Hydrogeochemical Evaluation of Groundwater and its Suitability for Drinking and Irrigation Using Water Quality Index, Statistical and Geochemical Modelling, Debila and El-Oued regions, Algeria

doi:10.21203/rs.3.rs-1855927/v1

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Hydrogeochemical Evaluation of Groundwater and its Suitability for Drinking and Irrigation Using Water Quality Index, Statistical and Geochemical Modelling, Debila and El-Oued regions, Algeria

https://doi.org/10.21203/rs.3.rs-1855927/v1

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The study area is located in the Debila and El-Oued regions in the northeast of the Algeria desert. The water samples were collected from the semi-confined Mio-Pliocene and Lower Pontian aquifers. Physicochemical parameters such as temperature, pH, EC, TDS, and major ions were measured and compared with WHO standards. There is significant water quality deterioration because of strong mineralization and anthropogenic activities. The hydrogeochemical evaluation of groundwater revealed that evaporation, dissolution of gypsum, and reverse ion exchange are the main controlling factors of the water composition in the study area. The two main hydro-chemical facies of the groundwater in the deep aquifers are Ca²⁺–Mg²⁺–Cl/SO₄²⁻ and Na⁺–Cl⁻. The water quality index (WQI) was calculated by using the weighted arithmetic method to determine the suitability of water for drinking. The groundwater in Debila and El-Oued regions is not suitable for drinking. The groundwater is suitable for irrigation according to Sodium adsorption ratio (SAR), Na%, Magnesium risk (MR), Permeability Index (PI), and residual Sodium carbonate index (RSC). The values of the saturated index (SI) indicated that the groundwater is undersaturated with halite, anhydrite, and gypsum but saturated to oversaturated by calcite, aragonite, and dolomite.The groundwater in the Debila and El-Oued regions is classified as brackish water. Using brackish water for drinking and irrigation will have an adverse effect on human health and increase soil salinity and decrease plant production. There is no need for using fertilizers containing calcium where the SAR has a low to medium value and the soil will not be affected by sodification or decrease in the capacity of infiltration.

Hydrogeochemistry

Water quality index

Geochemical modeling

Reverse ion exchange

water salinity impacts.

Semi-arid countries such as Algeria are suffering from water shortage due to the pollution risks to water resources. The groundwater in the northeast Algerian desert is the second main resource for irrigation, drinking, and industry (Khalil et al., 2018). Increasing the population, agriculture and industrial sectors in this area led to the withdrawal more quantity of water from deep and shallow aquifers. The aquifer in the northeast of Algerian Sahara is one of the largest aquifers in the world consisting of a Continental Intercalaire and Complex terminal aquifer (UNESCO, 1972; OSS (Observatoire Sahara et Sahel), 2003). The abstraction of groundwater in this region increased from 600Mm3/year to 2120 Mm3/year in the period from 1970 to 2020 (DRE, 2019). The abstraction of groundwater from the complex terminal aquifer is used for drinking and irrigation and the total production wells raised to 203 boreholes in 2019 (Bouselsal et al., 2015; Khechana et al., 2011; Bouselsal & Kherici, 2014). The most concentrated area of production wells with over-abstraction is in the El-Oued and Debila regions. For this reason, hydrochemical evaluation and water quality monitoring are required for the sustainability and management of groundwater resources in this semiconfined aquifer (Allia, 2018; Saibi et al., 2016; Zaiz et al., 2017; Guendouz and Moulla, 1995; Moulla et al., 2012; Guendouz et al., 2003; Paix, 1956; Cornet, 1964). This work aims to evaluate the groundwater by using a water quality index, geochemical and statistical modeling, and determine its suitability for drinking and irrigation and the effect on human health and the soil environment. The result from this study gives recommendations for suitable groundwater management in Souf valley to avoid more deterioration of water quality, soil salinity, and human body diseases.

The selected sampling locations were concentrated in Debila, and El-Oued sectors in addition to a few samples around these regions to check the spatial variations with the direction of groundwater flow (fig. 1). By April 2020, 45 water samples were collected in acidified polyethylene bottles after filtration for laboratory analysis. The field measurements included temperature, pH, EC, TDS, and ground surface elevation. A portable multimeter (HI 9829 type) was used for measuring EC and pH. The chemical parameters such as Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^-, HCO₃^-, CO₃^2-, SO₄^2-, and NO₃^- were measured in the laboratory. Spectrophotometer HACH (DR2000 type) was used for measuring SO₄^2-, Cl^-, and NO₃^- while K⁺, Ca⁺, and Na⁺ were measured by flame spectrophotometer. The complexometric method was used to analyze Mg²⁺. and the titrimetric method for measuring CO₃^2- and HCO₃^-. Surfer and QGIS were used for creating the location map and spatial distribution map for the different parameters. Excel and DIAGRAMMES software were used for graphical representation such as Piper plot, Gibbs plot, binary plot, Durov diagram, Wilcox, and USSL diagram.

