Groundwater Quality Assessment at East El Minia Middle Eocene Carbonate Aquifer: Water Quality Index (WQI) and Health Risk Assessment (HRA)

Abstract

Around the world, groundwater supply is critical for vital needs such as drinking and irrigation. This work investigates groundwater in the carbonate aquifer of the Middle Miocene in the east El Minia area, Egypt. In this regard, thirty-two groundwater samples were collected. The water samples were analyzed for Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl⁻, SO₄²⁻, NO₃⁻, CO₂⁻, HCO₃⁻, Fe, Mn, Cd, As, Cr, Cu, and Pb. Groundwater has been evaluated using two methods, which are water quality index (WQI) and health risk assessment (HRA). The predominant groundwater is soft water, and the samples range in salinity from fresh to slightly salty. The groundwater mostly falls into the alkaline water type. All the groundwater samples under study are deemed low quality for human consumption due to water contamination. Fe, Mn, Cd, Cu, and Pb have high HQnc values, which can result in non-carcinogenic health issues in adults, while Mn, Cu, and Pb can give rise to non-carcinogenic health issues in children.

1. Introduction

During the past few decades, there has been a constant demand for more water to meet Egypt’s population growth and land expansion projects. At present, exploring new water resources is an important issue for desert reclamation, where rainfall and surface water availability are scarce. Thus, the development of groundwater projects is urgent in Egypt. The source of the groundwater, the bearing rocks, and the movement of water are the key determinants of water quality [1]. The carbonate aquifer is considered the principal aquifer in the area (east El Minia province). Many karst features of the western and eastern deserts characterize it. The carbonates that make up the fissured and karstified limestone aquifer have been examined by [2,3,4,5,6,7,8,9,10,11,12,13]. Understanding various parameters of groundwater, such as the sources, mechanisms of recharge, and the hydrogeochemical development along its flow pathways in the aquifer, is critical to sustainable groundwater usage [14]. Generally speaking, the Nubian sandstone complex is covered with carbonate rocks. The Nubian sandstone aquifer beneath it leaks water upward, and occasionally, local rainfall also contributes to the aquifer’s replenishment [15]. The Samalut formation represents the carbonate aquifer in the study area. It comprises hard, white, extremely fossiliferous limestone with thin shale and marl intercalations, characterized by great thickness and an average value of nearly 100 m [16].

The quality of groundwater is influenced by various natural and artificial elements, such as terrain, geology, local structures, evaporation/precipitation rates, weathering, water–rock interactions, fertilizers, industrial effluents, and other factors [17]. Overuse of groundwater for human consumption, pesticide pollution, heavy fertilizer application, and industrial waste disposal have all impacted groundwater quality [18]. Groundwater quality is influenced by anthropogenic, geochemical, geological, and climatic variables. Its appropriateness for industrial use, irrigation, and human consumption depends on the concentration of these factors.

Water quality is more significant than quantity, attributable to its direct impact on biota life [19,20]. Many methods were proposed for water quality investigation, including WHO, CCME, and EPA guidelines. WQI and HHR modules have been applied widely recently for water quality assessment and impact on human health [20,21]. HHR of polluted water and foodstuff with heavy metals is applied widely in developed countries compared to developing countries [22]. It can efficiently describe the possible groundwater influence on human health and provide a basis for water quality management works to confirm water security [23], while the WQI is utilized to convert huge quantities of water quality datasets into a single number, which characterizes the water quality level [24].

This paper assesses WQI and HHR for the groundwater in the carbonate aquifer of the Middle Eocene in the east El Minia district using conventional and multivariate statistical analysis. It displays the spatial distribution of water quality using ArcGIS 10.3. The WQI assessment is based on [25], while the HHR assessment is based on [26].

Location and Climate

The investigated area sited in the eastern portion of the Nile Valley, and it extends from Deirma was in the south to Maghagha in the north and is bounded from the west by the River Nile and from the east by the Red Sea governorate (Figure 1).

It is located between latitudes 27°10′ and 28°48′ N and longitudes 30°30′ and 31°30′E. The investigated area lies in the arid belt of North Africa, so its climate is hot with a high evaporation rate, rainless and dry in summer, and warm and mild with rare rainfall in winter. The rainfall months in this area are from October to May, with about 19.6 mm/year as the highest rainfall record. The evaporation rate is proportionally increased relative to the air temperature and wind speed [28]. According to the collected data from the Egyptian Meteorological Authority (EMA) and the National Oceanic and Atmospheric Administration (NOAA) for the years 1961 to 1990, the mean, maximum, and minimum values are represented in Figure 2A, while the data for the years 1991 to 2022 are described in Figure 2B.

Geologically, the investigated zone is principally covered by carbonate rocks of the Middle Eocene and the Quaternary sediments (Figure 1). Mainly, the Eocene carbonate rocks are composed of limestones and chalk intercalated by thin beds of sandy, clayey, and cherty limestone [31]. These limestones are divided into the Minia, the Samalut, the Maghagha, the Qarara, and the Observatory formations [27,32]. The Quaternary sediments are signified by (a) a narrow strip of the Nile silt deposits, which are considered the old, cultivated lands, and (b) the weathering product of the country rocks represented by wadi deposits (silt, sand, and gravel).

The dominant structures affecting the study area are normal faults, represented by many major NW-SE faults with a few NE-SW faults, as shown in Figure 3. The large number of faults gives rise to other structural features such as horst and graben systems.

