Assessment of Environmental Impacts on Geochemical Evolution

International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1552 ISSN 2229-5518

Assessment of the environmental impacts on geochemical evolution of groundwater resources in Nubaria area, west of Nile Delta area, Egypt

Fattah . M. K.1, Dahab, K. A. 2 and Ahmed,M. G1 1-Environmental Studies and Research Institute, University of Sadat city, Egypt. 2- Faculity of science, Menofiya University, Egypt. * Corresponding author: Dr: Mohamed Kame Fattah Environmental Studies and Research Institute (ESRI), University of Sadat city, Egypt. E-mail: [email protected]. , [email protected]

Abstract During the last decade, the continuous development of human society as well as the side effects of land reclamation projects left negative impacts on water resources in Nubaria area, west of Nile Delta area. Such negative impacts are pronounced in continuous groundwater deterioration and water pollution.

The present work focus on the environmental impacts on geochemical evolution of the Quaternary aquifer in the study area and determine geochemical type, origin, evolution of groundwater and their relation to the prevailing hydrogeological and environmental conditions, and finally evaluate the suitability of ground water for different uses. Most of groundwater samples are good to moderate water class and suitable for irrigation purposes.

Key words: Hydrogeochemistry, Quaternary aquifer, Netpath program, Nubaria area, west of Nile Delta area, Egypt. Introduction groundwater systems [2] .Hydrochemical evolution The area of study is a partIJSER of the western Nile is commonly used to reconstruct geochemical Delta fringe. This area is limited by latitudes 30º 15′ evolution of groundwater from one point in an - 30º 50′ N and longitudes 30º 00′ - 30º 48′ E, with aquifer to another point located in the inverse 2 direction along the groundwater flow path [3]. Nile area of about 3100 kmP .P It is bounded by El Nubariya canal from the northeast, El Nasr canal Delta area, is one of the most important areas for the from the northwest, El Rayah El Naseri from the land living. Accordingly, extensive need to the east and Cairo – Alex. desert road from the south water as a supplement for irrigation and domestic (Fig. 1). The chemistry of groundwater is an use attracted more attention, and great efforts were essential parameter for assessing the environmental established to evaluate water resources in the characteristics of an area [1]. The main factors investigated area. Variation of groundwater quality affecting water quality changes are lithofacies in an area is a function of physical and chemical geographical conditions, groundwater recharge and parameters that are greatly influenced by geological runoff conditions, and the degree of openness of formations and anthropogenic activities [4].

Mediterranean Sea 50 31 82 30

30 80 81 79 18 Rosetta 171966 Damietta 64656315 16 Lake Idku Kafr El Sheikh 21 6869 Damanhur 61 31 El Mansoura 71 60 2067 7270 62 Abu El Matamir 59 55 00 7473 Tanta 83 Kafr Bolin 35 34 5856 33 12101157 1314 Shibin 30 El Kom Kafr 32 30 Dawoud El Sadat City Banha 24 El Khatatba 7825 84 26 36 The Study Area 3130 77 85 1 51 86 30 52 Cairo 9 00 Km. 76 2829 0 10 20 30 232275 3 5 8 4 7627 30 00 30 30 31 00 31 30 2 30

53 37 54 30

50 30 49 43 30

40 44

39 48 38 41

47 42 45 46

Legand Main Road Main irrigation Canal 30 Secondary irrigation Canal 10 0 4 12 20 Km. Shallow well ( 65 m ) 10

30 Deep well ( 65 m - 170 m ) Scale

30 00 30 30 31 00 Fig. (1) Location well map for the production wells in the study area Material and methods global positioning system (GPS) Garment 12 was used Complete chemical analysis of 50 groundwater for location and elevation readings. The NETPATH samples collected from the study area, (Fig. 1). computer code was used to model the major groundwater analyses were carried according to the hydrogeochemical reactions contributing to the methods adopted by [5]. The analyses conducted both evolution of groundwater chemistry in the study area. in the field and laboratory include total dissolved The model is described in detail by [6]. It can provide solids (TDS), measurement of pH, electrical a useful insight into the probable processes governing IJSER+2 +2 + groundwater chemistry [7] and [8] conductivity (EC), concentrations of Ca , Mg , Na + -2 - -2 - and K as cations, CO3 , HCO3 , SO4 and Cl as anions, and determination of the trace elements Fe3+ , I.Geological and hydrogeological setting: 2+ +3 2+ Mn , Al and Zn . ). The water pH, temperature, 1.2 Geological setting electrical conductivity (EC), salinity and total The geology of the considered area and its dissolved solids (TDS) were measured in the field. vicinities concluded that, the rocks of Miocene, Water samples were filtered at the time of collection Pliocene, and Quaternary times are the most using 25 mm puradisc syringe filtration unit of 0.45 outcropping sediments. The surface geologic structure µm pore size and acidified to pH 2 with concentrated is relatively simple; however in the subsurface many HNO3 acid and analyzed directly using flame (air- complicated structures are detected.The study area is acetylene burner) atomic absorption spectrometry covered by extensive exposures of sedimentary (FAAS – Zeeman AAS Z-5000, Hitachi, Japan)to + + 3+ 2+ +3 2+ 2- successions ranging from Late Cretaceous to measure Na , K , Fe , Mn , Al and Zn . SO4 Quaternary. The surface geological structure is was measured using a HACH (DR/2040 – Loveland, 2+ +2 - 2– relatively simple, however many complexities are CO, USA) meter, Ca ,Mg ,Cl and HCO3 were detected in the subsurface. The subsurface succession analyzed using argentometric and titration methods is characterized by the occurrence of many respectively, where the procedures of analyses adopted unconformity surfaces and considerable faulting and in this study were based on the methods described in folding structures, which directly affect the ASTM (2002). Also, saturation indices were calculated groundwater occurrences. with the help of NETPATH computer program [6]. A 1.3- hydrogeological setting