Hydrogeology of the study area

The Souf valley is located between latitude 33°12`00``/33°35`00`` N and longitude 6°40`00`/7°5`00``E covering an area of about 80000 cubic meters and the population is about 900,000 (Khechana et al., 2011). This area is characterized by hot and dry weather with evapotranspiration of 1224mm per year (ONM, 2019). The hydrogeological system of El-Oued consists of three main aquifers from up to down (fig. 2) as follow, shallow quaternary aquifer, Complex terminal (Mio-Pliocene and lower Pontian), and continental Intercalaire (CI) (UNESCO, 1972; Boulifa, 2012; Bouselsal, 2016; Busson, 1971). The geological composition of CT starts with limestone and dolomite (Senonian-Eocene) in the lower part, gravel (lower Pontian) in the middle, and the upper part composed mainly of sand and sandstone (Mio-Pliocene). The thickness CT aquifer is 300m with a depth of 220m. The groundwater flows from southwest to northeast where the piezometric level is high in Mih-Ouensa and decreases in the direction of El-Oued and Trifaoui (Bouselsal and Belksier 2018). There is overexploitation of groundwater for drinking in the El-Oued area and for irrigation in Trifaoui and El-Oued (fig. 3) which cause depression in the piezometric head in some locations.

General chemistry of the Complex Terminal aquifer

The summary of the analyzed physicochemical parameters of groundwater samples is reported in Table 1. The result showed decreasing in salinity with the groundwater flow direction. From the statistical analysis, the minimum and maximum values were calculated to assess the water quality according to the world health organization standards (WHO 2011). The minimum value of electrical conductivity is 2640 µS/cm exceeding the permissible limits of WHO (1000 µS/cm). TDS also exceeds the permissible limits (Fig. 4). The groundwater of the study area is classified as brackish water according to Freeze and Cherry (1979) and neutral to slightly alkaline with pH values ranging from 7 to 7.89. The temperature of 55% of the water samples in the Complex terminal exceeds the acceptable limits of WHO (18–25°C) with values between 13.9 and 38.8°C. The concentration of calcium in 88.8% of water samples is higher than WHO standards for drinking water (200mg/l) and ranges from 168.33 and 340.68 mg/L. The reason for the high concentration of Ca²⁺ in the water could be due to the dissolution of gypsum and limestone rock and gypsiferous formations of the lower Senonian in the lower part of the CT aquifer. The analyses of water in the Debila area showed the highest value for Ca²⁺. Only 6.6% of the water samples have a high concentration of Mg²⁺ exceeding the permissible limits of drinking with a maximum value of 157.9 mg/l in the eastern part of the El-Oued area while the rest are below 150 mg/l. The concentration of K⁺ in all locations is higher than the acceptable standard of drinking (12mg/l) with a minimum value of 24 mg/l. For Na⁺, the groundwater in Complex Terminal has a concentration higher than the WHO standard of drinking (200mg/l) with values varying between 210 mg/l and 540 mg/l which can cause an unpleasant taste and make the water brackish (Rodier, 1984). The water samples in the western part of the study area are more enriched in sodium. The main dominant anions in the groundwater of Souf valley is SO₄²⁺ and Cl⁻ with high concentration level and an average value of 698.03 mg/L, and 821.3 mg/l respectively. Their concentration in all water samples is higher than the permissible level of drinking water. The main factor responsible for the high concentration of sulfate and chloride in CT is the evaporite dissolution such as gypsum (CaSO₄.2H2O) and halite (NaCl). The high level of Cl⁻ in water causes an unpleasant taste and corrosion to the tanks and pipelines. The lower Senonian limestone and dolomite exist as a substrate for the Mio-Pliocene aquifer in the south part of the study area releasing HCO₃⁻ with a high concentration in the direction of groundwater flow. It is only 15.5% of the water samples are within the acceptable limits of drinking while the maximum values were recorded in the Robbah and Debila regions. There is a link between chemical pollution and the availability of nitrates in groundwater. There are many sources of nitrate in groundwater besides the nitrogen cycle such as industrial and agricultural drainage, chemical fertilizers, and livestock facilities (Antonakos and Nicolaos, 2000). Although the concentration of nitrates is within the acceptable limits of drinking water (50 mg/l), the normal concentration that exists in water naturally shouldn't exceed 10 mg/l. The average value of nitrates in the study area is 15.8 mg/l which gives an indication of chemical pollution of groundwater from anthropogenic activities (Adimalla, 2020).

