EWASH & TI Journal, 2020 Volume 4 Issue 3, Page 431-441 Environmental and Water Sciences, Public Health & Territorial Intelligence Env.Wat. Sci. pub. H. Ter. Int. J. ISSN Electronic Edition : 2509 - 1069 Acces on line : http://revues.imist.ma/?journal=ewash-ti/

Section Environmental and Water Sciences Publication type Full Paper

Physicochemical and bacteriological quality assessment of spring waters in the Tetouan region () Évaluation de la qualité physicochimique et bactériologique des eaux de sources dans la région de Tétouan (Maroc)

Received 16 June 2020 NOUHA ACHAHBAR1, NADIA AMAJOUD2, OUISSAL OULED ZIAN2, ABDELLAH Accepted 25 Jul. 2020 EL MAFTAHI2, MOUAD BEN ZAKOUR2 & EL KHALIL BEN DRISS1 On line 30 Sep. 2020 (1) Laboratory Applied Biology and Pathology / Department of Biology Faculty of Sciences Tetouan / Abdelmalek Essaadi University PO Box : 93020, Tetouan, Morocco Email : [email protected], [email protected] (2) Communal Environment Laboratory and Pollution Control Faculty of Sciences Tetouan / Abdelmalek Essaadi University PO Box : 93020, Tetouan, Morocco Email : [email protected]

KEY WORDS Abstract The analysis of 16 physicochemical and bacteriological parameters of Bacteriological spring water in Tetouan city (Morocco) and its surroundings was conducted in parameters, order to establish its quality especially because they are used a lot by the physicochemical population. Samples were collected from 29 stations during the years 2014, 2015 parameters, rural area, and 2016. Three-way ANOVA (station, season, and year) was performed to urban area, spring water analyse the variance according to station, season and year. The results of analysis quality, Tetouan. showed spatial and seasonal variance. "Bonferroni" fit for a correlation network based on Pearson correlations showed strong correlations between calcium, TH, Sulphates, chlorides, TDS, Salinity, CT, CF, SF, and temperature. The PCA and its factorial map of the stations showed two different groups according to their physicochemical and bacteriological quality; the first group was formed by stations located in urban areas of Tetouan city with high level in TH, magnesium, calcium and sulphates; the second group was formed by stations located in rural areas with high level of nitrates and nitrites.

MOTS CLES Résumé L'analyse de 16 paramètres physicochimiques et bactériologiques des Paramètres eaux des sources de la ville de Tétouan (Maroc) et ses environs a été réalisée afin bactériologiques, d'établir leur qualité parce qu’elles sont très utilisées par la population. Des paramètres physico- échantillons ont été prélevés dans 29 stations au cours des années 2014, 2015 et chimiques, zone rurale, 2016. Une ANOVA à trois voies (station, saison et année) a été réalisée pour zone urbaine, qualité de analyser la variance selon la station, la saison et l'année. Les résultats de l'analyse l'eau de source, Tétouan. ont montré une variance spatiale et saisonnière. "Bonferroni" digne d'un réseau de corrélation basé sur les corrélations de Pearson a montré de fortes corrélations entre le calcium, le TH, les sulfates, les chlorures, le TDS, la salinité, les CT, les CF, les SF et la température. L'ACP et la carte factorielle des stations ont montré deux groupes différents selon leur qualité physicochimique et bactériologique; le premier groupe était formé de stations situées dans les zones urbaines de la ville de Tétouan avec un niveau élevé de TH, de magnésium, de calcium et de sulfates; le deuxième groupe était constitué de stations situées dans des zones rurales à forte teneur en nitrates et nitrites.