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1554 ISSN 2229-5518 Pleistocene aquifer represents the main water aquifer, (Fig. 2).The aquifer is built up of sand, gravel and clay resource of water supply for domestic, industrial and deposits belonging to the Quaternary time (Holocene and irrigation purposes in the study area. The Pleistocene Pleistocene). Environmentally, the Pleistocene sediments aquifer is mainly composed of fluviatile graded sand belong to Deltiac facies composed of gravelly sands and sands and gravel intercalated with clay lenses. The thickness intercalated with thin clay layers and capped by lagoonal facies of aquifer increasing in northeast and northern composed of sands, clay and gypsiferous clay .The saturated direction, it reaching its minimum values near Wadi thickness of the aquifer in the study area shows variable El Natrun, El Sadat City, while it reach its maximum values, it increases gradually in the northeast direction , it values at near Nile Delta aquifer. Groundwater in the ranges from 100 m to 200 m in the southwestern portion study area is under phreatic condition with the near Cairo-Alex. Desert Road and from 260 m to 280 m exception of some localities, which display a semi- at El-Sadat City, while it reaches its maximum values at confined condition From hydrogeological cross section the northeastern part ranging from 300 m to 320 m. was constructed to describe the lithological facies, hydrostructural setting and hydrogeological properties of the

00 30 30 30 31 00 30 50

Mediterranean Sea 50 31 30 30 Rosetta Damietta

Lake Idku Kafr El Sheikh

Damanhur 31 El Mansoura 00 Abu El Matamir

Tanta Legand: Kafr Bolin

Shibin 30 El Kom Kafr 30 Dawoud El Sadat City Banha El Khatatba Gravelly sand Flow direction C The Study Area 30 W 18 Cairo 00 Km. 0 10 20 30

30 00 30 30 31 00 31 30 30 W 17

Water table 30 sand 30 30

W 16 Clay W 15 W 14 C

Legand

Main Road 30

10 Main irrigation Canal 10 Secondary irrigation Canal 0 4 12 20 Km. 30 NW Area of study Scale 30 00 30 30 31 00 (M.) SE 100 100 W 14 W 15 W 16 W 17 W 18 0.0 0.0 Pleistocene Pleistocene Pleistocene

- 100 - 100

- 200 - 200 Pliocene Pliocene

- 300 - 300 0 5 10 Km. IJSERH.Scale C C Fig. (2) Hydrogeological cross section of the Quaternary aquifer in the study area [9] The depth to groundwater varies less than one from (–4 m) and (– 5 m) (bmsl) at the southern part meter near El Nubariya canal (northern parts) to about (Fig.3). The low values of groundwater levels 20 m. at El Bustan area (central part), while it exceeds recorded at the southern part reflect impact of large 60 m below the ground surface in Sadat City and its scale groundwater extraction rates and limited vicinities(southern part).Groundwater levels ranges groundwater recharge to these localities. from + 5 m to + 4 m (amsl) in the northern part and

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Mediterranean Sea 50 31 30 30 16 Rosetta 9 Damietta

Lake Idku Kafr El Sheikh

Damanhur 31 El Mansoura

Abu El Matamir 1110 00 Re 55 30 Tanta 1312 Kafr Bolin c 22 h 21 6 Ar Shibin a 78 r 30 El Kom e g 57 Kafr a e Dawoud 20 30 El Sadat City Banha El Khatatba 15 51 54 The Study Area 19 Rec 30 Cairo 5 har 00 Km. 53 A 58 0 10 20 30 14 18 rea 1 ge 4 2 30 00 30 30 31 00 31 30 3 17 30

49 56 50 30 48 30 47 52 26 43

30 42

Di s 41 cha 40

25 r 24 ge 46 28 23 45 29 3231 27 Ar 39 30 37 33 ea 3536 38

Legand

Main Road 30

10 Main irrigation Canal 0 4 12 20 Km. 10 Water level contour line

30 Scale Observation well

30 00 30 30 31 00

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1555 ISSN 2229-5518 (Fig. 3): Water levels contour map of the Pleistocene aquifer in the study area II-Groundwater chemistry in the study area: study area have salinity content ranging from 1024 mg/l II.1- Salinity content distribution (TDS): to 2688 mg/l represented in northern and southern parts of The majority of samples in shallow groundwater the study area (Fig. 3) wells (less than 65m)of the Pleistocene aquifer in the

00 00 30 30 30 30 31 00 30 30 30 31 00 30 50 50 50 Mediterranean Sea Mediterranean Sea 50 31 31 30 30 30 Rosetta 30 Rosetta Damietta Damietta

Lake Idku Lake Idku Kafr El Sheikh Kafr El Sheikh

Damanhur Damanhur 31 El Mansoura 31 El Mansoura

00 Abu El Matamir 00 Abu El Matamir

Tanta Tanta

Kafr Bolin Kafr Bolin

Shibin Shibin 30 El Kom 30 El Kom Kafr Kafr Dawoud Dawoud 30 Banha 30 El Sadat City El Sadat City Banha El Khatatba El Khatatba