Table 1

Physicochemical parameters of the groundwater samples
Sample	TDS (mg/l)	Total Hardness	EC uS/cm	Temp °C	pH	Ca²⁺ (mg/l)	Mg²⁺ (mg/l)	Na⁺ (mg/l)	K⁺ (mg/l)	HCO₃⁻ (mg/l)	Cl⁻ (mg/l)	SO₄²⁻ (mg/l)	NO₃⁻ (mg/l)
1	2547	1140	3980	13.9	7.42	280.56	106.94	381	37	195.2	744.51	730.24	19.72
2	2419	1250	3780	16.4	7.28	268.53	140.96	281	15	185.44	872.14	760.21	20.57
3	2522	1140	3940	16	7.69	200.4	155.55	460	42	152.5	985.59	680.14	24.09
4	2643	1170	4130	24.8	7.6	292.58	106.94	360	16	137.86	985.59	810.02	26.48
5	2336	1210	3650	28.5	7.66	288.57	119.09	325	32	123.28	1012.02	754.23	18.02
6	2060	1200	3220	28.9	7.84	280.56	121.52	322	32	183	701.96	568.32	20.12
7	2572	1240	4020	19.3	7.45	248.49	150.69	281	15	128.1	971.41	760.21	20.72
8	2592	1110	4050	19.1	7.32	340.68	63.19	340	36	124.44	815.41	602.39	25.4
9	2685	1200	4040	27.2	7.27	280.56	121.52	340	37	137.86	843.78	625.32	1.25
10	2598	1350	4060	26.7	7.31	280.56	157.98	380	40	143.96	631.06	828.45	17.24
11	2672	1000	4020	27	7.47	280.56	72.91	375	37	128.1	843.78	689.57	1.25
12	2666	1100	4010	26.5	7.51	260.5	109.37	380	37	122	701.96	711.34	2.14
13	1789	900	2640	24.5	7.06	272.54	53.47	350	37	134.2	560.15	698.03	1.05
14	1702	920	2660	24.9	7.02	168.33	122	430	38	121.53	560.15	721.21	1.68
15	1804	920	2820	38.8	7.17	252.50	70.48	210	22	152.5	560.15	532.2	0.83
16	2496	1100	3900	37	7.3	260.52	109.37	340	33	128.1	772.87	620.33	18.51
17	2752	1150	4300	34	7.58	312.62	89.92	370	38	134.2	730.33	815.21	25.85
18	2400	1220	3750	28	7.49	308.61	109.37	315	28	146.4	985.59	745.25	27.81
19	1789	890	2796	24.3	7.07	172.34	111.80	540	39	118.34	787.05	572.32	4.15
20	1964	900	3070	22.1	7.34	184.36	106.94	350	32	122	914.68	632.01	14.25
21	2508	1100	3920	22.7	7.58	220.44	133.67	380	37	113.46	1013.9	790.01	20.16
22	2233	1090	3490	35.9	7.14	208.41	138.53	350	35	112.24	999.77	720.45	2.92
23	2771	1260	4330	28.9	7.47	332.66	104.51	350	32	158.6	843.78	840.27	23.04
24	2692	1140	4050	22.9	7.8	296.59	97.22	360	38	109.8	1127.4	689.45	1.25
25	2419	1190	3780	24.4	7.87	260.52	131.24	360	35	118.34	985.59	625.37	29.49
26	2400	1150	3750	27.3	7.31	280.56	109.37	390	38	140.3	701.96	670.12	19.25
27	2547	1000	3980	24.2	7.71	252.50	89.92	300	38	122	815.41	725.03	24.02
28	2400	1100	3750	24.4	7.56	280.56	97.22	360	35	109	701.96	657.23	19.50
29	2246	900	3510	24.6	7.65	320.64	24.30	350	37	122	588.51	761	7.40
30	1932	950	3020	24.6	7.5	240.48	85.06	370	35	112.24	631.06	654.01	19.2
31	1753	830	2740	27.6	7	168.33	99.65	450	40	134.2	631.06	598.35	1.748
32	1728	880	2700	26.1	7.02	172.34	122	460	39	109.37	701.96	620.35	1.665
33	1708	950	2670	31.5	7.33	220.44	97.22	420	39	170.8	602.7	604.32	1.045
34	2790	1250	4360	21.3	7.55	276.55	136.1	350	32	143.96	914.68	598.65	28.31
35	1817	860	2840	29.8	7.21	224.44	72.91	360	38	163.48	701.96	601.25	1.045
36	2730	1250	4360	21.3	7.55	276.55	136.1	340	30	143.96	914.68	830.27	28.32
37	2131	1000	3330	33.1	7.51	240.48	97.22	440	39	128.1	843.78	670.14	13.45
38	2496	1150	3900	34.3	7.37	260.52	121.52	380	39	146.4	1127.4	730.54	29.93
39	2496	1150	3900	33.1	7.61	280.56	137.86	340	39	137.86	815.41	833.21	28.12
40	2643	1250	4130	33.1	7.48	240.48	157.98	370	37	146.4	957.23	799.21	31.53
41	2560	1130	4000	22.3	7.7	296.59	97.12	350	35	105.8	1124.4	684.44	1.2
42	2355	1130	3680	35.6	7.81	228.45	136.1	350	15	122	772.87	800.01	14.9
43	2317	980	3620	32.8	7.41	248.49	87.49	450	39	122	701.96	670.14	23.84
44	2374	1250	3710	23.8	7.87	280.56	133.67	271	12	128.1	843.78	750.21	22.8
45	2572	1350	4020	27	7.51	320.64	133.67	345	35	128.1	914.68	630.25	26.07
min	1702	830	2640	13.9	7	168.33	24.30	210	12	105.8	560.15	532.2	0.83
max	2790	1350	4360	38.8	7.87	340.68	157.98	540	42	195.2	1127.40	840.27	31.53
mean	2347.24	1097.78	3652.80	26.68	7.45	259.18	110.62	363.91	33.58	134.83	821.30	698.03	15.81
WHO (2011)	500–1000		500–1500	18.25	6.5–8.5	75–200	30–150	200	12	120	200–500	200–400	50