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1. Introduction 2. Material and methods Availability of safe drinking water is treaned by 2.1. Study zone urbanization, increased population and climate change across the world [1]. The deterioration of the quality of The study zone with an area of 2541 km2 (Cf. Fig. 1), water resources is therefore becoming a concern on a includes Tetouan city and the surrounding rural areas. global scale. Several studies have been made on water Tetouan city is located in North of Morocco about 10 km quality, especially in the African and Asian continents, from the Mediterranean Sea, in a valley dug by Martil where a large part of the population does not have access river between the Dersa and Ghorghiz mountains of the to drinking water or have access to poor quality water [2] limestone chain of the Western Rif [14], it is made up of [3] [4] [5] [6]. the Paleozoic or axial layer of the Rif chain with a Morocco is ranked among the water stress country [7]. predominance of flyschs. The city of Tetouan is part of the Several studies have been carried out in Morocco Rif chain in its outer part which includes allochthonous units (flysch sheets), pelitico-sandstone superstructure on concerning the physicochemical and bacteriological an autochthonous to para-autochthonous unit with pelitic quality of water in order to prevent and limit diffuse pollution in groundwater and even surface water. This dominance. The types of soil distinguished in the study area are composed of limestone, marl or flyschy pollution increases the risk of deterioration of the quality formations [14]. of these resources water-borne and creates a healthy risk for the population, who usually use these waters [8] [9] The city knows the existence of two seasons, a humid [10]. Similar studies were conducted in -Tetouan season from October to April and another dry from May region to assess the degree of water pollution, to acquire to September, which makes it possible to classify the basic knowledge, to develop monitoring, to detect study zone among the climatic regions of mediterranean disturbances and to set up a follow-up to feedback on type [14]. Reputed to have the highest average rainfall in water management [11] [12] [13]. the Kingdom, the Tangier-Tetouan region experiences rainfall that is generally spread over a long period of the Water resources in Tetouan region are part of those of year with peaks in December, January and February the Loukkos-Tangier-Mediterranean coastal basin [14]. Spring waters of the calcareous dorsal surrounding the reaching up to 2,000 mm / year and on land higher up, precipitation is abundant and can exceed 1000 mm / year city of Tetouan still widely used and continue to play a key [14]. The Oued Martil watershed is located in the western role as water supply particularly for rural population. Urbanization and population of Tetouan region are part of the Rif mountain range, it has a fairly dense permanently growing [14]. The degradation of natural hydrographic network and of capital importance not only for the watershed that it drains but for the entire water resources under the effect of urbanization and northern region, where it is one of the largest anthropic activities can make its use dangerous. Physicochemical and microbiological pollution may affect hydrosystems in northern Morocco. the quality of these waters by the presence of chemical or The Oued Martil takes its source in marnocalcary microorganism at a concentration that may render them formations at 1000 m of altitude; it is subdivided into an unfit for consumption or use. As natural water intended upper section with a steep slope which crosses the for direct consumption even without prior treatment, limestone ridge and another with a low slope which runs spring water must therefore comply with the drinking along the city of Tetouan [15]. The Oued Martil crosses water criteria based on the current drinking water the city of Tetouan and thus finds itself bordered by standards. multiple agricultural and domestic activities (Cf. Fig. 1). As mentioned above, there is a relatively abundance of The urban commune of Tetouan has experienced development and significant urban activity in recent literature on the effect of pollution on water resources in years, and many major infrastructure projects are Tangier-Tetouan region. This study attempt to analyse the physicochemical and bacteriological quality of spring underway. water in the region of Tetouan. The analysis concern 29 The urban area of Tetouan has 397,973 inhabitants, stations that were chosen to cover the urban and rural compared to 152,401 in rural areas [14]. areas of Tetouan city in order to know and to explain the The 29 sampling points were chosen to cover the entire evolution of the pollution indicators of water in the space city of Tetouan (Cf. Fig. 1) and Table 1). and over time.

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Fig. 1: Distribution of the 29 spring water sampled in the urban and rural areas of Tetouan city with the different pollution sources Source : Google maps Maroc 2020 Tab. 1 : Location and Lambert coordinates of the urban and rural spring water of Tetouan Station ID Station Latitude Longitude Station type Altitude (m) Torreta 1 35°32’50.9’’ N 05°22’16.7’’ W Rural 124 Bouanane 2 35°32’50.1’’ N 05°22’46.9’’ W Rural 212 Mjaz lhjar 3 35°33’22.7’’ N 05° 22’18.9’’ W Rural 3 Boussemlal haut 4 35°32’52.2’’ N 05°23’15.2’’ W Rural 180 Boussemlal bas 5 35°32’54.5’’ N 05°23’15.3’’ W Rural 156 Bouiller 6 35°32’56.9’’ N 05°23’18.4’’ W Rural 174 Ain hamma 7 35°33’04.9’’ N 05°23’37.4’’ W Rural 104 Ain dekken 8 35°32’ 48.3’’ N 05°23’56.8’’ W Rural 148 Ain soufla 9 35°32’54.5’’ N 05°23’55.7’’ W Rural 121 Ain chekkouh 10 35°34’16.9’’ N 05°24’50.5’’ W Urban 66 Sidi bahrouri 11 35°35’11.5’’ N 05°23’53.4’’ W Rural 167 Sidi talha 12 35°34’33.5’’ N 05°22’54.0’’ W Urban 104 Bab mkabar 13 35°34’30.5’’N 05°22’01.3’’W Urban 72 Aouina 14 35°34’06.4’’ N 05°21’51.5’’ W Urban 46 Sidi abdellah fakhar 15 35°33’57.4’’ N 05°21’41.4’’ W Urban 22 A côté de l’école 16 35°33’41.9’’ N 05°21’38.3’’ W Urban 19 abdesslam ben mchich Sedraouia 17 35°34’58.3’’ N 05°21’14.8’’ W Urban 35 Ain melloul 18 35°35’00.5’’ N 05°20’15.8’’ W Urban 10 Rass lma (samsa) 19 35°35’46.1’’ N 05°24’21.2’’ W Rural 242 Ain lhssa (samsa) 20 35°35’47.7’’ N 05°24’23.6’’ w Rural 234 Mhajeb (samsa) 21 35°35’44.8’’ N 05°24’25.4’’ W Rural 211 Ben frij (samsa) 22 35°35’32.0’’ N 05°24’13.3’’ W Rural 184 Hawma foukia (samsa) 23 35°35’42.9’’ N 05°24’26.7’’ W Rural 210 Derdale (samsa) 24 35°35’40.0’’ N 05°24’24.8’’ W Rural 198

