Study location
Al-Baha region is located between latitudes 19o 27` 17`` and 20o 49` 75 `` N and longitudes 40o 46` 30 and 42o 10` 10`` E (Fig. 1). The total area of Al-Baha region is 11221 km2. It has six administrative governorates (Al-Aqiq, Belgrashi, Al-Mandq, Al-Qora, Al-Mkhwah, and Qolwah) in addition to Al-Bahaa city. Al-Baha region is characterized by diverse soils, varied plant cover, and different patterns of topography and climate. Al-Baha region is located on the Arabian Shield, and its soils are mostly consisting of crystalline basement composed of Precambrian continental crust (Mohammed 2011). The weather is generally moderate to hot in summer and warm to cold in winter, with average temperatures ranging between 12° and 23°C. The average annual precipitation rate is about 150–200 mm, with moisture between 50–70% (Al-Barakah et al. 2020).
In this study, we focused our investigation on the area representing the middle part of Al-Baha region, which is known as Sarat Al-Baha, and is consisting of Al-Qora, Al-Mandq, Al-Baha, and Belgrashi Governorates (Fig. 1). The area of Sarat Al-Baha represents only 26.7% of the total area of Al-Baha region. Nevertheless, Sarat Al-Baha has the largest population percentage in the entire Al-Baha region. In addition, Sarat Al-Baha area includes the largest cultivated area, forest and mountainous areas, and, therefore, is a major area of interest for future socioeconomic development in Al-Baha region. With groundwater being a major resource for drinking and irrigation in Al-Baha region, it is, therefore, of crucial importance to assess its quality as impacted by climatic changes in the region. We obtained historical daily climatological reports for Al-Baha region from the General Authority for Meteorology and Environmental Protection in KSA. The data included average daily temperature and precipitation for 25 years (1995–2019) in Al-Baha region.
Groundwater sampling and analysis
Groundwater samples were collected from 88 locations in 1.0 L air tight plastic bottles during August 2020 (Fig. 2). Five different samples were collected from each location, which were placed in ice-boxes and moved to the laboratories in the Department of Soil Sciences at King Saud University, Riyadh for analyses. A portion of the groundwater sample was acidified by concentrated HNO3 to a pH < 2 for accurate determination of heavy metal concentration (APHA 1998).
The samples were analyzed for pH using pH meter (pH meter - CG 817), and total dissolved salts (TDS) by measuring electrical conductivity (EC) in dS m− 1 at 25°C (Test Kit Model 1500_20 Cole and Parmer). Magnesium and calcium ions were determined by titration by versenate as described by Sparks (1996). The potassium and sodium ions were measured by flame photometer (Corning 400) (Matiti 2004). Bicarbonates and carbonates ions were determined by acid titration (Sparks 1996). Chloride ion was determined by titration with silver nitrate (Matiti 2004). Sulfate was measured by the turbidity method (Tabatabai 1996), while the phenoldisulfonic acid method was used for the determination of nitrate (NO3−) (APHA 1998). Heavy metal concentrations of As, Co, Cd, Cr, Fe, Cu, Pb, Ni, Mo, Mn, and Zn were determined by inductively coupled plasma (ICP) (Perkin Elmer Model 4300DV).
Blanks and standard solutions examination were frequently run to check for probable inaccuracies in the analysis. The accuracy of the chemical analysis was estimated by calculating ion balance errors (IBEs). The IBE was determined based on the measured concentrations of cations and anions in the collected groundwater (Appelo and Postma 1996). IBE values equal to ± 3% were considered satisfactory. Samples with an IBE out of this range were re-estimated. More than 97% of the analyzed water samples were in the acceptable range with regard to the IBE values, indicating the suitability of the obtained results to carry out geochemical modeling and assessment of groundwater quality in the study area.