The Study Area The Study Area 30 30 Cairo Cairo 00 Km. 00 Km. 0 10 20 30 0 10 20 30

30 00 30 30 31 00 31 30 30 00 30 30 31 00 31 30 30 30 30 30 30 30 30 30

Legand Legand Main Road Main Road Main irrigation Canal 30 Main irrigation Canal 30 Secondary irrigation Canal 10 0 4 12 20 Km. 10 Secondary irrigation Canal 0 4 12 20 Km. 10 800 10 Salinity contour line 500 Salinity contour line 30 Scale 30 Scale Shallow well ( 65 m ) Deep well ( 65 m - 170 m )

30 00 30 30 31 00 30 00 30 30 31 00 (Fig. 3): Salinity distribution contour map (Fig. 4): Salinity contour map of deep of shallow production wells in the study area production wells in the study area

The majority of groundwater samples of deep (HCOR3R)R2R, Ca (HCOR3R)R2R wells (more than 65m ) ranging from 320 mg/l a the (17% of the total groundwater samples) south to 1200 mg/l at the north. But in some region of Assemblage II: NaCl, NaR2RSOR4 R, MgSOR4R,R R Mg (HCOR3R)R2R, the southwestern parts (El SadatIJSER City and Cairo - Alex. Ca (HCOR3R)R2 Desert Road) display relatively high salinity ranging from R R(37% of the total groundwater 1200 to 2253 mg/l (Appendix I), the increase in salinity samples) contents that recorded at these parts reflect the over Assemblage III: NaCl, Na R2RSOR4R,R RMgSOR4 R, CaSOR4R , Ca pumping and leaching processes of salts from clay present (HCOR3R)R2 in the aquifer materials. The relationship between salinity (44% of the total groundwater samples) contents and the other ions in deep wells indicates that Assemblage IV: NaCl, MgClR2 R, MgSO4,R R CaSOR4R , Ca sodium, calcium, potassium, sulphate and chloride are the (HCOR3R)R2 effective ions which caused an increase of water salinity (2% of the total groundwater samples) and change in groundwater quality. Salinity displays good Most groundwater samples of the Pleistocene aquifer linear relationship with calcium, sodium, sulphate and are characterized by the assemblages of salt chloride ions with high correlation coefficients 0.80, 0.96, combination (II and III); assemblage II (37% of the 0.93 and 0.95 respectively, moderate linear relationship total groundwater samples) represents an earlier stage with potassium ions with correlation coefficient 0.58, of chemical development than that of assemblage III. poor linear relationship with magnesium and bicarbonate Assemblages I and II (two bicarbonate salts) reflects with correlation coefficient 0.26 and 0.31 respectively. the effect of pure rain water or surface water on

II.2U - U U Hypothetical salts groundwater and also reflects recent recharge. Regarding hypothetical salt combinations of Assemblage III (three sulphate salts) reflects the the Pleistocene aquifer in the study area, groundwater effects of leaching and dissolution of evaporates samples have the following assemblage: deposits and represent intermediate stages of chemical development. Very few groundwater samples (2% of Assemblage I: NaCl, Na R2RSOR4R, Na (HCOR3R)R2R, Mg

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1556 ISSN 2229-5518 the total groundwater samples) are characterized by aquifer materials. assemblage IV which represents an advanced stage of The value of the hydrochemical coefficient chemical development, this salt assemblage reflect the (rMg+rCa/rNa) in the Pleistocene groundwater effect of marine salt pollution (marine facies aquifer samples varies from 0.062 (sample No. 69) to groundwater type) with possible contribution of cation 1.28 (sample No. 85) with an average 0.67 in shallow exchange phenomena resulting from the presence of groundwater wells and from 0.08 (sample No. 20) to the clay intercalated with the Pleistocene aquifer in the 1.96 (sample No. 6) with an average 1.02 in deep study area. groundwater samples. This ionic ratio is more than II.3-. Hydrochemical coefficients: unity in some groundwater samples 9 %), the majority The hydrochemical coefficient gave good of samples have value less than unity which indicate indication of geochemical processes occurring in predominance of sodium over calcium and magnesium groundwater solution and groundwater origin as well as leaching processes of sodium bearing (Appendix IV). The hydrochemical coefficients minerals such as halite and Sodic - plagioclase that