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Station ID Station Latitude Longitude Station type Altitude (m) Choumissa (samsa) 25 35°35’37.4’’ N 05°24’23.5’’ W Rural 178 Jamboudar (samsa) 26 35°35’34.5’’ N 05°24’21.5’’ W Rural 179 Mkasba (samsa) 27 35°35’41.1’’ N 05°24’31.7’’ W Rural 180 Afrane (samsa) 28 35°35’37.3’’ N 05°24’26.9’’ W Rural 172 Oued sikha (samsa) 29 35°35’29.4’’ N 05°24’22.2’’ W Rural 148 Source : Data taken from GPS during the sampling 2.2. Sampling Since spring water is generally used as drinking water for rural populations and for irrigation, we have shown in The sampling covered a period of 3 years (2014, 2015 and (Cf. Table 2) the quality of these waters during the study 2016) once per dry season and once per cold season for period. each station. Samples for bacteriology were placed in sterilized glass vials and stored at a temperature of about Tab. 2: The quality of spring water in Tetouan city during 4 °C during transport to the laboratory in a cooler. For the study period physico-chemistry, the samples were put in rinsed polyethylene bottles before use with water from the Station Quality sampling point. Torreta Good Bouanane Good 2.3. Methods of analysis Mjaz lahjar Very bad Boussemlal haut Good The analyses were performed on the same sampling day. Boussemlal bas Good The membrane filtration technique using a filtration Bouiller Good ramp was used for bacteriological analysis as discripted by

Ain hamma Good Hmid (1997) [16], it was originally followed at the National Ain dekken Good Center for Scientific Research in France, is used to Ain soufla Bad enumerate the 3 bacteria in our sampled water (total Ain chekouh Average coliforms (CT), faecal coliforms (CF) and faecal Sidi bahrouri Good streptococci (SF)). Sidi talha Average The physicochemical analyses of the 13 parameters Bab mkabar Bad studied were performed as follow: Aouina Bad Sidi abdellah fakhar Bad Temperature (T°) by a mercury thermometer, potential A coté d'école Bad hydrogen (pH) by pH meter in situ and by Orion Research abdesslam ben model 420A thermometers (G.Boyer) in the laboratory, mchich turbidity (Tur) by turbidimeter (Digital Direct-Reading Sedraouia Bad TURBIDIMETER. G. Boyer), conductivity (Cond), salinity Ain melloul Bad (Sal) and total dissolved solids (TDS) by specific electrode Rass lma Bad (Orion Research model 150), calcium (Ca), hydrotimetric Hssa Good title (TH) and magnesium (Mg) by complexometry method

Mhajeb Average (determination with E.D.T.A) [17], chlorides (Cl) by Mhor's

Ben frij Good method [17], nitrates (NO3-) by sodium salicylate method Hawma foukia Average [17] with UV-visible spectrophotometry, nitrites (NO2-) by

Derdale Average diazotization reagent method [17] with UV-visible 2- Choumissa Good spectrophotometry, sulphates (SO4 ) by reagent method

Jamboudar Good with hydrochloric acid [17] and UV-visible Mkasba Average spectrophotometry. Afrane Bad 2.4. Data analysis Oued sikha Average Descriptive statistics (average, standard deviation, Source: Data from the municipal Environment and pollution control minimum and maximum values) were performed for laboratory in Tetouan physicochemical and bacteriological parameters. This change in quality from one station to another is due to contamination by local agents (domestic waste, To quantify the magnitude of the variation on three agriculture, etc.), which implies that the spring waters of scales, ANOVA three-way analysis of variance was used Tetouan are not polluted in general but rather in points for the total results to explore the differences between specific because of mainly anthropogenic factors and physico-chemical and bacteriological parameters of water which can be recovered by appropriate practices. between stations, seasons and years.

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Pearson's pairwise correlation was used to test the linear For conductivity, only station 3 (Mjaz lahjar) exceeds the correlation between the different physicochemical and Moroccan standard of 2800 μS / cm with a value of bacteriological parameters of water. We used network 5824 μS / cm in winter. correlation analysis coupled with Bonferroni fit to For turbidity, only station 19 (Rass lma samsa) exceeds visualize relevant relationship between physicochemical the Moroccan standard of 5 NTU with a value of 6,6 NTU and bacteriological water proprieties, using the "qgraph" in winter. software. For nitrites, the two stations that exceed the Moroccan The principal component analysis (PCA) showed us the standard of 0,5 mg/l are 21 (Mhajeb samsa) and correlation between the different parameters. Statistical 24 (Derdale samsa) with values of 2 mg / l and 0,88 mg/l analysis was performed using software in R language. successively in summer. 3. Results and Discussion For other physicocheminal parameters; calcium, TH, 3.1. Descriptive analysis magnesium and nitrates; and bacteriological indicators: CT, CF and SF; several stations exceed the limit values Temperature, pH, salinity, TDS, chlorides and sulphates (Cf. Fig. 2 (a, b, c, d, e, f and g)) and do not comply with analysis results meet Moroccan standards [18] and do not Moroccan standards [17]. For bacteriological indicators, exceed the limit values for all study stations. Moroccan standards are 0 CFU / 100 ml.