The hydrochemical characterization of major ions (Ca2+, Mg2+, Na+, K+, HCO3−, Cl−, and SO42−) of groundwater samples were plotted on Piper, Gibbs, and US salinity diagrams for the identification of groundwater type and quality (Piper 1944; Gibbs 1970; Richards 1954). The ratios of
Na++K+/(Na++Ca2++Mg2+) and Cl−/ (Cl−+HCO3−)as a function of TDS were employed to evaluate the sources (e.g. rock dominance, precipitation dominance, and evaporation dominance) of dissolved chemical compounds in groundwater (Gibbs 1970)..
Calculation of Water Quality Index (WQI)
WQI was computed to assess the quality of groundwater for drinking and irrigation purposes in the study area. Computation of WQI was carried out according to Al-Barakah et al. (2017). Ten measured parameters (i.e.: pH, TDS, Fe, Zn, Cu, Cd, Cr, Pb, As, and NO3-N) were included in the calculation of WQI. Each parameter was allocated a weight (wi) conferring to its significance in the quality of groundwater (Table 1). Parameters with the largest significance (i.e.: As, Pb, Cd, and NO3-N) were given a weight of 5. Whereas, parameters with the lowest significance (i.e.: Fe, Zn, and Mn) were given a weight of 1 (Ramakrishnalah et al. 2009). The remaining parameters (i.e.: pH, TDS, Cu, and Cr) were given a weight value between 1 and 5 (Table 1). A Relative weight (RWi) was calculated for each measured parameter (i) according to the equation:

where RWi is the relative weight of the ith parameter, Wi is the weight assigned to ith parameter, and n is the total number of measured parameters. RWi values of measured parameters are presented in Table 1.
Table 1
Standards of the World Health Organization (WHO), assigned weights and relative weights values for the calculation of Water Quality index (WQI) of groundwater in Sarat Al-Baha region.
Assessment criteria
|
|
Measured parameters
|
-
|
(mg L− 1)
|
pH
|
|
TDS
|
Fe
|
Zn
|
Cu
|
Cd
|
Cr
|
Pb
|
As
|
NO3-N
|
WHO Standards
|
8.5
|
|
700
|
0.30
|
5.0
|
2.0
|
0.003
|
0.05
|
0.01
|
0.01
|
50
|
Weight (Wi)
|
3
|
|
3
|
1
|
1
|
3
|
5
|
2
|
5
|
5
|
5
|
Relative weight (RWi)
|
0.09
|
|
0.09
|
0.03
|
0.03
|
0.09
|
0.15
|
0.07
|
0.15
|
0.15
|
0.15
|
A Quality Rating Scale (QRSi) was calculated for each measured parameter (i) according to the equation:
Where Ci is the measured value of the ith parameter (mg L-1), and Si is the WHO acceptable standard limit of the ith parameter (Alexakis 2011; WHO 2011).
A parameter index value (PIi) was calculated by multiplying the relative weight (RWi) by the quality rating scale (QRSi) for each measured parameter. The final value of the WQI was calculated as the sum of all computed parameter index values (PIi) according to the equation:
where PIi is the parameter index value of the ith parameter, and n is the total number of measured parameters. According to Ramakrishnalah et al. (2009), the quality of groundwater, for drinking purposes, based on the values of the WQI is classified into five classes: excellent, good, poor, very poor, and unsuitable for drinking, with value ranges of < 50, 50.1–100, 100.1–200, 200.1–300, and > 300, respectively.
Geochemical modeling
Interactions amongst the groundwater and the surrounding rocks are the main processes controlling the chemical features of groundwater. The water’s deviation from equilibrium with respect to dissolved minerals is defined by the saturation index (SI). The SI of a mineral is calculated using the following equation:
SI = log IAP/kt (4)
where IAP is the ion activity product of the dissociated chemical species in solution and kt is the equilibrium solubility product of the chemical involved (Alexakis 2011). The PHREEQC model (Ramakrishnalah et al. 2009) was used to obtain the SI of groundwater samples in Sarat Al-Baha region with respect to the main mineral phases. Saturation indices (SI) are usually used to assess mineral dissolution in groundwater. If the SI of the mineral is equal to zero, the mineral is in equilibrium with groundwater. SI values smaller than zero indicate that the mineral is under-saturated, whereas SI values greater than zero indicate the mineral is over-saturated.