(rNa/rCl), (rCa/rMg), (rMg+rCa/rNa), (rSO4/rCl) and dominant aquifer materials. - -2 (rHCO3/rCl) were calculated (appendix VII). r Cl / r (HCO3 + CO3 ) ratio The value of the hydrochemical coefficient Todd (1959) [11] categorized groundwater according (rNa/rCl) of groundwater of the Pleistocene aquifer to this ratio as follows: varies from 1.17 (sample No. 60) to 6.95 (sample No. 70) 1- Normal good groundwater (less than 1) with an average of 4.06 in shallow groundwater wells and 2- Slightly contaminated water (more than 1 and from 0.86 (sample No. 47) to 4.15 (sample No. 20) with less than 2) an average 2.5 in deep groundwater wells. The excess of 3- Moderately contaminated water (2-6) sodium over chloride water samples reflects meteoric 4- Seriously contaminated water (more than 6 and water origin. [10] concluded that the increasing Na+ ions less than 15) might have theoretically originated by dissolution of 5- Highly contaminated water (more than 15) sodium bearing silicates from the country rocks. This is The values for the main aquifer range from due to the complete flushing of marine deposits or old sea 0.178 (well No. 55) to 26.366 (well No. 54) in shallow water through movement of rain water that horizontally or groundwater wells, and from 0.267 (well No. 46) to vertically infiltrated and settledIJSER in siliceous aquifer 14.334 (well No. 42) in deep groundwater wells. These materials in the past time values are less than that in sea water (220) and more The value of the hydrochemical coefficient than in rain water (0.68). Most of groundwater samples (rSO4/rCl) varies from 0.59 (sample No. 59) to 5.95 (31 % shallow wells and 37% deep wells) are (sample No. 85) with an average of 3.27 of shallow considered moderately contaminated water (2-6).This wells. It has values ranging from 0.4 (sample No. 14) means that the groundwater has a mixed origin that is to 2.67 (sample No. 35) with an average 1.53 in deep possibly pure meteoric water affected by trace of groundwater wells. Predominance of saulphate over marine deposits. chloride in the majority of samples reflect leaching and II.4. Geochemical classification of groundwater: dissolution of sulphate bearing minerals such as Piper's trilinear diagram [12], this diagram illustrates evaporites and Gypsum that dominant in aquifer the trend of geochemical evolution of groundwater materials. through mixing with other sources and through water- The value of the hydrochemical coefficient rock interaction. (rCa/rMg) of the Pleistocene groundwater aquifer Piper's trilinear diagram for shallow and deep samples ranges from 0.33 (sample No. 75) to 6.6 groundwater wells consequently show that (Figs. 5. and (sample No. 83) with an average of 3.46 in shallow 6), the projection of chemical composition of shallow groundwater wells and from 0.13 (sample No. 33) to groundwater on the diamond field revealed that most of 5.35 (sample No. 13) with an average 2.74 in deep water chemical compositions are plotted in subarea 7 (32 groundwater samples. The excess of calcium over wells), and in subarea 9 (3 wells) (Fig. 5). Piper's trilinear magnesium in the majority of samples reflect leaching diagram for deep groundwater wells show that, the and dissolution of carbonate minerals that dominant in projection of chemical composition of deep groundwater

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1557 ISSN 2229-5518 ++ + -- SO R4RP andP sodium + ־on the diamond field revealed that most of water chemical characterized by NaP P + KP P > Cl compositions are plotted in subarea 7 (42 wells) and in chloride salts (Fig. 5.26). The appearance of NaCl water subarea 9 (9 wells), where subarea 9 reflects fresh water type with high percentage of MgSO R4R and CaSO R4R reveals and that reflects Na-HCOR3R and Ca-HCOR3R water type, high phase of groundwater mineralization. while subarea 7 reflects primary salinity properties

0 5 5 5 0 6 50 0 6 100 50 100 50 1 4 9 1 4 9 5 7 5 7 2 3 9 2 3 9 0 5 8 50 0 50 8 50 80 5 0 80 5 80 80 Subdivisions of the diamond shaped Subdivisions of the diamond shaped field of Piper trillinear diagram field of Piper trillinear diagram 60 60 60 60 SO 4 + Cl 50 50 Ca + Mg SO 4 + Cl 50 50 Ca + Mg 40 40 40 40

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CO3 + HCO3 CO3 + HCO3 Na + K 0 0 Na + K 0 0 100 100 100 100

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40 40 40 40 60 60 60 60 50 50 50 50 Mg SO4 Mg SO4 60 60 60 60 40 40 40 40

80 80 80 80 20 20 20 20

100 0 100 0 100 80 60 40 20 0 0 20 40 60 80 100 100 80 60 40 20 0 0 20 40 60 80 100 Ca Cl Ca Cl Cations Anions Cations Anions

(Fig. 5): Geochemical classification of (Fig. 6): Geochemical classification of

shallow groundwater in Piper trilinear diagram deep groundwater in Piper trilinear diagram

IV- Environmental impacts on geochemical final (evolutionary) water. In hydrochemical systems mass-balance reactions: the number of reacting phases is often larger than the IV.1- Mineral precipitationIJSER / dissolution process number of constraints necessary to define their (Geochemical modeling). composition. NETPATH solves a set of linear NETPATH was used to environmental simulate net equations that account for conservation of mass, and geochemical mass-balance reactions between initial (optionally) conservation of electrons and selected and final waters along a hydrologic flow path. The isotopes to find every subset of the selected phases program uses chemical data for waters samples. The (every model) that satisfies the chosen constraints. processes of dissolution, precipitation, ion exchange, Each mass-balance model can be treated as an isotope oxidation/reduction, degradation of organic evolution problem solving isotope mass balance and compounds, incongruent reaction, gas exchange, Raleigh distillation problems to predict the isotopic mixing, evaporation, dilution can be considered. This composition at the final point on the flow path. program simulates selected evolutionary waters for 5.4.1.U Input data: every possible combination of the plausible phases that Water analyses are entered through the interactive account for the composition of a selected set of data base (DB) program. DB allows editing and chemical constraints in the system (Table 2 ). The processing of the data through the WATEQF NETPATH software includes a data-base program equilibrium model [13], [14] and [15] to produce an (DB) for storing and editing chemical data for use in input file (filename. PAT) to NETPATH DB (and NETPATH. A mass-balance is defined as the masses NETPATH) accept laboratory and field analytical data (per kilogram H2O) of a set of plausible minerals and for waters containing the elements Na, K, Ca, Mg, Cl, gases that must enter or leave the initial solution in S, C, Fe, Mn, N and P. Temperature and pH are order to define exactly a set of selected elemental, required for every water analysis, the rest are optional. electron transfer, and isotopic constraints observed in a All files and data used by DB are interactively updated