Fig. 2 : Variation of station parameters according to seasons (a) Calcium average, (b) TH average, (c) Magnesium average (d) Nitrates average, (e) total coliforms average, (f) feacal coliforms average and (g) faecal streptococci average (MS : Moroccan Standard, ID Station : Tab. 1) Source : By analyzing sample data using the spss program N. ACHAHBAR & al 435

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According to the results of the descriptive analysis, we Tab. 4: Variation of (a) physicochemical and (b) notice a variability between the different stations and bacteriological parameters between winter and summer even from one season to another, that is why one must of 29 sampled stations in the urban and rural areas of make detailed statistical analysis in order to well study Tetouan city this variability. Parameters Season Average± SD Min Max (a) pH Winter 7,45 ± 0,29 6,43 8,14 3.2. Statistical analysis Summer 7,48±0,26 6,97 8,12 3.2.1. Detailed results Tur (NTU) Winter 1,38±1,58 0,1 9,1 Summer 0,85±0,77 0,1 3,2 3.2.1.1. Descriptive statistics Cond Winter 1004,45±981,96 235 5962 (µS/cm) Summer 850,41±334,65 384 1776 The detailed results of the physicochemical and Sal (‰) Winter 0,45±0,16 0,2 0,8 bacteriological analyses of all Tetouan city stations are Summer 0,45±0,17 0,2 0,9 shown in (Cf. Table 3). This table gives the average values TDS (mg/l) Winter 466,40±163,73 233 886 for each parameter as well as the standard deviations of Summer 471,12±180,07 230 910 the parameters studied and the Minimal and Maximal Ca (mg/l) Winter 129,37±43,50 62,88 232,26 values during the 3 years of study. Summer 133,63±50,19 66,61 260,27 TH (mg/l) Winter 38,92±13,17 21,86 73,44

Summer 39,01±13,48 22,97 75,98 Tab. 3 : Physicochemical and bacteriological parameters Mg (mg/l) Winter 64,58±38,73 5,06 180,1 of the 29 sampled stations in the urban and rural areas Summer 55,34±34,13 9,72 193,04 of Tetouan city. The results of the descriptive statistics Cl (mg/l) Winter 54,25±28,53 17,7 135,22 between the stations Summer 58,83±38,38 7,5 177 3- NO (mg/l) Winter 27,46±25,97 5 134,25 Parameters Descriptive statistics Summer 27,05±20,57 6,51 131,49 Min Max Average ± SD 2- NO (mg/l) Winter 0,05±0,05 0 0,25 (a) Temperature (°C) 14,00 23,00 18,99±1,90 Summer 0,14±0,44 0 2,4 Potential hydrogen 7,04 7,88 7,47±0,20 2- SO4 (mg/l) Winter 75,64±90,35 2,09 298,66 Turbidity (NTU) 0,20 3,88 1,11±0,90 Summer 77,92±96,61 2,36 313,58 Conductivity 499,67 3414,00 927,43±568,38 (b) CT Winter 151,58±282,33 0 1200 (µS/cm) (UFC/100 Summer 105,28±236,14 0 1520 Salinity (‰) 0,25 0,80 0,45±0,15 ml) Total dissolved 256,00 806,17 468,76±165,89 solids (mg/l) CF (UFC / Winter 55,66±163,23 0 1000 Calcium (mg/l) 79,70 236,07 131,50±43,55 100 ml) Summer 89,75±203,72 0 1000 Hydrotimetric title 25,45 73,61 38,96±12,51 SF (UFC / Winter 54,09±161,66 0 1000 (°F) 100 ml) Summer 20,04±1,60 15 23 Magnesium (mg/l) 19,54 143,00 59,96±32,06 Source : By analyzing sample data using the spss program Chlorides 18,03 135,61 56,54±28,55 Min : Minimum value ; Max : Maximum value ; Average ± SD: (mg / l) Average and Standard Deviation. Nitrates (mg/l) 8,42 63,42 27,26±15,93 Nitrites (mg / l) 0,01 1,02 0,09±0,20 The (Cf. Tables 3 and 4) show a variation between the Sulphates (mg/l) 8,53 293,76 76,78±93,31 parameters from one station to another and from one (b) Total coliforms 9,50 1300,00 240,39±328,30 season to another, to find out which parameters vary with (UFC / 100 ml) the space (stations) and which ones vary with time Faecal Coliforms 0,50 753,33 80,47±172,07 (season and same year), an ANOVA three-way study is (UFC/100 ml) done to clarify the results. Fecal Streptococci 0,33 672,00 71,92±150,18 (UFC/100 ml) 3.2.1.2. Nested three-way ANOVA Source : By analyzing sample data using the spss program Three-way ANOVA (station, season and year) was Min : Minimum value ; Max : Maximum value ; Average ± SD: performed to analyze the variance among parameters Average and Standard Deviation. from one station to another, from season to season or from year to year. The characteristics studied are ranked The (Cf. Table 4) shows the averages per season for the from top to bottom according to the percentage of different parameters and shows a difference between the variance (Cf. Fig. 3). Minimal and Maximal values for each parameter.