Hydrologically, the primary water-bearing rocks in the investigated area are the Minia, Samalut, and Maghagha formations [33,34]. The Minia formation comprises alveolinal cross-bedded limestone with intercalations of chalk at the bottom. It becomes harder, massive, and karstic limestone with many holes, vugs, and caves at the top. The Samalut formation comprises white, highly cavernous, soft, Nummulitic limestone intercalated with clayey, marly, and coquina beds characterized by many voids, vugs, and extensive caves. The Maghagha formation is formed of marly limestones with interbeds of chalky limestones and a few clay intercalations. The Samalut formation represents the main productive aquifer in the east of El Minia [35]. The main recharge of this aquifer is from the occasional storms in the eastern watershed (about 32% of the recharge) and in the west by the infiltration of Nile water (about 36% of the recharge) [36,37] and possibly from the upward seepage from the Nubian sandstone aquifer through deep-seated faults [38,39]. The discharge takes place mainly through the pumping wells, which are used for irrigation.

2. Materials and Methods

2.1. Sampling and Analyses

Thirty-two groundwater samples were collected from pore wells, as shown in Figure 1. After collecting, these samples were transported and hydrochemically analyzed for various parameters:pH, total hardness (TH), electrical conductivity (EC), and total dissolved solids (TDS) as CaCO₃, calcium (Ca²⁺), magnesium (Mg²⁺), sodium (Na⁺), potassium (K⁺), bicarbonate (HCO₃⁻), sulfate (SO₄²⁻), chloride (Cl⁻), nitrate (NO₃⁻) and ammonia (NH₄⁺). Some of these parameters were immediately measured in the field by using temperature, TDS, pH, and electrical conductivity (EC) meter (HANNA HI-991300, HANNA istruments, Woonsocket, RI, USA). The Ca, Na, Mg, K, Cl⁻, SO₄²⁻, and HCO₃ concentrations were measured using Flame Photometer Jenway-PFP7 at the Agricultural Governorate, El Minya, Egypt.

The sampling locations were detected using a handheld Garmin (GPS, version 11.30) and plotted on the map using the Arc Map (Ver. 10.8) program. The geological cross-sections between different investigated points that determined the structure of the study area were made using the Global Mapper (Ver. 18) and Surfer (Ver. 12) software programs. The chemical dataset of the investigated groundwater samples was plotted using the Aquachem software (https://www.waterloohydrogeologic.com/) a Piper diagram.

2.2. Water Quality Evaluation for Irrigation

Some irrigation quality indicators were applied to evaluate the irrigation suitability of groundwater in the examined area. These indicators include sodium adsorption ratio (SAR), residual sodium carbonate (RSC), sodium percentage (Na%), and Kelly’s ratio (KR). These indicators were considered using the following equations.

High values of SAR show a hazard of sodium replacing the adsorption of calcium and magnesium. This replacement causes damage to the soil structure. The concentration of sodium plays a vital role in the evaluation of the groundwater quality to express reactions with the soil and know the permeability reduction. The SAR is important in evaluating the irrigation water quality and is calculated via the following equation [40,41].

$$\mathrm{S}\mathrm{A}\mathrm{R}={\displaystyle \frac{{\mathrm{Na}}^{+}}{\sqrt{\frac{{\mathrm{Ca}}^{2+}+{\mathrm{Mg}}^{2+}}{2}}}}$$

Residual sodium carbonate is considered one of the most important parameters that influence groundwater quality for irrigation as it affects soil’s physical properties through organic matter dissolution, which remains a black stain on its surface upon drying. The calculating equation of RSC can be estimated by [42,43] as the following:

RSC = (CO₃ + HCO₃) − (Ca + Mg) (epm)

In natural waters, the sodium hazard is considered one of the most important parameters of water appropriateness assessment for irrigation purposes. The sodium percentage is detected through the following equation according to [44]:

$$\mathrm{Na}\%={\displaystyle \frac{(\mathrm{Na}+\mathrm{K})}{(\mathrm{C}\mathrm{a}+\mathrm{M}\mathrm{g}+\mathrm{N}\mathrm{a}+\mathrm{K})}}\times 100 (\mathrm{e}\mathrm{p}\mathrm{m})$$

Ref. [45] detected a relation between the alkaline earths and sodium, where the excess sodium content relative to the alkaline earths concentration makes the groundwater unsuitable for irrigation.

$$\mathrm{K}\mathrm{I}={\displaystyle \frac{\mathrm{N}\mathrm{a}}{\left(\mathrm{C}\mathrm{a}+\mathrm{M}\mathrm{g}\right)}}\left(\mathrm{e}\mathrm{p}\mathrm{m}\right)$$

2.3. Water Quality Index (WQI)

The WQI calculation followed three steps, as detected by [25]. Three factors that comprise the quality index essential calculated were F1, F2, and F3. The CCME WQI was computed identically to the following equation:

$$\mathrm{W}\mathrm{Q}\mathrm{I}=100-\left[{\displaystyle \frac{\sqrt{{\mathrm{F}1}^2+{\mathrm{F}2}^2+{\mathrm{F}3}^2}}{1.732}}\right]$$

F1 is the scope and expresses the percentage of the variables that do not fit their objectives at least once throughout the period under attention, i.e., failed variables, relative to the total f measured variables.