Hydrogeochemical Classification

Piper plot (Piper, 1944) was created to classify the hydrochemical facies in groundwater (Fig. 5). From the cationic triangle, 15.5% of the total water samples (south of El-Oued and west of Debila) fall within the Na⁺+K⁺ dominant type and the rest fall within the no-dominant type. 93.3% of the total samples belong to Cl⁻ the dominant class in the anionic triangle and three samples (Mih-Ouensan Robbah and west Debila) fall within the no-dominant type. The water samples are divided into three hydrochemical facies in the diamond shape of the piper diagram. 31 samples fall within the Ca²⁺-Cl⁻ facies zone (Type 1) with permanent hardness which can be because of reverse ion exchange. The salinity of such water is very high owing to elevated concentrations of calcium and chloride, especially in the Debila region. 6 Samples from El-Oued and Debila belong to Na⁺-Cl⁻ facies (type 2) due to the evaporation process as a main controlling factor governing the water chemistry. The rest are in mixed Ca²⁺–Mg²⁺–Cl⁻ class zone (type 3) distributed in Hassi Khalifa, El-Oued, and Debila.

The statistical analysis by using the relationships and ratios between the different major ions is used to show the main processes that govern the groundwater chemistry in the study area. The effect evaporation process in the study area can be described by using the relationship between EC and Na⁺/Cl⁻ ratio (Fisher and Mullican 1997). The ratio of Na⁺/Cl⁻ declines with increasing electrical conductivity owing to the depletion of Na ion due to reverse ion exchange (Fig. 6A). The origin of chloride ions from anthropogenic sources can be detected clearly by using isotope analysis. CAI-I, CAI-II (chloro-alkaline index), different ionic plots, and a Chadha diagram were applied to confirm the influence of reverse ion exchange as a significant factor in the water chemistry of Souf-valley. The linear relationship between Na⁺ and Cl⁻ showed that there is no balance between these two Ions where few samples fall on a 1:1 line graph owing to the common source such as halite dissolution (Fig. 6B). Most of the samples are located below the 1:1 line graph due to enrichment of chloride as an indication of an extra different source for chloride ion or removing Na⁺ from the groundwater. The elevated concentration of chloride can be because of anthropogenic activities such as seepage the excess irrigated water from agricultural land and waste disposal (Srinivasamoorthy et al., 2008; Jacks et al., 1999) or atmospheric deposition of chloride (Biswas et al., 2012). The silicate weathering can be a significant factor if the Na⁺/Cl⁻ ratio is greater than 1 (Mayback, 1987), but at the present, the ratio in all samples is less than 1 which means the absence of silicate weathering. The relationship between the Na⁺+K⁺ versus Ca²⁺+Mg²⁺ showed that the water samples were divided into three groups where most of the samples fall above the 1:1 line graph (Fig. 6C), three samples cross the line, and 5 samples below the line. The dominance of Ca²⁺ and Mg²⁺ over Na⁺ and K⁺ in most of the water samples reveal that Na⁺ ion is replaced by Ca²⁺ and Mg²⁺ ions through the base ion exchange process (Jankowski and Acworth, 1997). The summation of Ca²⁺ and Mg²⁺ ions versus the summation of HCO₃⁻ and SO₄²⁻ were plotted on a linear graph (Fig. 6D) and showed that all the groundwater samples fall above the 1:1 line referring to the reverse ion exchange process. Only one sample crosses the 1:1 line owing to gypsum/calcite/dolomite dissolution. The relative increase of Ca²⁺+Mg²⁺ ions compared to SO₄²⁻+HCO₃⁻ ions is due to reverse ion exchange (Rajmohan and Elango, 2004). The ratio between Ca²⁺+Mg²⁺ and HCO₃⁻ can be used to confirm the source of calcium and magnesium in the groundwater (Fig. 6E). If the ratio is close to 0.5, it means the Ca²⁺ and Mg²⁺ come only from the weathering carbonate and silicate minerals (Sami, 1992). The ion exchange or bicarbonates enrichment can be the main reason for the depletion of calcium and magnesium if the ratio is less than 0.5. All the water samples showed a very high ratio of Ca²⁺+Mg²⁺/HCO₃⁻ more than 0.5. The water is under a slightly alkaline condition which neglects the depletion of HCO₃⁻ (carbonic acid) as a reason for this high ratio so the only reason for falling all samples far above 1:1line (ratio = 0.5) is the process of reverse ion exchange (Spears, 1986). The meteoric nature and the fresh groundwater recharge can be determined also by the value of the Ca²⁺+Mg²⁺/HCO₃⁻ ratio. If the value of this ratio is less than 1, it means the water is meteoric and there is groundwater recharge (Nazzal et al., 2014). In Souf valley, all groundwater samples have a very high ratio ranging from 3.2 to 6.5 referring to the absence of the meteoric nature and groundwater recharge. The plotting between Na⁺/Cl⁻ and Cl⁻ (Fig. 6F) showed a reverse relationship indicating to replacement of sodium that originated from halite dissolution by calcium and magnesium in the clay minerals of the Complex terminal aquifer (Rajmohan and Elango, 2004). The water samples were plotted on the Chadha diagram to confirm the main dominant geochemical process governing the water chemistry in the present study (Chadha, 1999). About 88% of the water samples fall within the reverse ion exchange zone. 12% of the samples were plotted in the field of seawater owing to the evaporation process and distributed in Hassi-Khalifa, Debila, and Trifaoui (Fig. 7).