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1558 ISSN 2229-5518 and maintained. DB produces full speciation output zero value means that the solution is in equilibrium state. for all waters in the format of WATEQF results (Fig. The saturation state is calculated as follows: 13 ), maintains the [filename]. LON data file of Ω = IAP / K Where, IAP = Ion Activity Produc K water analyses and produces the [filename]. PAT input = solubility product file to NETPATH. Files for checking charge If Ω > 1, the supersaturating state prevails, imbalances in original data and data reports of water Ω < 1, the sub-saturating state prevails, Ω = 1, the analyses are optionally produced from DB. equilibrium state prevails. NETPATH automatically updates the minerals data file, NETPATH.DAT, upon normal termination, saves For the large deviations from the equilibrium a model input files and model result files. logarithmic scale can be useful like the saturation index Samples were analyzed and the major anions and (SI). The index is expressed as: cations were processed into the program WATEQF as an input file for each sample. The program converts the SI = Log (IAP/K) concentrations into mol/l and calculates the activities of If SI = 0, there is equilibrium state between the minerals elements and species of each sample. The program and the solution. calculates the saturation indices of Calcite, Aragonite, Dolomite, Siderite, Rhodochr, Gypsum, Anhydrite, SI < 0, there is sub-saturation state prevails, SI > 0, there is supersaturating state prevails, and Hematite, Goethite, Vivianit, H2 Gas and Partial carbon consequently precipitation processes occurred and the dioxide P-CO2. The positive signs of the saturation index (SI) mean that the solution is supper saturated and the solution unable to dissolve any quantity of minerals. negative signs reflect that the solution is sub-saturated and

INPUT DATA Ionic Strength Activity of ions Activity of (Chemical complex Analysis)

Mol. conc. of Ionic activity product complexes (IAP) Log Solubility product (KT)

Mol. conc. of IJSER species SATURATION INDEX (SI) SOLUBILITY PRODUCT (KT)

> 0.0 = 0.0 < 0.0 SUPERSATURATION EQUILIBRIUM SUBSATURATION

(Fig. 13 ): Flow chart of WATEQF program (Plummer et al., 1988). Table ( 2 ): shows the constraints and Phases used by DB and NETPATH in the study area.

NO. CONSTRAINTS PHASES 1 Sodium Na-Mont. 2 Potassium K-Mont. 3 Calcium Ca-Mont. 4 Magnesium Dolomite 5 Chloride Sodium Chloride

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1559 ISSN 2229-5518 6 sulfur Gypsum 5.4.2. Model 7 Carbon Aragonite into the results: 8 Iron Geothite model as 9 Manganese Rhodochr constraints The . Na- results 10 Nitrogen NH3 gas montmorill obtained from 11 Phosphorus Vivianit onite, K- NETPATH montmorillonite, Ca-montmorillonite, Dolomite, have been established (Tables 3&4 ) The net Sodium Chloride, Gypsum, Aragonite, Goethite, geochemical mass-balance reactions between initial Rhodochr, NH3 gas and Vivianit were selected as and final waters of ten Profiles selected along the interactive phases of the aquifer. The results of mass – groundwater flow path of the Pleistocene aquifer (Fig. balance transfer along groundwater flow path are 14 ) was preceded, Sodium, Potassium, Calcium, presented in (Tables 3&4 ) . magnesium, Chloride, Sulfur, Carbon, iron, Manganese, Nitrogen and Phosphorus were introduced

00 30 30 30 31 00 30 50

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42 Final Point 45 46

Legand Main Road Main irrigation Canal 30 Secondary irrigation Canal 10 0 4 12 20 Km. Shallow well ( 65 m ) 10

30 Deep well ( 65 m - 170 m ) Scale IJSER30 00 30 30 31 00 (Fig.14 ): Profiles selected along the groundwater flow path in shallow and deep groundwater wells of the Pleistocene aquifer in the study area.

Table (4): Minerals results of mass balance transfer (NETPATH MODEL) along a flow path in shallow groundwater wells of the Pleistocene aquifer in the study area.

Well Na- K- Ca- Sodium Dolomite Gypsum Aragonite Geothite Rhodochr Vivianit No. Mon Mon Mon Chloride 85 & 6.929 0.156 -2.724 0.0421 2.247 17.638 -1.232 -0.011 0.0005 0.0047 54 55 & 3.971 0.311 11.880 0.372 4.852 18.005 -6.132 0.00015 0.0015 0.0016 54 70 & 22.01 2.099 -18.29 3.360 7.933 17.816 -8.355 -0.0089 0.0034 0.0040 75

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1560 ISSN 2229-5518 70 & 23.686 2.566 -15.46 2.186 9.240 19.233 -7.760 -0.011 0.00124 0.0029 64 o Positive sign (+): dissolution of mineral (m.mole/Kg) Negative sign (-): Precipitation of mineral (m.mole /Kg) aTable ( 5 ): Minerals results of mass balance transfer (NETPATH MODEL) along a flow path in deep groundwate wells of the Pleistocene aquifer in the study area.