$$\mathrm{F}1=\left[{\displaystyle \frac{\mathrm{N}\mathrm{u}\mathrm{m}\mathrm{b}\mathrm{e}\mathrm{r} \mathrm{o}\mathrm{f} \mathrm{f}\mathrm{a}\mathrm{i}\mathrm{l}\mathrm{e}\mathrm{d} \mathrm{v}\mathrm{a}\mathrm{r}\mathrm{i}\mathrm{a}\mathrm{b}\mathrm{l}\mathrm{e}\mathrm{s}}{\mathrm{T}\mathrm{o}\mathrm{t}\mathrm{a}\mathrm{l} \mathrm{n}\mathrm{u}\mathrm{m}\mathrm{b}\mathrm{e}\mathrm{r} \mathrm{o}\mathrm{f} \mathrm{v}\mathrm{a}\mathrm{r}\mathrm{i}\mathrm{a}\mathrm{b}\mathrm{l}\mathrm{e}\mathrm{s}}}\right]\times 100$$

F2 is known as “Frequency” and expresses the percentage of the individual tests that do not fit the objectives (frequency of failed tests).

$$\mathrm{F}2=\left[{\displaystyle \frac{\mathrm{N}\mathrm{u}\mathrm{m}\mathrm{b}\mathrm{e}\mathrm{r} \mathrm{o}\mathrm{f} \mathrm{f}\mathrm{a}\mathrm{i}\mathrm{l}\mathrm{e}\mathrm{d} \mathrm{t}\mathrm{e}\mathrm{s}\mathrm{t}\mathrm{s}}{\mathrm{t}\mathrm{o}\mathrm{t}\mathrm{a}\mathrm{l} \mathrm{n}\mathrm{u}\mathrm{m}\mathrm{b}\mathrm{e}\mathrm{r} \mathrm{o}\mathrm{f} \mathrm{t}\mathrm{e}\mathrm{s}\mathrm{t}\mathrm{s}}}\right]\times 100$$

F3 is known as the “Amplitude” and signifies the amount by which values of failed tests do not fit their objectives. F3 is calculated in three main steps (when the test value does not surpass the objective):

• The number of times through which a separate concentration is more than (or less than, when the objective is a minimum) the objective is termed an “excursion” and is expressed as follows:

$$\mathrm{E}\mathrm{x}\mathrm{c}\mathrm{u}\mathrm{r}\mathrm{s}\mathrm{i}\mathrm{o}\mathrm{n}\left(i\right)=\left[{\displaystyle \frac{\mathrm{f}\mathrm{a}\mathrm{i}\mathrm{l}\mathrm{e}\mathrm{d} \mathrm{t}\mathrm{e}\mathrm{s}\mathrm{t} \mathrm{v}\mathrm{a}\mathrm{l}\mathrm{u}\mathrm{e}}{\mathrm{o}\mathrm{b}\mathrm{j}\mathrm{e}\mathrm{c}\mathrm{t}\mathrm{i}\mathrm{v}\mathrm{e}}}\right]-1$$

2.

The collective amount by which specific tests are out of compliance is found by summing the excursions of separate tests from their objectives and dividing by the total number of tests (both those meeting objectives and those not meeting objectives). This variable, referred to as the normalized sum of excursions, or nse, is calculated as follows:

$$\mathrm{n}\mathrm{s}\mathrm{e}={\displaystyle \frac{\sum _{\mathrm{i}=1}^{\mathrm{n}}\mathrm{e}\mathrm{x}\mathrm{c}\mathrm{u}\mathrm{r}\mathrm{s}\mathrm{i}\mathrm{o}\mathrm{n}\left(i\right)}{\mathrm{t}\mathrm{o}\mathrm{t}\mathrm{a}\mathrm{l} \mathrm{n}\mathrm{u}\mathrm{m}\mathrm{b}\mathrm{e}\mathrm{r} \mathrm{o}\mathrm{f} \mathrm{t}\mathrm{e}\mathrm{s}\mathrm{t}\mathrm{s}}}$$

3.

F3 is then found by an asymptotic function that scales the normalized sum of the excursions from objectives (nse) to produce a range between 0 and 100.

$$\mathrm{F}3=\left[{\displaystyle \frac{\mathrm{n}\mathrm{s}\mathrm{e}}{0.01 \mathrm{n}\mathrm{s}\mathrm{e}+0.01}}\right]$$

The divisor 1.732 normalizes the resultant values to a range between 0 and 100, where the “worst” water quality has a 0 value, and the “best” water quality has a 100% value [25].

2.4. Health Risk Assessment (HRA)

Ramadan et al. [8] stated that the groundwater shows high pollution levels caused by Pb and Fe in some localities of the west Nile River in Minia Governorate due to the effects of pollution from the industrial wastewater from the sugar factory of Abou-Qarqas city, El-Moheet drain, the fertilizer leaching process, and pesticides seeping into groundwater from soils and agricultural wastewater.