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The turbidity of a water varies according to the seasons; it increases in winter when the waters are turbid with high precipitation. The significance of the variance from one year to another is not very serious except in small percentage for salinity (1,21), CF (6,44) and SF (16,45) which explains that the state of the place of our study area does not change during the three years of study. For the various and multiple error, there is not a remarkable variance, only (3,89) for SF and (4,03) for CF. Tab. 5 : Variance distribution of (a) physico-chemical parameters and (b) bacteriological parameters on three Fig. 3 : Variance distribution of (a) physicochemical scales: sites, years and seasons parameters and (b) bacteriological parameters on three Parameters Sites Year Season Divers 2- scales: stations, years and seasons (a) SO4 96,78 0,00 3,22 0,00 Source : Statistical analyzes of sampling data using the spss program TDS 90,06 0,00 9,93 0,01 Mg 88,56 0,00 11,44 0,01 From Table 5, the high variance is given to the differences Sal 86,14 1,21 10,93 1,72 between the study stations whose concentration rate of TH 83,28 0,00 16,71 0,01 the different parameters is dissimilar from one station to Ca 80,63 0,00 19,36 0,01 another. The majority of the parameters vary from one T° 70,24 0,00 29,74 0,02 Cl 63,48 0,00 36,51 0,01 station to another with a significance of : sulphates Cond 50,37 0,00 49,61 0,02 (96,78), TDS (90,06), Magnesium (88,56), Salinity (86,14), pH 47,52 0,00 52,46 0,02 TH (83,28), calcium (80,63), temperature (70,24) and Tur 39,48 0,00 60,50 0,02 chlorides (63,48) ; similarly for bacteriological NO3- 34,89 0,00 65,08 0,03 parameters : CT (75,65), SF (63,97) and CF (63,93). Their NO2- 26,66 0,00 73,32 0,02 contents and concentrations therefore depend on their (b) CT 75,65 0,00 24,34 0,01 locations, the factors and characteristics related to each SF 63,97 16,45 15,69 3,89 point separately (natural elements, pollution in this CF 63,93 6,44 25,61 4,03 region, etc.). The value of the temperature is influenced Source : By analyzing sample data using the spss program by the ambient temperature but also by possible After we know that the physicochemical and discharges of waste water, waste, the depth of the bacteriological parameters vary from one station to sources, etc., for this reason it varies according to the another and from one season to another, we must know stations not according to the seasons. what is the connection between these different parameters. The significance of the variance between seasons is :

(49, 61) for conductivity, pH (52,46), turbidity (60,65), nitrates (65,08), nitrites (73,32) and on average 3.2.2. Correlation between the physicochemical percentage microorganisms also comes from fact that for and bacteriological parameters studied these parameters there is a fluctuation between the dry season and the wet season. The difference between Min To investigate the Principal Component Analysis (PCA), 29 and Max values of parameters such as turbidity, stations and all the 16 of physicochemical and conductivity and microorganisms are given in Table 3. This bacteriological parameters analyses results were difference is probably due to the runoff and leaching of performed on a data matrix (average of 3 samples for the grounds in winter, the increase of the atmospheric each station). temperature which causes several reactions and the 3.2.2.1. "Bonferroni" fit for a correlation network evaporation of the water which increases the (based on Pearson correlations) concentration of the different ions in the water in summer [19]. To show the threshold of the significant relationships Conductivity reflects the total mineralization of water and between physico-chemical and bacteriological parameters its value varies with the ambient temperature and the in multiple comparisons, the results are plotted after the level of water stored. "Bonferroni" fit (Cf. Fig.4). The dashed lines indicate the negative relations and the simple lines the positive Since nitrates and nitrites are mainly dependent on relations. The width of the lines is proportional to the high agricultural activities, their concentrations increase during significance. the season in which these activities take place. N. ACHAHBAR & al 437

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dissolving, the salts dissociate into pairs of ions (anions and cations) which allow the passage of the electric current. The more mineralized the solution, the more ions in solution and the higher the electrical conductivity [24]. The temperature acts favorably on the proliferation of coliforms, which explains the correlation between these two parameters. Compared with coliforms, faecal streptococci are more resistant to harsh environmental conditions and persist longer in water, where the temperature is generally colder and nutrient-poor [25], so there is no need for correlation between them. Bacteria are destructive and mineralising organisms of living organic matter, their existence pushes the mechanism of destruction to

