values were (599 and 619) ppm, respectively in dry period ,while in wet period are (572 and 598) respectively. It is clear that the salinity in the dry period was higher than that in the wet period, which is due to the dilution occurring in the wet period as a result of rainfall ( Figure-(3A,B).

Chemical Properties Cations and Anions
Calcium ion concentration in groundwater samples varied from 118 to 423 ppm and 112 to 402 ppm in dry and wet periods, respectively. The values in the springs (S1, S2) were (75 and 77) ppm and (70 and 69) ppm in dry and wet periods, respectively. Calcium concentration decreases in wet periods due to the precipitation dilution effect. Magnesium ion concentration in the groundwater samples varied from 37 to 216 ppm and from 33 to 268 ppm in dry and wet periods, respectively. The values in the springs (S1, S2) were (18 and 19) ppm and (16 and 17) ppm in dry and wet periods, respectively. Sodium ion concentrations in the groundwater samples ranged between 148-499 ppm in dry period and 143-483 ppm in wet period, whereas in the springs (S1, S2) they were (66 and 69) ppm and ( 51 and 54 ) ppm in dry and wet periods, respectively. Potassium ion concentrations in the groundwater samples varied from 9 to 20 ppm and 8 to 18 ppm in dry and wet periods, respectively, whereas in the springs (S1, S2) they were (2 and 3) ppm and ( 2 and 1) in the dry and wet periods, respectively.
Chloride concentrations in the groundwater samples ranged between 199-756 ppm in dry period and 154-679 ppm in wet period, whereas in springs (S1 , S2) they were (91 and 101) ppm and (84 and 87) ppm in dry and wet periods respectively. The groundwater samples of the study area are classified as being of normal chloride except (w12,w15 and w16) in dry period may be classified as Oligochloride water, so the springs are classified as normal chloride, for two periods, whereas the springs are classified as being of normal chloride for the two periods (Table-5). Sulfate ion concentrations in the groundwater samples ranged between 358.6-1488 ppm in dry period and 350-1406 ppm in wet period, whereas in springs (S1,S2) they were (164 and 167) ppm and (121 and 125) ppm in dry and wet periods, respectively. The groundwater samples of study area are classified as having normal sulfate to oligosulfate water for the two periods, while (S1 and S2) may be classified as having normal sulfate (Table-5). Bicarbonate ion concentrations in the groundwater samples varied from 145 to 463 ppm in the dry period and 134 to 434 ppm in the wet period, whereas in springs (S1 and S2) they were (135 and 137) ppm and (131 and 131) ppm in dry and wet periods, respectively, (Tables-5, 6 and 7).

Trace Elements
In the present study, seven trace elements, including Fe, Ni, Cu, Cd, Pb, Zn and Cr, were analyzed. It should be noted that concentration of (Cr) could not be tested in all water samples. By comparing

Fakhre and Abdulhussein
Iraqi Journal of Science, 2020, Vol. 61, No. 9, pp: 2277-2292 7743 the water samples from two periods according to the standards criteria for trace elements in drinking water [7,8], all water samples were found to be within the limits.

Groundwater classification Piper Diagram
According to the application of a previously published diagram [10], all water samples from the two periods were falling into class e, which represents earth alkaline water with increased alkaline portion and predominant sulfate and chloride Figures-(6 and 7).   Figures-(8 and 9) illustrate the results of the application of Schoeller classification on water samples for the two periods. The results appear to almost fit those of the hydrochemical formula.

Water uses Water suitability for human drinking
All of groundwater samples, according to from TDS and T.H results, are not suitable for drinking water, but the springs are suitable for drinking water. All trace elements in water samples, and for both periods, are within the limits specified by earlier reports [7,8].
Schoeller Diagram  Usually, sodium alkali hazard is expressed as a ratio of sodium adsorption (SAR). The index quantifies the proportion of sodium to calcium and magnesium ions in a sample. High SAR values indicate a sodium risk that replaces absorbed calcium and magnesium, which eventually destroys the soil structure [5]. This index measures the impact of sodium accumulation in the soil as related to relative cations concentration. SAR values are determined on the basis of [13]: SAR = r Na /√ where: r: Concentration of ions by (epm) units. According to this classification, all the groundwater samples are lying in class S1.

Soluble Sodium Percentage ( Na%)
Increasing sodium ion levels in irrigation water can influence the soil, where it causes its porosity and permeability to decrease, thereby impacting plant growth or causing stunted growth. The percentage of sodium is also an important element, like SAR (Na%) values, for the evaluation of water quality for irrigation purposes and is calculated according to the following equation [5]: Na% = × 100 % where: The concentrations of ions by (epm) units

Conclusions
This research provided a detailed overview of the reservoir's physicochemical properties in the Qazaniyah region of Diyala Province, East Iraq. There was no significant difference between springs and groundwater in the pH values. Concentrations of TDS indicated that groundwater samples in both periods were considered of brackish or salty water, while fresh water was found in the spring's samples. EC of groundwater and spring samples in both periods showed heavily mineralized water. Total hardness indicated that all water samples (groundwater and springs) are classified as very hard and exceed the permissible limits, due to the wide exposures to limestone and dolomitic limestone in the study area, which are rich in calcium and magnesium. Sodium was a predominant cation and sulphate was a predominant anion in groundwater samples, while calcium was a predominant cation and sulphate was a predominant anion in spring samples, which may indicate the presence of gypsum and anhydrite mineral and limestone rocks as the main sources of these ions. As related to springs and groundwater suitability for irrigation, some wells (w1, w 3, w 4, w 11, 15,w17and w18) and all springs (S1 and S2) were falling within permissible limits of irrigation water quality for the two periods, while other wells (w2,w5,w6,w7,w8,w9 and w10) were within the doubtful limits , and the remaining samples (w12,w13,w14 and w16) were within the unsuitable limit.