The HRA model was innovated by the United States Environmental Protection Agency [46] and was applied by several researchers [47,48,49]. Human health problems have recently increased because of the contamination of drinking water, unplanned drainage systems, air pollution, absence of seasonal rainfall, and high temperatures, signifying the arid regions in Egypt. According to [50], the HRA, non-carcinogenic (HQnc), and carcinogenic (HQc) hazards were calculated through the following equations:

$$\mathrm{H}\mathrm{Q}\mathrm{n}\mathrm{c}={\displaystyle \frac{\mathrm{C}\mathrm{D}\mathrm{I}}{\mathrm{R}f\mathrm{D}}}$$

HQnc is the ratio between heavy metal’s calculated mean chronic daily intakes (CDIs) and the oral reference dose (RfD).

$$\mathrm{C}\mathrm{D}\mathrm{I}={\displaystyle \frac{\mathrm{C}\times \mathrm{I}\mathrm{R}\times \mathrm{E}\mathrm{D}\times \mathrm{E}\mathrm{F}}{\mathrm{B}\mathrm{W}\times \mathrm{A}\mathrm{T}}}$$

where CDI, C, EF, IR, BW, ED, AT, and RfD stand for body weight (for adults, 70 kg and for children, 28 kg), average daily intake amount (for adults, 2 L d⁻¹ and for children, 1.2 L d⁻¹), exposure period (10 years), exposure regularity (180 d), average time (lifetime × 365 for carcinogenic risk and ED × 365 d for non-carcinogenic), and toxicity reference dose. The toxicity reference dose for Mn, Fe, Pb, Cd, Cr, Cu, and As, according to [51], is 0.014, 0.007, 0.0035, 0.0005, 0.0003, 0.04, and 0.0003, respectively. The adult’s average lifetime is 65 years, and 6.5 years for children.

$$\mathrm{H}\mathrm{Q}\mathrm{c}=\mathrm{C}\mathrm{D}\mathrm{I}\times \mathrm{S}\mathrm{F}$$

where HQc is the result of multiplying the calculated mean chronic daily intakes (CDIs) with the slope factor (SF). The Total Hazard Index (THI) was calculated separately for both adults and children as non-carcinogenic risks through the following equation:

$$THI=\sum {HQ}_{(all studied heavy metals)}$$

3. Results and Discussion

3.1. Hydrogeochemistry

The hydrogeochemical analyses records of groundwater samples for the area under study are represented in

Table 1. Statistical summary found in groundwater quality parameters analysis and comparison with the [53] standards for drinking purposes.

Parameters	Concentration in Groundwater Samples			WHO MAL (2017)	Percent of Samples
	Maximum	Minimum	Mean		Below MAL	Above MAL
Hydrogen ion concentration (PH)	9.70	7.50	7.85	9.2	96.8%	3.2%
Total dissolved solids (mg/L)	2327.80	271.20	668.20	1000	93.8%	6.2%
Electric conductivity (µS/cm)	4235.60	509.40	1218.23	1500	84.4%	15.6%
Total hardness (mg/L)	1035.44	32.19	196.83	500	93.8%	6.2%
Calcium (mg/L)	271.97	11.02	58.71	75	87.5%	12.5%
Magnesium (mg/L)	165.03	3.34	21.90	50	96.8%	3.2%
Sodium (mg/L)	415.48	60.39	145.54	200	87.5%	12.5%
Potassium (mg/L)	10.58	3.77	5.20	10	96.8%	3.2%
Chloride (mg/L)	385	49.15	124.65	250	93.8%	6.2%
Bicarbonates (mg/L)	1708.28	89.57	277.3	100	9.4%	90.6%
Sulfates(mg/L)	414.26	10.60	101.59	400	96.8%	3.2%
Nitrates(mg/L)	12.80	0.67	4.11	50	100%	-
Ammonia (mg/L)	1.68	0.34	0.88	0.5	15.6%	84.4%

. Hydrogen ion concentration (pH) values of the groundwater samples fluctuated from 7.50 to 9.70, with an average of 7.85, which indicates a slightly alkaline media. The values of total dissolved solids (TDS) vary from 271.20 to 2327.80 mg/L and average 668.20 mg/L. The groundwater is classified according to TDS values where values below 1000 mg/L, groundwater is considered freshwater; values from 1000 to 3000 mg/L, groundwater is slightly saline; values from 3000 to 10,000 mg/L, groundwater is moderately saline; and values between 10,000 and 35,000 mg/L, groundwater is highly saline [52]. The TDS values for the area under study indicate the leaching and dissolution of the aquifer materials in two studied wells (1 and 29), while 30 samples are classified as freshwater. The electrical conductivity (EC) values extended from 509.40 to 4235.60 µS/cm, averaging 1218.23 µS/cm. The total hardness (TH) values of the studied groundwater samples range from 32.19 to 1035.44 mg/L with an average of 196.83 mg/L; the high values of TH are due to the leaching and dissolution of calcium and magnesium-bearing deposits (limestone). In contrast, 30 samples are acceptable according to [44] maximum allowable limits.

Makhlouf et al. [10] proved the impacts of spatial distribution of surface water on groundwater quality in West Minia. They mentioned that this correlation should be considered in sustainable groundwater management in the investigated area.