Fig. 4 : Bonferrobi network correlation between water mineralization and their absence ; raw materials (Carbon, characteristics (physicochemical and bacteriological) Nitrogen, Sulfur) would be lacking [26]; this is why there is Source : [Statistical analyzes of sampling data using the spss program] a correlation between the different types of bacteria (CT, CF and SF) and minerals in water (sulphates, The strong correlation of calcium with TH and magnesium magnesium, TDS, etc.). is normal since the hardness of a water (or hydrotimetric titer) is a quantity related to calcium and magnesium ions, 3.2.2.2. The distribution of parameters according to the more water contains calcium and magnesium, the a factorial plan of the PCA analysis higher the hardness will be. The correlation of these parameters with the sulphates indicates that the sulfur The analysis of the results shows that most of the present often comes from the rock crossed, this rock is informations are explained by the first two factorial axes. part of the rifaine chain in its external part which includes In the factorial plane F1xF2, the eigenvalues of the two allochthonous units (layers of the flyschs) pelitico- components F1 (axis1) and F2 (axis2) and their sandstone in superstructure on a unit indigenous to para- contribution to the total inertia are shown in (Cf. Table 5). indigenous predominantly pelitic denominated unit of The two axes taken into account to describe the Tangier [20] [21]. Similarly, the correlation of these with correlations between the variables related to the spatial other minerals in water, especially chlorides, is important structures, alone hold 63,93% of the total information because of the degree of mineralization of the water [22]. with, respectively, 49,79% for axis 1 and 14,14% for axis 2 It has been found that the leaching of calcium from the (Cf. Table 6). soil increases markedly with the acidity of the water [23]; Tab. 6 : Principal Component Analysis (PCA) results using this might explain the negative correlation between pH physicochemical and bacteriological parameter data and calcium in our study. The pH is also negatively from spring water correlated with TDS, and this is explainable because when Parameters Axis 1 Axis 2 Axis 3 the pH is low (acid), the dissolution of the substances in pH -0,392 -0,436 0,625 the water increases. Tur 0,488 0,466 0,401 Cond 0,539 -0,254 -0,487 TDS have a strong correlation with salinity that similarly Sal 0,891 0,252 -0,178 correlates with different parameters (calcium, TH, TDS 0,866 0,158 -0,194 magnesium, sulphates, chlorides) and that is because Ca 0,882 0,183 0,025 these parameters contain salts in their constituents. TH 0,925 -0,007 0,023 Mg 0,602 -0,627 0,004 Turbidity indicates the existence of mineral and organic Cl 0,584 0,222 -0,271 particles. The correlation of turbidity with nitrates returns NO3- 0,312 0,700 0,291 to particles coming from the decomposition of plant and NO2- 0,095 0,532 0,336 2- animal matter in water. Nitrite is the intermediate stage SO4 0,856 0,000 -0,110 between nitrates and ammonium ions NH4 +; this is why CT 0,869 -0,309 0,176 the correlation between nitrates and nitrites is counted CF 0,845 -0,315 0,326 normal. SF 0,773 -0,341 0,382 Eigen values 7,468 2,121 1,426 Conductivity is positively correlated with the different % Variance 49,78 14,13 9,50 ions present in the water regardless of the parameter. It % Cumulative variance 49,78 63,92 73,43 depends on the quantity of salts in solution; in fact, by Source : By analyzing sample data using the spss program

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Axis 1 (F1); contributing with 49.79% of inertia, is defined The presence of CT, CF and SF in water reveals by parameters namely TH (0,925), salinity (0,891), calcium contamination by faeces, domestic sewage and infiltration (0,882), TDS (0,866), sulphates (0,856), CT (0,869), CF of sanitary sewers. (0,845), SF (0,773), magnesium (0,602) and conductivity Group II: formed by stations located in rural areas. The (0,539). level of nitrates and nitrites is high in this group. With an inertia of 14, 14% the second component, axis 2 Nitrates and nitrites come mainly from agricultural (F2); is defined by the parameters: nitrates (0,700), activity (as is the case of the samsa, boussemlal and dar nitrites (0,532), turbidity (0,466) on the positive side and zkiek stations (Ain Hamma, Ain Dekken and Ain Soufla)); magnesium (0,627), pH (0,436), conductivity (0,254) on their use to improve agricultural yields makes them flow the negative side (Table 5). into the waters. Indeed, any excessive or poorly The factorial map of the stations (Cf. Fig. 5) released by controlled use of these fertilizers will lead to increased the F1 (horizontal) x F2 (vertical) plane shows the concentrations of these compounds as a result of soil representation of two different groups according to their leaching and rainwater runoff [30]. As with nitrates, some physicochemical and bacteriological quality: indicators of water pollution in rural areas may be caused by livestock rearing, households and poor waste management. The turbidity of the water is almost the same for both groups. In rural areas, it may be caused by organic particles such as decomposed animal or plant matter, inorganic particles (silt and clay) and landslides. In the center of the city, it can originate from human activities (construction sites, domestic wastewater, etc.). 4. Conclusion The diagnosis made through the physicochemical and bacteriological quality assessment of spring waters from 29 samples during three years shows that spring water resources in the region of Tetouan are vulnerable. Consumption of these spring waters without prior treatment may be harmful to health. This degradation

Fig. 5 : Principal component analysis (PCA) factorial map for could be explained mainly by population growth, urban the physicochemical and bacteriological characteristics of the expansion, agricultural activities, sewage seepage and water in the 29 sampling stations in the urban and rural areas waste black spots in the region. The three-factor nested of Tetouan city. The numbers on the factorial map represent ANOVA analysis showed that the variance of the the stations studied (Table 1) parameters which informed us about the quality of the Source : Statistical analyzes of sampling data using the spss program spring waters is related to space and to season. Principal Group I: formed by stations located in the urban area of component analysis (PCA) of physicochemical and Tetouan city. bacteriological data highlighted a zonality of the quality of the water sources in the Tetouan region. The urban area The elements (TH, magnesium, calcium and sulphates) of Tetouan city (stations 10, 13, 14, 15, 16, 17 and 18) is which have a high level in group 1, might be caused by the subject to seepage and discharge of sewage as well as action of the weathering of rocks, particularly that of garbage dumps. In rural areas (stations 1 to 9, 11, 12, and limestone and marl, and by training from the soil in 19 to 29), agricultural fertilizer, livestock and soil leaching seepage, leaching and runoff [27] [28] [29]. are the main causes of spring water quality deterioration. The concentration of these elements depends probably on the residence time of the water in the geological We all know that water is the base of life and it is formations, as well, the water of the downtown springs, essential in our existence. On this principle, I have which are at low altitudes (Cf. Table 1) and which stack prepared my project aiming to show how the matter of the total of these existing elements in all the rocks and water is important and because we all discover that day supports traversed; have higher concentrations. after day this precious element is exposed to great dangers amoung them ; the pollution. The conductivity values of spring waters depend mainly on the local geology, when significant changes in Contribution of the authors conductivity are observed in the water, this is an Nouha ACHAHBAR: Main author, PhD student in biology, indication of an increase in the contributions of dissolved health and environment discipline at Abdelmalek Essaadi substances from water contaminated by human activities University, the Faculty of Sciences of Tetouan, Laboratory (urban development, industrial activities, waste, etc.) [19]. of Applied Biology and Pathology. N. ACHAHBAR & al 439