Well Na- K- Ca- Sodium Dolomite Gypsum Aragonite Geothite Rhodochr Vivianit No. Mon Mon Mon Chloride 43 & 5.285 2.797 3.564 1.0029 7.815 15.918 -5.460 -0.0009 0.00115 0.00084 42 51& - 1.979 2.582 0.540 -0.0193 9.039 -0.781 -0.0007 0.0018 0.00056 37 6.925 - 12 & 1 0.372 8.517 1.361 2.043 10.731 -4.186 -0.0004 0.00184 0.00065 3.482 20 & - 0.388 3.704 1.841 2.743 4.802 -3.244 -0.0007 -0.00151 -0.0004 18 7.276 ositive sign (+): dissolution of mineral (m.mole/Kg) egative sign (-): Precipitation of mineral (m.mole /Kg) he results obtained from NETPATHIJSER have been established Chloride, 0.0005 mmole Rhodochr and (Tables 3 and 4 ) The net geochemical mass-balance 0.0047 mmole Vivianit (all expressed mmole reactions between initial and final waters of ten per kg of groundwater). Profiles selected along the groundwater flow path of b) Profile (B): The mass–balance transfer along this the Pleistocene aquifer (Fig. 14 ) was preceded, profile reflect precipitation of -6.132 mmole aragonite Sodium, Potassium, Calcium, magnesium, Chloride, and dissolution of 3.971mmole Na- Mont, Sulfur, Carbon, iron, Manganese, Nitrogen and 0.311mmole K- Mont, 11.880 mmole Ca- Mont, 0.372 Phosphorus were introduced into the model as mmole Dolomite, 4.852 mmole Gypsum, 18.005 constraints. Na-montmorillonite, K-montmorillonite, mmole Sodium Chloride, 0.00015 mmole Goethite, Ca-montmorillonite, Dolomite, Sodium Chloride, 0.0015 mmole Rhodochr, 0.0016 mmole Vivianit.

Gypsum, Aragonite, Goethite, Rhodochr, NH3 gas and c) Profile (C): The mass–balance transfer along this Vivianit were selected as interactive phases of the profile precipitation -18.29 mmole of Ca- Mont, - aquifer. 8.355 mmole of Aragonite, -0.0089 mmole of The following can be concluded: Goethite and dissolution of 22.01 mmole Na-Mon, a) Profile (A): The results of mass–balance 2.099 mmole K-Mon, 3.360 mmole Dolomite, 7.933 transfer along this profile reflect precipitation mmole Gypsum, 17.816 mmole Sodium Chloride, of -2.724 mmole of Ca-mon, -1.232 mmole 0.0034 mmole Rhodochr, 0.0040 mmole Vivianit. Aragonite, -0.011 mmole Goethite and d) Profile (D): The mass–balance transfer along this dissolution of 6.929 mmole Na-mon, 0.156 profile reflect precipitation of -15.46 mmole of Ca- mmole K- mon, 0.0421 mmole Dolomite, Mont, -7.760 mmole of Aragonite, -0.011mmole of 2.247 mmole Gypsum, 17.638 mmole Sodium Goethite and dissolution of 23.686 mmole Na-Mon,

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1561 ISSN 2229-5518 2.566 mmole K-Mon, 2.186 mmole Dolomite, 9.240 of of Ca-mon, Aragonite, Goethite – with different mmole Gypsum, 19.233 mmole Sodium Chloride, values . So there is increase in salinity in all profile in 0.00124 mmole Rhodochr, 0.0029 mmole Vivianit. the same direction of groundwater flow, also dissolution e) Profile(E): The results of mass–balance transfer of both Rhodochr and Vivianit leads to increase the along this profile reflect precipitation of -5.460 mmole concentration of nitrates and phosphate as a result of Aragonite, -0.0009 mmole Goethite and dissolution of extensive use of chemical fertilizer and pesticides . 5.285 mmole Na-Mon, 2.797 mmole K-Mon, 3.564 Even through primary silicate minerals (clay mmole Ca-Mon, 1.0029 mmole Dolomite, 7.815 minerals) predominate in the mineralogy of the mmole Gypsum, 15.918 mmole Sodium Chloride, Quaternary aquifer in the study area, the mass balance 0.00115 mmole Rhodochr and 0.00084 mmole modeling indicates that reactions with these minerals are Vivianit. secondary to those of the more reaction carbonate , f) Profile (F): The results of mass–balance transfer sulfate and chlorides and precipitation of Ca-mon, K- along this profile reflect precipitation of -6.925 mmole mon , and Na-mon. in different profiles. [16] and Na-Mon, -0.0193 mmole Gypsum, -0.781 mmole [17] . Aragonite, -0.0007 mmole Goethite and dissolution of This reaction agreement with the sequence of 1.979 mmole K-Mon, 2.582 mmole Ca-Mon, 0.540 cations (Na+>Ca++ > Mg++), (Na+>Mg++ > Ca++) and mmole Dolomite, 9.039 mmole Sodium Chloride, - — - anions (Cl > SO4 >HCO3 ). From these profiles 0.0018 mmole Rhodochr and 0.00056 mmole Vivianit. we notes the groundwater change from less advanced g) Profile (G): The results of mass–balance transfer - — - stage of mineralization (HCO3 > SO4 > Cl ) to along this profile reflect precipitation of -3.482 mmole - — more advanced stage of mineralization (Cl > SO4 Na-Mon, -4.186 mmole Aragonite, -0.0004 mmole >HCO3-) Goethite and dissolution of 0.372 mmole K-Mon, V- Evaluation of groundwater according to U.S. 8.517 mmole Ca-Mon, 1.361 mmole Dolomite, 2.043 Salinity Laboratory Staff (1954): mmole Gypsum, 10.731 mmole Sodium Chloride, Groundwater of the Pleistocene aquifer in the 0.00184 mmole Rhodochr and 0.00065 mmole study area is evaluated according to [18] based on the Vivianit. Sodium Adsorption Ratio (SAR), and the specific h) Profile (H): The results of mass–balance transfer conductance (Fig. 15). The U.S. Salinity Laboratory along this profile reflect precipitationIJSER of -7.276 diagram is divided into four classes C1, C2, C3 and C4, mmole Na-Mon, -3.244 mmole Aragonite, -0.0007 which denote the conductance and S1, S2, S3 and S4 mmole Goethite, -0.00151 mmole Rhodochr, -0.0004 which denote the sodium adsorption ratio (SAR). The mmole Vivianit and dissolution of 0.388 mmole K- recommended classification of water for irrigation Mon, 3.704 mmole Ca-Mon, 1.841 mmole Dolomite, according SAR ranges are shown in (Table). 2.743 mmole Gypsum and 4.802 mmole Sodium SAR = Na+/ (ca++ + Mg++) /2 Chloride. Where, the concentrations of these cations are expressed The predominant reactions for all profiles appear in mq/l according to √the U.S. Salinity Laboratory to be dissolution of Sodium Chloride, Gypsum, diagram. Dolomite, Rhodochr and Vivianit ., and precipitation