The major ions concentration in the studied wells is presented in Figure 4A. The Ca²⁺ ion concentration ranges from 11.02 to 271.97 mg/L with an average value of 58.71 mg/L, representing gypsum-bearing deposits leaching and dissolution in four studied wells (1, 2, 29 and 32). At the same time, 28 samples are acceptable according to [53] maximum allowable limits. The Mg²⁺ concentration values vary from 3.34 to 165.03 mg/L with an average value of 21.90 mg/L, indicating leaching on the limestone in only one well sample (29), while the rest of the samples are acceptable. Na⁺ ranges in the investigated area from 60.39 to 415.48 mg/L, with an average value of 145.54 mg/L, indicating old marine water origin in limestone in four samples (1, 2, 29 and 32), while the remaining samples are acceptable. The K⁺ concentrations vary from 3.77 to 10.58 mg/L with an average value of 5.20 mg/L, indicating the presence of Maghagha and Qarara shale in the well (29). At the same time, the rest of the samples are acceptable according to [44] maximum allowable limits. Cl⁻ ranges from 49.15 to 385 mg/L with an average value of 124.65 mg/L, indicating the chlorine-bearing deposits leaching laid down under marine conditions in wells (5 and 24). The rest of the studied samples are acceptable. HCO₃⁻ ranged from 89.57 to 1708.28 mg/L with an average of 313.86 mg/L, indicating carbonate rocks dissolution and the carbon dioxide (CO₂⁻) content in the soil zone in all the studied wells except wells (12 and 13). SO₄²⁻ concentrations ranged from 10.60 to 414.26 mg/L with an average value of 101.59 mg/L, indicating the excessive use of fertilizers and irrigational sewage in well (29) in addition to the presence of evaporates such as gypsum and anhydrite in Maghagha and Qarara shales. At the same time, the rest of the samples are acceptable. NO₃⁻ ranges from 0.67 to 12.80 mg/L with an average value of 4.11 mg/L (Figure 4B), which indicates that all studied samples are acceptable according to [53] maximum allowable limits. NH₄⁺ concentrations range from 0.34 to 1.68 mg/L with an average value of 0.88 mg/L, indicating waste water and fertilizer contamination in all studied wells except (5, 21, 26, 27 and 32).

High ammonia concentrations may result in many dangerous diseases, such as liver disease, kidney failure, and genetic disorders. It may also irritate and burn the skin, mouth, throat, lungs, and eyes [54]. These high concentrations of NH₄⁺ in the study area result from fertilizer contamination due to N-fertilizers usage, Minia-azote, and Biogen fertilizers [55]. The ammonia-zoning map (Figure 5) indicates that the ammonia concentrations increase in the northern direction of the area as a primary effect of N-fertilizer usage.

The Piper diagram is essential in making four basic conclusions: water type, precipitation or solution, mixing, and ion exchange. From Figure 6, according to [56], it determined that alkalis exceed alkaline earths. Predominant groundwater samples (68.8%) are classified as alkaline water with prevailing SO₄²⁻ and Cl⁻ [57], indicating the excess gypsum and halite dissolved in the water samples. This class suggests an excess of alkalis in alkaline earths (Na+K > Ca+Mg) and an excess of stronger acidic anions than weaker acidic anions (Cl+SO₄ > CO₃+HCO₃). This class indicated the halite weathering [58] and the surface salt infiltration into groundwater attributable to irrigational practices in the area. This also means that fertilizers have contaminated these water courses, and sewage appears, shifting the results to the middle of the Piper plot [59]. The left triangle (for cations) demonstrates that the common of the water samples is present in the sodium type field, while in the right triangle (for anions), mainly the water samples are of no dominant anion, and only 25% are plotted in the bicarbonate type field.

3.2. Appraisal of WQI and HRA

The WQI value was specified, and water quality was graded into five categories by [60]; these categories are (1) poor quality, WQI<45; (2) marginal, WQI from 45 to 65; (3) fair, WQI from 65 to 80; (4) good, WQI from 80 to 95; and (5) excellent, WQI ≥ 95 (

Table 2. Water quality index classification for the studied groundwater.

Sample No.	WQI Value	WQI Class	Sample No.	WQI Value	WQI Class
1	36.53	Poor	17	41.27	Poor
2	38.52	Poor	18	41.27	Poor
3	41.27	Poor	19	41.27	Poor
4	41.27	Poor	20	41.27	Poor
5	41.27	Poor	21	41.98	Poor
6	41.27	Poor	22	41.27	Poor
7	41.27	Poor	23	41.27	Poor
8	41.27	Poor	24	40.11	Poor
9	41.27	Poor	25	41.27	Poor
10	41.27	Poor	26	41.98	Poor
11	41.27	Poor	27	41.98	Poor
12	41.98	Poor	28	41.27	Poor
13	41.98	Poor	29	28.57	Poor
14	41.27	Poor	30	41.27	Poor
15	41.27	Poor	31	41.27	Poor
16	41.27	Poor	32	38.52	Poor

). From Table 2, it was detected that all the studied groundwater samples are classified as poor quality for human drinking uses due to the water pollution with the discharge of irrigation wastewater and fertilizers contamination.

According to

Table 3. Statistical parameters of non-carcinogenic health risks for the groundwater.