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Nadia AMAJOUD and Ouisal OULED ZIAN: Responsibles for Maharashtra, India. Environments. 2019; the laboratory of Communal Environment and Pollution https://doi.org/10.3390/environments5050061. Control where the bacteriological analyzes were carried [7] World Resources Institute (WRI). Hofstle R.W, Reig P, out. Schleifer L. 7 Countries, Home to One-Quarter of the World's Population. Face Extremely High Water Abdellah EL MAFTAHI: Responsible for the laboratory of Stress. August 2019; Available from: Communal Environment and Pollution Control where the https://www.wri.org/blog/2019/08/17-countries- physico-chemical analyzes were made. home-one-quarter-world-population-face-extremely- high-water-stress Mouad BEN ZAKOUR: Co-supervisor of thesis and [8] Ben Moussa A, Chahlaoui A, Rour E.H. Qualité de la Communal Environment and Pollution Control laboratory source Ain Hamma et effet du déversement de ses manager eaux sur la qualité physico-chimique et bactériologique des eaux de l’Oued Khoumane, El Khalil BEN DRISS: Supervisor of thesis Maroc [Quality of the Ain Hamma source and effect of the discharge of its waters on the physicochemical Acknowledgement and bacteriological quality of the waters of Oued Great appreciate to Mr. Jalal Kassout, doctoral student Khoumane, Morocco]. Afrique SCIENCE. 07(2): 2011; from Botanical laboratory applied at the Faculty of 115 – 130. (French) Sciences in Tetouan Morocco for his help in the statystical [9] Ghazali D, Zaid A. Etude de la qualité physic-chimique analysis. et bactériologique des eaux de la source ain Salama- Jerri (Région de Méknes-amaroc) [Study of the References physico-chemical and bacteriological quality of the [1] GWP (Global Water Partnership). Towards a water water source ain Salama-Jerri (Region of Meknes secure world: water & urbanisation, water & climate Morocco)]. Larhyss Journal. ISSN 1112-3680, n°12: change. January 2014; Available 2013; pp.25-36. (French) from:https://www.gwp.org/en/CRITICAL- [10] Belghiti M.L, Chahlaoui A, Bengoumi D, El Moustaine CHALLENGES1/Water-and-Urbanisation/ R. Etude de la qualité physico-chimique et [2] Palamuleni L, Akoth M. Physico-Chemical and bactériologique des eaux souterraines de la nappe Microbial Analysis of Selected Borehole Water in plio-quaternaire dans la region de Meknès (Maroc) Mahikeng. South Africa, Environmental Research and [Study of physico-chemical and bacteriological quality Public Health. 2015; 12(8):8619–8630. of groundwater in the plio-quaternary table in the https://doi.org/10.3390/ijerph120808619 region of Meknes (Morocco)]. Larhyss Journal. ISSN [3] Orelien & Frantzy. Etude de la qualité de l'eau 1112-3680, n°14: 2013; pp.21-36. (French) destinée à la consommation humaine dans le sous- [11] Errochdi S, El Alami M, Bennas N, Belqat B, Ater M, bassin versant de Ravine Diable (Anse-a-Veau) [Study Fdil F. Étude de la qualité physicochimique et of the quality of water intended for human microbiologique de deux réseaux hydrographiques consumption in the Ravine Devil subwatershed (Anse- nord marocains: Laou et Tahaddart [Study of the a-Veau)]. Master's degree in Environmental Science physicochemical and microbiological quality of two and Management in Developing Countries. University northern Moroccan river systems: Laou and of Liège, Belgium. 2016-2017 (French). Tahaddart]. Journal of medirteranen geography. http://hdl.handle.net/2268.2/3245 2012; p. 41-51. (French) DOI : [4] Sila Onesmus N. Physico-chemical and bacteriological 10.4000/mediterranee.6221 quality of water sources in rural settings, a case study [12] Benajiba M.H, Saoud Y, Lamribah A, Ahrikat M, of Kenya, Africa. Scientific African. Volume 2, 2019; Amajoud N, Ouled-Zian O. Évaluation de la qualite https://doi.org/10.1016/j.sciaf.2018.e00018 microbienne des eaux de la nappe phréatique de [5] Ayenuddin H, Abu Sayed J, Papia S. Assessment of Martil au Maroc [Assessment of the microbial quality physicochemical and bacteriological parameters in of waters of the Martil water table in Morocco]. surface water of Padma River, Bangladesh. Applied Journal of Water Science. Vol. 26, n° 3: 2013; p. 223- Water Science. 2019 ; 233. (French) https://doi.org/10.7202/1018787ar DOI: 10.1007/s13201-018-0885-5 [13] Lamribah A, Benajiba M.H, Saoud Y, Ahrikat M, [6] Dhawde R, Surve N, Macaden R, Wennberg A.Ch, Benzakour M. Impact de la pollution urbaine sur la Seifert-Dähnn I, Ghadge A, Birdi T. Physicochemical contamination par les nitrates et les nitrites de la and Bacteriological Analysis of Water Quality in nappe phréatique de Martil (Maroc) [Impact of urban Drought Prone Areas of Pune and Satara Districts of pollution on the contamination by nitrates and nitrites of the Martil natural table (Morocco)]. Larhyss