Applying Chloro-alkaline Indices (Cai)

The base reaction of ion exchange between the material of the CT aquifer and the groundwater can be interpreted by using chloro-alkaline indices (Schoeller, 1977). CAI-I and CAI-II were calculated by using these equations;

CAI-I = [Cl⁻ - (Na⁺ + K⁺)]/ Cl⁻

CAI-I = [Cl⁻ - (Na⁺ + K⁺)]/ (HCO₃⁻ + SO₄²⁻ + NO₃⁻)

If the value calculated from CAI-I and CAI-II is negative, it indicates the ion exchange process controls the water chemistry while the positive value indicates that the main controlling process is reverse ion exchange. It is noted that the average value is 0.24 and 0.37 for CAI-I and CAI-II respectively owing to the reverse ion exchange process as a main dominant factor (Fig. 8A-B). Such results reveal that Sodium and potassium in the groundwater were replaced by calcium and magnesium in the rocks or sediments of the CT aquifer. The negative value of both indices was recorded with only 7 water samples located in Hassi-Khalif, Mih-Ouensa, and the southern El-Oued area.

1/2Ca²⁺-X + Na⁺→1/2Ca²⁺ + Na⁺-X reverse ion exchange

Na⁺-X + 1/2Ca²⁺→Na⁺ + 1/2Ca²⁺-X ion exchange

The scatter plot of the Gibbs diagram is commonly used to explain the effect of different mechanisms controlling the water chemistry by dividing the diagram into three main zones (Fig. 9). The first zone is atmospheric precipitation dominance with very low TDS and a high ratio of Cl⁻/ (Cl⁻ + HCO₃⁻) and Na⁺/ (Na⁺ + Ca²⁺). The second zone is characterized by moderate TDS and the previous ratio of cations and anions representing rock weathering. The last mechanism is evaporation/crystallization in the upper part of the Gibbs plot with very high TDS (Gibbs, 1970). The scatter plot reveals that all water samples fall within evaporation/crystallization dominance. Durov diagram was used by different researchers as a visualization technique in hydrogeology where it connects the major ions, pH, and TDS (Durov, 1948). The three main processes that can be explained by the Durov diagram are ion exchange, mixing/dissolution, and reverse ion exchange (Fig. 10). 100% of the samples fall within the reverse ion exchange zone with TDS higher than 1500 mg/l confirming the previous statistical explanation.

Geochemical Modeling Of The Groundwater

The availability of various solutes in the groundwater which come from different sources such as rock weathering, soil erosion, and atmospheric deposition can affect its natural quality (Saleh et al., 1999). The dissolution of different mineral species results mainly from water-rock interaction. The groundwater can be saturated with some minerals and still dissolve more mineral species till it reaches the equilibrium state. When the groundwater is above the equilibrium conditions with mineral species, it is called to be oversaturated with this mineral and starts to precipitate (Deutsch, 1997). The saturation index (SI) is used for the prediction of the reactive minerals in the aquifer from the samples of water without the need for solid-phase samples and mineralogy analysis (Appelo and Postma, 1993). The SI was calculated by the following equation;

SI = log (IAP/Ksp)

Where IAP refers to the ion activity product and Ksp is the solubility product at a given temperature.

If the value of the saturation index equals zero, it means the water is saturated and under an equilibrium state with mineral species. The positive value of SI indicates that the groundwater is oversaturated with mineral species while the negative refers to it being undersaturated concerning this mineral. From the results of the saturation index in the CT aquifer, it is noted that all water samples are undersaturated with halite, anhydrite, and gypsum minerals (Table 2, Fig. 11). This result confirms the possibility of groundwater in the CT aquifer dissolving more from these minerals. Most of the water samples are oversaturated concerning calcite, dolomite, and aragonite indicating the possibility of groundwater precipitating these mineral species and confirming the same result from the Gibbs plot. The SI for only 7 samples, 8 samples, and 13 samples have a negative value for calcite, dolomite, and aragonite and it is located in Hassi-Khalifa, Debila, Baydah, Robah, and Mih-Ouensa regions. The climate of the study area is semi-arid which indicates that the evaporation and very low rainfall can cause precipitation of calcite, dolomite, and aragonite (Kumar and Singh, 2015). The soluble component of sodium, calcium, chloride, and sulfate are not limited by their mineral equilibrium (gypsum, anhydrite, and halite) (Gu¨ler and Thyne, 2004).