S. No	HQnc (Adults)							THI	HQnc (Children)							THI
	Fe	Mn	As	Cd	Cr	Cu	Pb		Fe	Mn	As	Cd	Cr	Cu	Pb
1	0.222034	0.008671	0.578052	0.052458	2.355562	0.000379	0.032206	3.249362	3.330509	0.130062	8.670781	0.786873	35.33343	0.00569	0.483086	48.74044
2	0.173725	0.013626	0.873581	0.049423	0.556375	0.000488	0.031586	1.698805	2.605879	0.204383	13.10372	0.741352	8.345627	0.007316	0.473796	25.48207
3	0.069986	0.001239	0.4214	0.049684	0.034683	0.000705	0.014493	0.592188	1.049784	0.01858	6.321	0.745254	0.520247	0.010568	0.217389	8.882821
4	0.215841	0.010529	0.823002	0.074135	2.926389	0.000108	0.034683	4.084686	3.237608	0.157932	12.34502	1.112028	43.89583	0.001626	0.520247	61.2703
5	0.134087	0.004552	0.456083	0.045088	0.12746	0.000163	0.034188	0.801621	2.011312	0.068282	6.841246	0.676321	1.911907	0.002439	0.512815	12.02432
6	0.247737	0.007122	0.422701	0.048383	0.199428	0.000217	0.014493	0.94008	3.716049	0.106836	6.340509	0.725744	2.99142	0.003252	0.217389	14.1012
7	0.120772	0.006348	0.358103	0.034596	0.177751	0.000217	0.031215	0.729002	1.811574	0.095224	5.371549	0.518946	2.666265	0.003252	0.468222	10.93503
8	0.153597	0.013161	0.395821	0.030434	0.368508	5.42 × 10−5	0.02081	0.982386	2.30395	0.197415	5.937317	0.456517	5.527623	0.000813	0.312148	14.73578
9	0.087946	0.001394	0.150294	0.081939	0.101159	0.000921	0.053883	0.477536	1.319197	0.020903	2.254403	1.229083	1.517387	0.013819	0.808241	7.163033
10	0.043044	0.012697	0.386717	0.029394	0.355502	0.000271	0.014121	0.841746	0.645664	0.190448	5.800753	0.440909	5.33253	0.004064	0.211815	12.62618
11	0.08423	0.006503	0.09061	0.066852	0.182086	0.001409	0.026384	0.458074	1.263457	0.097546	1.359145	1.002776	2.731296	0.021135	0.395759	6.871114
12	0.041496	0.0096	0.584411	0.007283	0.268794	0.000325	0.016722	0.928631	0.622438	0.143997	8.76616	0.109252	4.031913	0.004877	0.250833	13.92947
13	0.071224	0.001084	0.1633	0.114888	0.657534	0.000325	0.014864	1.023219	1.068364	0.016258	2.449496	1.723318	9.863014	0.004877	0.222963	15.34829
14	0.039328	0.004645	0.208966	0.050724	0.130062	0.000596	0.025269	0.45959	0.589923	0.069676	3.134487	0.760861	1.950926	0.008942	0.379037	6.893852
15	0.03747	0.006503	0.521981	0.019249	0.182086	0.000325	0.024898	0.792513	0.562052	0.097546	7.829715	0.288737	2.731296	0.004877	0.373463	11.88769
16	0.017651	0.001548	0.113587	0.066245	0.043354	0.000325	0.024154	0.266865	0.264768	0.023225	1.703809	0.993672	0.650309	0.004877	0.362315	4.002975
17	0.075869	0.011148	0.885865	0.087575	2.478398	5.42 × 10−5	0.012387	3.551297	1.13804	0.167222	13.28797	1.313623	37.17597	0.000813	0.185802	53.26945
18	0.062863	0.0096	0.357236	0.06321	0.268794	0.000325	0.021553	0.783582	0.942947	0.143997	5.358543	0.94815	4.031913	0.004877	0.323296	11.75372
19	0.05605	0.007122	1.13226	0.066331	0.354057	0.000596	0.041496	1.657913	0.840756	0.106836	16.98389	0.994972	5.310854	0.008942	0.622438	24.86869
20	0.172177	0.0096	0.540479	0.043787	0.513021	0.000596	0.035302	1.314963	2.582654	0.143997	8.10718	0.656812	7.695318	0.008942	0.529537	19.72444
21	0.049857	0.006193	0.132229	0.052458	0.468222	0.000271	0.026012	0.735244	0.747855	0.092901	1.983441	0.786873	7.023333	0.004064	0.390185	11.02865
22	0.15081	0.017342	0.629354	0.066765	2.89026	0.000542	0.042735	3.797807	2.262145	0.260123	9.440313	1.001475	43.35391	0.008129	0.641018	56.96711
23	0.129752	0.006503	0.321686	0.052285	0.182086	0.000379	0.016351	0.709042	1.946281	0.097546	4.82529	0.784272	2.731296	0.00569	0.245259	10.63563
24	0.292949	0.006101	0.976908	0.086708	3.251543	5.42 × 10−5	0.041496	4.655758	4.394228	0.091508	14.65362	1.300617	48.77314	0.000813	0.622438	69.83637
25	0.040257	0.003097	0.585278	0.070233	3.172061	0.000108	0.017342	3.888376	0.603858	0.046451	8.779166	1.0535	47.58091	0.001626	0.260123	58.32564
26	0.075869	0.011613	0.297841	0.019249	0.325154	0.000434	0.021058	0.751218	1.13804	0.17419	4.46762	0.288737	4.877314	0.006503	0.315864	11.26827
27	0.02787	0.023999	0.576173	0.036677	0.671986	0.000542	0.012387	1.349635	0.418056	0.359992	8.642601	0.550161	10.07978	0.008129	0.185802	20.24452
28	0.03778	0.006348	0.2107	0.056967	0.177751	0.000379	0.017094	0.507019	0.566697	0.095224	3.1605	0.854505	2.666265	0.00569	0.256407	7.605289
29	0.314625	0.010684	0.621261	0.043007	0.299142	0.000163	0.022916	1.311798	4.719382	0.160255	9.318922	0.645106	4.487129	0.002439	0.343735	19.67697
30	0.054502	0.007122	0.41692	0.061563	1.358422	5.42 × 10−5	0.021058	1.919641	0.817531	0.106836	6.253801	0.923438	20.37634	0.000813	0.315864	28.79462
31	0.122939	0.016722	0.424146	0.067199	2.875809	0.000163	0.029109	3.536087	1.844089	0.250833	6.362186	1.007978	43.13714	0.002439	0.436636	53.0413
32	0.088256	0.008206	0.38585	0.147403	1.44513	0.000813	0.042115	2.117774	1.323842	0.123094	5.787747	2.211049	21.67695	0.012193	0.631728	31.76661
Min.	0.017651	0.001084	0.09061	0.007283	0.034683	5.42 × 10−5	0.012387	0.266865	0.264768	0.016258	1.359145	0.109252	0.520247	0.000813	0.185802	4.002975
Max.	0.314625	0.023999	1.13226	0.147403	3.251543	0.001409	0.053883	4.655758	4.719382	0.359992	16.98389	2.211049	48.77314	0.021135	0.808241	69.83637
Mean	0.109769	0.008457	0.470087	0.057569	0.918705	0.000384	0.026074	1.591046	1.646529	0.126854	7.05131	0.863529	13.78058	0.005766	0.391114	23.86568