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Journal. ISSN 1112-3680, n°14: 2013; pp.79-91. [23] Overrein L.N. Sulfur pollution patterns observed: (French) leaching of calcium in forest soil determined. Ambio. [14] HCP (High Commissioner for Plan of Morocco) Report. 1972; 1: 145. Doi: EDB-84-151444 Regional Direction of Tangier-Tetouan. Monograph of [24] ISSeP (Institut Scientifique de Service Public). the Tangier-Tetouan region. 2015 (French) Méthode de mesure in situ de la conductivité [15] Kettani K, Vilchez A, Calle D, El Ouazzani T. Nouvelles électrique de l’eau [(Scientific Institute of Public cultures de Chironomidae (Diptera) du Maroc: Service), In situ measurement method of electrical Chironomidae d'Oued Martil (Rif) [New crops of conductivity of water]. 2014; ISO 7888, Belgium. Chironomidae (Diptera) from Morocco: Chironomidae (French) from Oued Martil (Rif)]. Annls Limnol. 1995; 31 253- [25] Gleeson C, Gray N. The coliform index and 261. waterborne disease, E & FN Spoon. 1997; 194 p. [16] Hmid K, Khallaf M, El Ouardi A, El Habib F, Zoutni B, [26] Wurtz A. Rôle et importance des bactéries dans l'eau Ameur N, Benabderrazak F, Mouhcine M, Fagraoui L, [Role and importance of bacteria in water]. Bull. Fr. Chliha K. Manuel de microbiologie alimentaire [Food Piscic. 144: 1947; 144-148. (French). Microbiology Manual]. Ministry of Public Health, https://doi.org/10.1051/kmae:1947015 Kingdom of Morocco. 1997; 40 p. (French) [27] Day E.H. The chemical elements in nature, London [17] Rodier J. Water analysis: Residual water. Sea water (U.K): George C. Harrap & Co. 1963. (9th edition). Paris: Dunod Ed., 1978; p 1125. [28] Nold M, Utttnger J, Wildi W. Géologie de la Dorsale [18] NM 03.7.001. Moroccan standard relating to the calcaire entre Tétouan et Assifane (Rif interne, quality of human food water. 16 March 2006; Official Maroc) [Geology of the calcareous Dorsal between Bulletin N° 5404. (French) Tetouan and Assifane (internal Rif, Morocco)]. [19] Hade A. Our lakes - to know them better to protect Editions of the Geological Service of Morocco. Rabat: them, Fides editions. Waterwatch Australia Steering Ministry of Energy and Mines. 1981; 205 pages. Committee. 2003; 360 p. (French) (French) [20] El Mrihi A. PhD thesis Structures and kinematics of [29] Amharref M, Chaouni A.A, Aouragh T. Master of Mauretanian flysch nappes (Rif external north-west): Science and Technology: Hydrologie de Surface et Development of a model.Tétouan (Morocco): Qualité des Eaux: Etude hydrogéologique et Abdelmalek Essaadi University. 2005; 376 p. (French) hydrochimique des principales sources de la dorsale [21] Tribak Y, El Morabiti K, Hlila R. Etude calcaire méridionale, Ras El Ma et Chrafate Hydrogéologique préliminaire de la zone des flyschs à (, Maroc) [Surface Hydrology and Water l’Ouest de Tétouan (Maroc) [Preliminary Quality: Hydrogeological and hydrochemical study of hydrogeological study of the flysch zone west of the main sources of the southern limestone ridge, Ras Tetouan (Morocco)]. International Journal of El Ma and Chrafate (Chefchaouen, Morocco)]. Fez Innovation and Applied Studies. ISSN 2028-9324 Vol. (Morocco): Sidi Mohamed Ben Abdellah University, 14 No. 3: 2016; pp. 653-667. (French) 2015. (French) [22] Toumi A, Reggam A, Alayat H, Houhamdi M. Physico- [30] Waters & Rivers of Brittany. La pollution par les chemical characterization of waters of the lake nitrates [Pollution by nitrates]. December 2014. ecosystem: Case of Lake of Birds (Far NE-Algerian). France. http://www.eau-et-rivieres.asso.fr/. (French) Journal of Materials and Environmental Sciences. 2016; 139-147.

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