Table 2

Saturation Index of the groundwater
Sample	Anhydrite	Aragonite	Calcite	Dolomite	Gypsum	Halite
1	-0.83	0.25	0.39	0.7	-0.61	-5.22
2	-0.85	0.06	0.21	0.48	-0.63	-5.28
3	-1.02	0.26	0.4	1.03	-0.8	-5.02
4	-0.78	0.28	0.42	0.74	-0.56	-5.13
5	-0.82	0.29	0.43	0.82	-0.6	-5.16
6	-0.92	0.65	0.79	1.57	-0.7	-5.31
7	-0.88	0.04	0.18	0.48	-0.66	-5.24
8	-0.8	0.06	0.2	0.01	-0.59	-5.22
9	-0.89	-0.04	0.1	0.19	-0.67	-5.21
10	-0.81	-0.01	0.14	0.37	-0.59	-5.29
11	-0.83	0.12	0.27	0.29	-0.61	-5.17
12	-0.86	0.11	0.25	0.47	-0.64	-5.24
13	-0.81	-0.26	-0.12	-0.61	-0.59	-5.37
14	-1.02	-0.56	-0.42	-0.63	-0.8	-5.28
15	-0.92	-0.1	0.05	-0.12	-0.7	-5.58
16	-0.91	-0.07	0.08	0.12	-0.69	-5.25
17	-0.74	0.28	0.42	0.65	-0.52	-5.24
18	-0.79	0.23	0.37	0.63	-0.57	-5.18
19	-1.11	-0.5	-0.36	-0.56	-0.89	-5.04
20	-1.03	-0.2	-0.05	0	-0.81	-5.16
21	-0.91	0.05	0.2	0.52	-0.69	-5.09
22	-0.96	-0.4	-0.25	-0.34	-0.74	-5.13
23	-0.72	0.26	0.41	0.65	-0.5	-5.2
24	-0.84	0.39	0.53	0.93	-0.62	-5.07
25	-0.93	0.44	0.59	1.22	-0.71	-5.12
26	-0.86	0.01	0.15	0.23	-0.64	-5.23
27	-0.85	0.29	0.43	0.76	-0.63	-5.28
28	-0.85	0.15	0.29	0.47	-0.63	-5.26
29	-0.71	0.34	0.48	0.18	-0.49	-5.35
30	-0.9	0.04	0.19	0.26	-0.68	-5.29
31	-1.08	-0.52	-0.38	-0.64	-0.86	-5.21
32	-1.07	-0.59	-0.44	-0.69	-0.85	-5.16
33	-0.97	0.02	0.17	0.32	-0.75	-5.26
34	-0.93	0.25	0.39	0.82	-0.71	-5.17
35	-0.95	-0.1	0.04	-0.06	-0.73	-5.26
36	-0.81	0.22	0.36	0.76	-0.59	-5.18
37	-0.91	0.1	0.24	0.43	-0.7	-5.1
38	-0.88	0.03	0.17	0.36	-0.66	-5.05
39	-0.8	0.27	0.41	0.86	-0.58	-5.23
40	-0.89	0.1	0.24	0.65	-0.67	-5.13
41	-0.84	0.28	0.42	0.7	-0.62	-5.08
42	-0.88	0.33	0.47	1.06	-0.66	-5.24
43	-0.89	-0.01	0.14	0.17	-0.67	-5.17
44	-0.83	0.5	0.64	1.31	-0.61	-5.31
45	-0.86	0.21	0.36	0.68	-0.64	-5.17
Min	-1.11	-0.59	-0.44	-0.69	-0.89	-5.58
Max	-0.71	0.65	0.79	1.57	-0.49	-5.02
Average	-0.88	0.076	0.22	0.4	-0.66	-5.21

Suitability Of Groundwater Of Deep Aquifers For Irrigation

The deterioration of groundwater quality used for irrigation can adversely affect the growth of crops and plants through physical or chemical changes. A high concentration of TDS in groundwater can cause a change in the osmotic process and metabolic reactions (Alam, 2014). The concentration of sodium ions in groundwater is one of the most significant factors that control its suitability for irrigation purposes. If the groundwater contains a high concentration of Na+, it will have a negative impact on soil texture and permeability (Sujatha and Reddy, 2003). If the percentage of sodium in groundwater exceeds 50% of the total cations, it causes the replacement of Ca and Mg fixed in the soil by Na ions in groundwater. The permeability and fertility of the soil decrease due to this process of reverse ion exchange between Ca²⁺, Mg^2+, and Na ions (Karanth, 1987). The presence of some salts in groundwater with high concentrations can damage the soil properties including aeration, fertility, and permeability, and hence restricts the plant's growth (Umar et al., 2001; Singh, 2000). USSL diagrams and specific parameters such as sodium adsorption ratio (SAR), Sodium percent (Na%), permeability index (PI), magnesium hazard (MAR), and residual sodium carbonate (RSC) were used to evaluate the quality of water samples for irrigation purposes.

Sodium Adsorption Ratio (Sar)

SAR parameter is used in irrigation water referring to the ability of the soil matrix in the aquifer to release Ca²⁺ and Mg²⁺ and absorb Na⁺ ions from groundwater at the sites of ion exchange and causing soil particles dispersion and reduction in the capacity of infiltration (Wang et al., 2012; Hanson et al., 1999). The sodium adsorption ratio was calculated by using the following equation;

SAR = Na⁺/√(Ca²⁺+Mg²⁺)/2

Where all parameters' units are in meq/l

Although high salinity of water can be useful for the soil structure by increasing the rate of infiltration, it gives more water stress conditions for the plants. The plants and crops exert a lot of energy for water extraction from the soil if the salinity of irrigation water is high (a water stress condition). To study the effect of irrigated water quality on the plants and crops production, the water samples were plotted on the USSL diagram (Richards, 1954). This diagram shows the relationship between SAR and EC and divided them into different classes (Fig. 12). 44 water samples of CT aquifer fall within the C4-S2 class (very high salinity-medium SAR) and one sample is located in the C4-S1 class (very high salinity-low SAR). The maximum value of SAR for all water samples does not exceed 10 (the max value is 7.8).

The results indicate that the plants will be adversely affected by the high salinity of irrigation water but there is no effect on the infiltration capacity of the soil due to low to medium SAR value (Fig. 13A) and no need for calcium conditions. The best management for using the groundwater in the study area for irrigation is selecting plants and crops that are resistant to the high salinity of the water.