, the HQnc mean values for Fe, Mn, As, Cr, Cd, Cu, and Pb in the studied groundwater samples for adults and children, respectively, are 0.109769 and 1.646529, 0.008457, and 0.126854, 0.470087 and 7.05131, 0.057569 and 0.863529, 0.918705 and 13.78058, 0.000384 and 0.005766, and 0.026074 and 0.391114. According to [61], Fe, Mn, Cd, Cu, and Pb can cause non-carcinogenic health problems in adults as a result of their high HQnc values, while Mn, Cu, and Pb can cause non-carcinogenic health problems in children. According to the graphical projection of the THI values in Figure 7, 46.87% and 100% of the samples have unsuitable values of THI (greater than 1) for adults and children, respectively. Therefore, the cumulative influence of Fe, Mn, As, Cr, Cd, Cu, and Pb in drinking water tends to be a health risk. Thus, children (THI mean: 23.87) are more vulnerable than adults (THI mean: 1.59) as a result of disproportionate intake of Fe, Mn, As, Cr, Cd, Cu, and Pb through drinking water. The health risk map of the adults (Figure 8A) indicates that most of the northeastern and southeastern portions of the study area are highly susceptible, as per the THI. According to the zonation map in Figure 8B, As is suitable for adults in all wells of the study area except (well 19). The zonation map in Figure 8C indicates that the Cr non-carcinogenic health risks for adults increase from the center of the study area toward the northern and southern directions. The zonation map in Figure 9A indicates Fe non-carcinogenic health risks for children in all of the areas except 12 wells in the northern portion. The zonation map in Figure 9B indicates that the Cd non-carcinogenic health risks for children increase mainly in wells in the northern portion of the study area. In comparison, the zonation map in Figure 9C indicates Cr non-carcinogenic health risks for children in the area except wells 3 and 16.

According to

Table 4. Statistical parameters of carcinogenic health risks for the groundwater.