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1562 ISSN 2229-5518 Sodium (alkali) Hazard 100 500 1000 5000 Very 30 30 High C3-S4 C4-S4 S4 28 C1-S4 C2-S4 26 24 High S3 22

20 C1-S3 C2-S3 20 18 16 Medium

S R S A C3-S3 S2 14 12 C1-S2 C2-S2 C4-S3 10 10 C3-S2 8 Low 6 C4-S2 S1 4

2 C1-S1 C2-S1 C3-S1 C4-S1 0 100 250 750 2250 Conductivity (micromhos/cm at 25 C) Shallow well C1 C2 C3 C4

Deep well Low Medium High Very High Salinity Hazard (Fig. 15): Water classification for irrigation according to US Salinity Lab. 1954) [19] As shown from figure 15, it clears that: most of manganese bearing deposits? groundwater samples are good to moderate water class Zinc contents in all the collected samples are less and suitable for irrigation purposes and only 17 % of than 5 mg/l, ranging from 1 mg/l to 5 mg/l in shallow shallow groundwater samples and 2 % of deep groundwater samples. Relatively high concentration of groundwater samples falls in the bad water classes (C3- zinc were recorded at few places and ranging from 0.2 S4) and (C4-S4) which are unsatisfactory. mg/l to 0.3 mg/l in deep groundwater wells Trace elements: Phosphate contents in the collected groundwater Iron content was measured in the collected samples are ranging from 0.02 mg/l to 0.1 mg/l of the groundwater samples, it ranging. ranging from 0.04 majority of groundwater samples . Generally, phosphates mg/l to 0.36 mg/l in shallow production wells, and enter the water supply from agricultural fertilizer run-off, ranging from 0.01 mg/l to 0.18 mg/l in the majority of water treatment, and biological wastes and residues. groundwater samples in deepIJSER production wells . Iron Results of chemical analysis show that nitrite is concentration increases gradually toward the southeastern not detected in all samples, while concentration of nitrate portions. According to the standard acceptable limits in studied area ranges from 6 mg/l to 33 mg/l in the major (0.3 mg/l) [19] and [20], , Egyptian standard for drinking and shallow groundwater samples and from 1mg/l to 6.8 domestic uses all samples of deep groundwater wells mg/l in the major deep groundwater samples high are suitable value of iron according to the same values of Phosphate and Nitrite content related to standard limits. also most of shallow groundwater excessive uses of chemical fertilizers and pesticide . wells are suitable value of iron according to the same Conclusion standard limits . Except 32.5 % of recorded samples There is great diversity in environmental polluted with iron according to the same standard impacts in the study area, these effects represented in limits . the effects of agricultural activity and increased Manganese contents in the collected reclamation land projects, an addition to activity groundwater samples ranging from 0.05 mg/l to 0.4 associated with the different interactions of salts which mg/l in shallow groundwater samples and ranging from leads to of dissolution and precipitation of minerals. 0.06 mg/l to 0.32 mg/l in deep production wells in the These environmental impacts lead to affects on the study area. The recommended maximum of manganese quality of water, and also on the evolution of water concentration for public water supplies is 0.05 mg/l and these appear through the results of the program [19]. The concentration of manganese content (Netpath). according to the Egyptian standard limits (0.1 mg/l), Using geochemistry as a tracer of most groundwater samples in the study area is polluted groundwater flow requires a clear understanding of with manganese. Which reflects effect of dissolution of the origin of the geochemical patterns, in line with

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1563 ISSN 2229-5518 the suggestion by [21], [22] and [15] and Netputh results increase the concentration of certain minerals program. There is a clear geochemical zonation in and decrease in others, this leads to an evolution in the the composition of the study area waters following quality of the water where water quality turned from - — the geological sequence. This zonation is the initial stages of mineralization ( HCO3 > SO4 characterized by a change of cation species from > Cl-) ) to a higher stage in the mineralization (Cl- > — - dominantly Ca and Mg near the east to Na- SO4 >HCO3 ) according to [23] and [24] dominated waters in the west. Mirroring this, anions Water was evaluated for irrigation using SAR change from HCO3 type to Cl and SO4 type. sodium adsorption ratio, the majority of groundwater So, The consequent of cations and anions change, the samples in the study area are suitable for irrigation.