Residual Sodium Carbonate (Rsc)

RSC was calculated to determine the potential precipitation of calcium and magnesium on the surface particles of the soil and the elimination of such cations from the soil solution. It is defined by the following formula;

RSC = (CO3²⁻ + HCO₃⁻ ) - (Ca²⁺ + Mg²⁺)

Where the units of used parameters in meq/l. It is reported that RSC in irrigation groundwater is high in arid to semi-arid regions which causes soil salinization and sodification (Prasad et al., 2001). The groundwater is classified into three classes according to RSC value (Fig. 13B). The irrigation water with an RSC greater than 2.5 is not suitable for irrigation while the water is good for irrigation purposes with RSC less than 1.25 and doubtful between 1.25 and 2.5. In the present study, all water samples recorded an RSC value of less than 1.25 referring to the good quality of groundwater for irrigation purposes. As mentioned before the groundwater of Souf-valley contain a high concentration of Ca²⁺ and Mg²⁺ ions and a low concentration of HCO₃⁻ ions but still can be used for irrigation.

Magnesium Hazard (Mar)

The magnesium adsorption ratio represents the ratio between magnesium and calcium in the water and it was calculated by using the following equation;

(MAR) = [Mg²⁺ / (Mg²⁺ +Ca²⁺)] *100

Where the concentrations of Ca²⁺ and Mg²⁺ ions in meq/l

The groundwater used for irrigation purposes can be divided into two main classes according to MAR value. The water is classified as suitable with a MAR value of less than 50% and unsuitable with a value higher than 50% (Paliwal, 1972). If the concentration of Mg ions in the irrigation water is 50% greater than calcium ions, it can affect the soil infiltration capacity owing to the adsorption of clay minerals to Mg²⁺ ions in water (Hanson et al., 1999). In the study area, 38 samples showed the suitability of groundwater for irrigation with a MAR value less than 50, and 7 samples are unsuitable for irrigation with a MAR value greater than 50 (Fig. 13C). These unsuitable samples are located in Hassi-Khalifa, Debila, Trifaoui, and Baydah.

Sodium Percentage (Na+%) And Permeability Index (Pi)

The irrigation water is divided to 5 classes according to sodium percent (Wilcox, 1948) which are excellent (< 20%), good (20–40%), permissible (40–60%), doubtful (60–80%) and unsuitable (> 80%). It was calculated by the following equation;

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

Where the concentrations of all constituents in meq/l. The groundwater in the study area showed that the value of Na% ranges from 32.6 to 57.9% indicating good to permissible quality for irrigation (Fig. 13D). The permeability index parameter was detected as follow;

(PI) = (Na⁺ + √HCO₃⁻) / (Na⁺+ Ca²⁺+ Mg²⁺) *100

And the concentrations of ions in meq/l. The value of PI (Doneen, 1964), was determined to evaluate the suitability of groundwater of CT aquifer for irrigation purposes according to the following standard; Excellent (PI > 75), good (PI = 25–75), and unsuitable (PI < 25). It was noted that the value of PI for all water samples falls within a good quality category with a value range from 35.9 to 60.2 (Fig. 13E).

Applying Water Quality Index (Wqi) For Drinking Purposes

The physicochemical parameters can be compared with the world health organization standards to evaluate the water quality for drinking purposes (WHO, 2011; Ayers and Westcot, 1994). The WQI is considered one of the best effective tools to assess water quality for drinking purposes by summarizing well-presented water quality data (Tiri et al., 2018). The weighted arithmetic method was developed to calculate the water quality index by using physical and chemical parameters to show the overall water quality according to the purity degree and different uses (Brown et al. 1972). This method was used by many authors (Amadi, 2011; Desai and Desai, 2012; Gebrehiwot et al., 2011; Aly et al., 2014; Goher et al., 2015; Amaliya and Kumar, 2015; Paul et al., 2015).

The physical and chemical parameters such as pH, EC, K⁺, Na⁺, Mg²⁺, Ca²⁺, SO₄²⁻, Cl⁻, and HCO₃⁻ were used to attain the WQI. The classification of WQI regarding WHO 2011 standards for drinking is excellent (WQI = 0–5), good (26–50), poor (51–75), very poor (76–100), and unsuitable (> 100) for drinking (Fig. 13F).

The calculation of the water quality index was done by using the following mathematical equation;

$$WQI={\sum }_{i=1}^{n}\text{Q}\text{i} \text{W}\text{i}/ {\sum }_{i=1}^{n} \text{W}\text{i}$$

where Qi represents the quality rating of ith parameter, W is the unit weight of every parameter, and n refers to the number of the parameters. The quality rating (Qi) was obtained by the following formula;

Qi = (V_i -V₀)/ (S_i-V₀)

Where V0 is the ideal value of the ith parameter in the pure water, V_i refers to the observed value of the ith parameter, all the parameters have V₀ = 0 except for the pH (V₀ = 7.0), Si means the standard permissible value of the ith parameter.