S. No.	HQc (Adults)				HQc (Children)
	As	Cd	Cr	Pb	As	Cd	Cr	Pb
1	0.00026	9.96706 × 10−6	0.000353334	6.19961 × 10−6	0.003902	0.00015	0.0053	9.29941 × 10−5
2	0.000393	9.39046 × 10−6	8.34563 × 10−5	6.08039 × 10−6	0.005897	0.000141	0.001252	9.12058 × 10−5
3	0.00019	9.43988 × 10−6	5.20247 × 10−6	2.78982 × 10−6	0.002844	0.000142	7.8 × 10−5	4.18474 × 10−5
4	0.00037	1.40857 × 10−5	0.000438958	6.6765 × 10−6	0.005555	0.000211	0.006584	0.000100148
5	0.000205	8.56673 × 10−6	1.91191 × 10−5	6.58112 × 10−6	0.003079	0.000129	0.000287	9.87168 × 10−5
6	0.00019	9.19276 × 10−6	2.99142 × 10−5	2.78982 × 10−6	0.002853	0.000138	0.000449	4.18474 × 10−5
7	0.000161	6.57332 × 10−6	2.66627 × 10−5	6.00885 × 10−6	0.002417	9.86 × 10−5	0.0004	9.01328 × 10−5
8	0.000178	5.78254 × 10−6	5.52762 × 10−5	4.0059 × 10−6	0.002672	8.67 × 10−5	0.000829	6.00885 × 10−5
9	6.76 × 10−5	1.55684 × 10−5	1.51739 × 10−5	1.03724 × 10−5	0.001014	0.000234	0.000228	0.000155586
10	0.000174	5.58485 × 10−6	5.33253 × 10−5	2.71829 × 10−6	0.00261	8.38 × 10−5	0.0008	4.07743 × 10−5
11	4.08 × 10−5	1.27018 × 10−5	2.7313 × 10−5	5.07891 × 10−6	0.000612	0.000191	0.00041	7.61837 × 10−5
12	0.000263	1.38386 × 10−6	4.03191 × 10−5	3.21903 × 10−6	0.003945	2.08 × 10−5	0.000605	4.82854 × 10−5
13	7.35 × 10−5	2.18287 × 10−5	9.86301 × 10−5	2.86136 × 10−6	0.001102	0.000327	0.001479	4.29204 × 10−5
14	9.4 × 10−5	9.63757 × 10−6	1.95093 × 10−5	4.86431 × 10−6	0.001411	0.000145	0.000293	7.29646 × 10−5
15	0.000235	3.65734 × 10−6	2.7313 × 10−5	4.79277 × 10−6	0.003523	5.49 × 10−5	0.00041	7.18916 × 10−5
16	5.11 × 10−5	1.25865 × 10−5	6.50309 × 10−6	4.64971 × 10−6	0.000767	0.000189	9.75 × 10−5	6.97456 × 10−5
17	0.000399	1.66392 × 10−5	0.00037176	2.38446 × 10−6	0.00598	0.00025	0.005576	3.5767 × 10−5
18	0.000161	1.20099 × 10−5	4.03191 × 10−5	4.14897 × 10−6	0.002411	0.00018	0.000605	6.22345 × 10−5
19	0.00051	1.2603 × 10−5	5.31085 × 10−5	7.98796 × 10−6	0.007643	0.000189	0.000797	0.000119819
20	0.000243	8.31961 × 10−6	7.69532 × 10−5	6.79572 × 10−6	0.003648	0.000125	0.001154	0.000101936
21	5.95 × 10−5	9.96706 × 10−6	7.02333 × 10−5	5.00738 × 10−6	0.000893	0.00015	0.001053	7.51106 × 10−5
22	0.000283	1.26854 × 10−5	0.000433539	8.2264 × 10−6	0.004248	0.00019	0.006503	0.000123396
23	0.000145	9.93411 × 10−6	2.7313 × 10−5	3.14749 × 10−6	0.002171	0.000149	0.00041	4.72124 × 10−5
24	0.00044	1.64745 × 10−5	0.000487731	7.98796 × 10−6	0.006594	0.000247	0.007316	0.000119819
25	0.000263	1.33443 × 10−5	0.000475809	3.33825 × 10−6	0.003951	0.0002	0.007137	5.00738 × 10−5
26	0.000134	3.65734 × 10−6	4.87731 × 10−5	4.05359 × 10−6	0.00201	5.49 × 10−5	0.000732	6.08039 × 10−5
27	0.000259	6.96871 × 10−6	0.000100798	2.38446 × 10−6	0.003889	0.000105	0.001512	3.5767 × 10−5
28	9.48 × 10−5	1.08237 × 10−5	2.66627 × 10−5	3.29056 × 10−6	0.001422	0.000162	0.0004	4.93584 × 10−5
29	0.00028	8.17134 × 10−6	4.48713 × 10−5	4.41126 × 10−6	0.004194	0.000123	0.000673	6.61689 × 10−5
30	0.000188	1.16969 × 10−5	0.000203763	4.05359 × 10−6	0.002814	0.000175	0.003056	6.08039 × 10−5
31	0.000191	1.27677 × 10−5	0.000431371	5.60349 × 10−6	0.002863	0.000192	0.006471	8.40524 × 10−5
32	0.000174	2.80066 × 10−5	0.00021677	8.10718 × 10−6	0.002604	0.00042	0.003252	0.000121608
Min.	4.08 × 10−5	1.38386 × 10−6	5.20247 × 10−6	2.38446 × 10−6	0.000612	2.08 × 10−5	7.8 × 10−5	3.5767 × 10−5
Max.	0.00051	2.80066 × 10−5	0.000487731	1.03724 × 10−5	0.007643	0.00042	0.007316	0.000155586
Mean	0.000212	1.0938 × 10−5	0.000137806	5.0193 × 10−6	0.003173	0.000164	0.002067	7.52895 × 10−5

, the HQc mean values for As, Cd, Cr, and Pb in the studied groundwater samples for adults and children, respectively, are 0.000212 and 0.003173, 1.0938 × ${10}^{-5}$ and 0.000164, 0.000137 and 0.002067, and 5.0193 $\times {10}^{-6}$ and 7.52895 ${\times 10}^{-5}$. According to [51], all heavy metals can cause carcinogenic health problems for adults and children as a result of their high HQc values.

4. Conclusions

This research uses multivariate statistical and geographical analysis to investigate heavy metals contamination of the groundwater in the Middle Eocene carbonate aquifer in east El Minia, Egypt. Ingestion has been used to examine the influence of heavy metals intake on health, including concerns about the carcinogenic and non-carcinogenic effects. The research yielded the following conclusions:

• Most examined water samples are categorized as fresh water and acceptable for drinking use; also, the majority of studied water samples, with total hardness (TH) values ranging from 32.19 to 1035.44 mg/L, are suitable for household use;
• The increase in ammonia concentrations in the research area’s northern direction is regarded as the use of N-fertilizers. Numerous serious illnesses, including liver damage, kidney failure, and genetic problems, could be brought on by these high quantities. Additionally, it might cause harm and irritate the eyes, lips, throat, and lungs;
• Most groundwater samples (68.8%) are classified as alkaline water with prevailing SO₄²⁻ and Cl⁻, indicating the excess gypsum and halite dissolved in the water samples;
• Of the samples collected, 46.87% and 100% had THI values unsuitable for adults (more than 1) and children. As a result, the combined effect of Fe, Mn, As, Cr, Cd, Cu, and Pb in drinking water tends to harm human health;
• According to the THI, most of the research area’s northeastern and southeastern regions are extremely sensitive.