References 1- Gallardo, A. H., and Tase, N. (2007): Hydrogeology and geochemical characterization of groundwater in a typical small-scale agricultural area of Japan. Journal of Asian Earth Sciences, 29(1), 18-28. [doi:10.1016/j.jseaes.2005.12.005] 2- Xu, Z. H., Li, Y. F., Jiang, L., Hou, G. C., and Hu, A. Y. (2009): Geochemical modeling of Huanhe water-bearing layers in South Ordos Basin. Journal of Arid Land Resources and Environment, 23(9), 160-168. (In Chinese). 3- Wang, P. M., Anderko, A., Springer, R. D., Kosinski, J. J., and Lencka, M. M. (2010): Modeling chemical and phase equilibria in geochemical systems using a speciation-based model. Journal of Geochemical Exploration, 106(1-3), 219-225. [doi:10.1016/j.gexplo.2009.09.003] 4- Belkhiri L, Boudoukha A, Mouni L, Baouz T. (2010): Application of multivariate statistical methods and inverse geochemical modeling for characterization of groundwater - A case study: Ain Azel plain (Algeria). Geoderma159:390–398. 5- ASTM, American Society for testing and material (2002). In "water and environmental technology". annual book of ASYM standars, Sec. 11, Vol. 11.01 and 11.02, West Conshohocken, U.S.A. 6- Plummer NP, Prestemon EC, Parkhurst DL.(1994). An interactive code NETPATH for modelling net geochemical reactions along a flow path_version 2.0. United States Geological Survey, 120 p. 7- Lyon WB, Bird DA. (1995): Geochemistry of the Madeira River Brazil comparison of seasonal weathering reactions using a mass balanceIJSER approach. J S Am Earth Sci ;8(1).:97-101 8- Soulsby C, Chen M, Ferrier RC, Helliwell RC, Jenkins R, Harriman R.(1998). Hydrogeochemistry of shallow groundwater in an upland Scottish catchment. Hydrol Process;12: 1111-1117. 9- El Abd, A.E. (2005): "The geological impact on the water bearing formations on the area southwest Nile Delta, Egypt". Ph.D. Thesis, Fac. Sci. Menofiya Universuty. 10- Starinsky, A.; Bielski, M.;Eckerr, A. and Steinitz, G.(1983). Tracing the origin of salts in groundwater by Sr isotopic composition (The crystalline complex of the southern Sinai, Egypt), Isotope Geoscience, 1: 257-267. 11- Todd, D. K. (1959). Groundwater Hydrology 2 nd edition., John Wiley and Sons Inc., New York, U.S.A., 336 12- Piper , A.M.(1953 ): "Agraphic representation in the Geochemical interpretation of groundwater analysis" Am. Geophis. Union Transactions, 25:914-923. 13- Truesdell, A. H., and Jones, B. F., (1974), WATEQ, a computer program for calculating chemical equilibria of natural waters: Journal of Research, U.S. Geological Survey, v. 2, p. 233-274. 14- Plummer, L.N. Parhurst, D.L; Fleming, G.W. and Dunkel, S.A. (1988): A computer program incorporating pitzers equations for calculation of geochemical reactions in brines. U.S. Geol. Surv., Water Resour. Inv. Rep. P. 88-4153. 15- Glynn PD, Plummer LN. (2005) Geochemistry and understanding of groundwater systems. Hydrogeology J. volume 13: pp 263–287. 16- Appelo CAJ and Postma D. (2005). Geochemistry, groundwater and pollution.A.A. ,second edition, Amesterdam, the Netherlands, Balkema 649 p. 17- Postma

IJSER © 2015 http://www.ijser.org International Journal of Scientific & Engineering Research, Volume 6, Issue 4, April-2015 1564 ISSN 2229-5518 18- Salinity Laboratory: ( 1954) ; "Diagnoses And Improvements of Saline And Alkaline Soil "S. S. Dept. of Agriculture , Hand Book , No. 60 ,pp. 160. 19- World Health Organization (WHO) (2005). International standards for drinking waters. 5th Edition, Vol. 1 Geneva, Switzerland 20- Environmental Protection Agency (E .P .A .); ( 1984 ): " National Intrim. Primary Drinking Water Regulation " U.S. E P A Part 141, Federal Register 40 (248 ), Dece.24 , pp. 59566 – 59588. 21- Domenico, P.A., and Schwartz, F.W.,(1990), Physical and chemical hydrogeology: John Wiley and Sons, New York, 824 p. 22- Hem, J. D., (1989): Study and interpretation of the chemical characteristic of natural water. U.S. geol. Surv., Water supply paper 2254, 3rd edition, 264 p. 23- Burdon, D.J. (1958). Metasomatism of groundwater at depth, UNESCO course on Hydrology, Desert Institute, Cairo, Egypt 24- Back, W. and Hanshaw, B. B. (1979): “Major geochemical processes in the evolution of carbonate aquifer system’’. Elsevier Scientific Publishing Company, Amsterdam, the Netherlands.

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