The unit weight (Wi) equals the proportionality constant of the weights (K) divided by the standard permissible value (Si) of the quality parameters as follows;

Wi = K/ S_i

Where the constant K can be obtained from this formula

$$K=\frac{1}{ {\sum }_{i=1}^{n} \frac{1}{Si}}$$

In the present study, the water samples showed the value of WQI range between 99.42 and 188.9 which falls within very poor (one sample) and unsuitable (44 samples) quality class for drinking purposes (Fig. 14).

Effect of the water salinity and hardness of the water on human health and crop production

The abstraction of the groundwater from the Debila and El-Oued regions is used for drinking and irrigation. It is classified as brackish water where the average concentration of salinity is 2347 mg/l. The drinking of brackish water has a serious impact on human health. It can cause problems such as dehydration of the body due to overproducing urine from the kidneys to eliminate the excess salts. Cardiovascular diseases, abdominal pain, high blood pressure, and diarrhea were found to be linked to drinking brackish and salty water (Vineis et al., 2011). The groundwater in the study area must be treated before drinking through different desalination techniques like distillation and reverse osmosis pressure to avoid such kinds of diseases. The average concentration of the total hardness is 1097 indicates very hard water which increases the risk of heart and cardiovascular disease. Decontamination of hardness from groundwater can be done by using natural materials such as Muscovite-based sodalite (Salam et al., 2021). Using brackish water for irrigation will have an adverse effect on the soil and crop production by changing the environment of the soil. It will result in salt accumulation, permeability changes water retention, and restrict water uptake by the roots of the plants (Chen et al., 2017; He et al., 2017) The best management for using the groundwater in the study area for irrigation is selecting plants and crops that are resistant to the high salinity of the water

The water samples from the complex terminal aquifer are not suitable for drinking where the value of the WQI higher than 100. The groundwater of CT in Souf valley is suitable for irrigation according to the results of SAR, Na%, MAR, PI, and RSC. All the water samples showed very high salinity exceeding the permissible limits for drinking and irrigation which can cause soil salinity and a decrease in crop production in the future. The hot and dry climate and anthropogenic activities have a strong effect on groundwater quality and increase water salinity. Piper diagram and Chadha diagram showed that the main hydrochemical facies of the groundwater are Ca²⁺-Mg²⁺-Cl⁻/SO₄²⁻ type and Na⁺-Cl⁻ type. The statistical analysis such as binary plots, Gibbs plots, and Durov diagrams revealed that the main hydrochemical processes that control the water chemistry in the CT aquifer are evaporation/crystallization, gypsum dissolution, and reverse ion exchange. The groundwater flows from the southwest to the northeast with a rapid decrease of the piezometric level in the El-Oued, Baydah, and Trifaoue regions due to overexploitation for irrigation purposes. There is no need for using fertilizers containing calcium where the SAR has a low to medium value and the soil will not be affected by sodification or infiltration capacity. All the water samples are undersaturated concerning halite, anhydrite, and gypsum while most of the samples are saturated to oversaturated by calcite, dolomite, and aragonite. The saturation index of the samples refers to the groundwater will continue to dissolve more halite, gypsum, anhydrite, and precipitate calcite and dolomite. Using brackish water from the complex terminal aquifer will have an adverse effect on human health and the soil environment. Desalination by using distillation and reverse osmosis pressure techniques and decontamination of hardness is required for drinking purposes to avoid high blood pressure, and cardiovascular and heart diseases. The best management for using the groundwater in the study area for irrigation is selecting plants and crops that are resistant to the high salinity of the water.

Complex terminal aquifer

WHO

World health organization

Electric conductivity

TDS

Total dissolved salts

Temperature

Permeability index

RSC

Residual sodium carbonates

SAR

Sodium adsorption ratio

Na%

Sodium percent

MAR

Magnesium adsorption ratio

WQI

Water quality index

IAP

Ion activity product

K_sp

Solubility product

CAI-I

Chloro alkaline index 1

CAI-II

Chloro alkaline index 2

USSL

United States Salinity Laboratory diagram

Saturation index

The quality rating of ith parameter

Unit weight of every parameter, and

Number of the parameters

V₀

Ideal value of the ith parameter in the pure water

V_i

Observed value of the ith parameter

Standard permissible value of the ith parameter.

Acknowledgments: The authors are appreciating the support of ADE (Algerienne Des Eaux) company to collect some of the quantitative data. I would like to thank Dr. Bouaicha Foued from Algeria for providing me with some information about the study area.

Funding: This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

Recommendations

Further studies will be conducted to investigate and apply some natural materials for desalination of the groundwater in the study area for drinking purposes.

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Hydrogeochemical Evaluation of Groundwater and its Suitability for Drinking and Irrigation Using Water Quality Index, Statistical and Geochemical Modelling, Debila and El-Oued regions, Algeria

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Abstract

Figures

Introduction

Materials And Methods

Result And Discussion

General chemistry of the Complex Terminal aquifer

Hydrogeochemical Classification

Applying Chloro-alkaline Indices (Cai)

Geochemical Modeling Of The Groundwater

Suitability Of Groundwater Of Deep Aquifers For Irrigation

Sodium Adsorption Ratio (Sar)

Residual Sodium Carbonate (Rsc)

Magnesium Hazard (Mar)

Sodium Percentage (Na+%) And Permeability Index (Pi)

Applying Water Quality Index (Wqi) For Drinking Purposes

Conclusion

Abbreviations

Declarations

References

Additional Declarations

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