Journal of Water Research.138 (2017) 361-370 https://sites.google.com/site/photonfoundationorganization/home/journal-of-water-research Original Research Article. ISJN: 3294-9473: Impact Index: 4.62

Journal of Water Research

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Capability of Natural Bentonite for Removing Organic and Inorganic pollutants from Wastewater Ali M.M.*a, El-Sayed E.Eb a

Deputy Director and Operation Manager at Central Laboratory for Environmental Quality Monitoring (CLEQM), National Water Research Center (NWRC), El-kanater, Qalubiya, Egypt b Researcher at CLEQM

Article history: Received: 17 June, 2017, Accepted: 20 June, 2017, Available online: 25 September, 2017 Keywords: Wastewater treatment, natural bentonite, adsorption, heavy metals, ammonia, removal efficiency. Abbreviations: NH4+: ammoniumion; Al: aluminium; Ba: barium; Cd: cadmium; Cr: chromium; Cu: copper; Fe: iron; Mn: manganese; Pb: lead; Ni: nickel; and Zn: zinc; XRD: XRay diffraction; XRF: X-Ray fluorescence; ESM: Electroscaning Microscope; COD: chemical oxygen demand; BOD: biological oxygen demand; TSS: total suspended solid; TN: total nitrogen; TP: total phosphorus. Corresponding Author: Ali M.M*, Professor of Analytical Chemistry Email: mah aali_59 ( at ) yahoo ( dot ) com Abstract: Currently, water scarcity challenges are facing many countries worldwide. The treatment and reuse of wastewater within the international guidelines can be present a solution of water scarcity. In this study, the adsorption capacity of natural local bentonite to different pollutants was investigated on two stages. Stage one concerned about selecting the optimum conditions (pH, weight of adsorbent, initial concentrations of pollutants and contact time) for removal of ammonia (ammonium ion) and heavy metals from aqueous solution. In stage 2, The optimum condition obtained from stage 1 were applied for the removal of chemical oxygen demand (COD), biological oxygen demand (BOD), total suspended solid (TSS), total nitrogen (TN), total phosphorus (TP) and turbidity from sewage samples collected from CLEQM septic tank. To improve the removal efficiency, the samples were left for settled down and precipitate the suspended matter before treatment at various contact time. The results revealed that the percentage of removal efficiency 58, 97, 88, 90, 76, 91, 69, 90 % for ammonium ions (NH4+), heavy metals, COD, BOD, TSS, TN, TP and turbidity respectively. This study revealed that bentonite can be used as a very low cost material, environmentally safe and good adsorbent for removing organic and inorganic pollutants. Citation: Ali M.M.*, El-Sayed E.E., 2017. Capability of Natural Bentonite for Removing Organic and Inorganic Pollutants from Wastewater. Journal of Water Research. Photon 138, 361370 All Rights Reserved with Photon. Photon Ignitor: ISJN32949473D870025092017

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1. Introduction The treatment of wastewater coming up from community and municipalities must be agreed with the environmental standard before it was reused or returned to surface water (Novoselov et al., 2004). There are various important parameters such as total suspended solids (TSS), major cations, turbidity and chemical oxygen demand (COD) are the main characteristics of the municipal and industrial wastewater effluents in addition to ammonia and heavy metals. The main problem of high levels of chemical oxygen demand results in reducing dissolved oxygen in water system then leads to death of aquatic organisms, while the contamination with suspended solids resulting from organic and inorganic substance can cause the water system being polluted by odor and dirt (Tahir et al., 2009) growth of the natural cycle, many of them become to be harmful at high amount. A few researches were conducted to enhance and develop a powerful and economic process for removal of toxic substance (Papayannis et al., 2010). The most developed techniques for hazard material removal are related to sorption mechanism, ion exchange processes. Over all the various absorbent materials used for toxic compound removal are bentonite, zeolite and activated carbon (Easton et al., 2007). Using of clay minerals as adsorbent in wastewater treatment has become more widely and efficient for heavy metal, organic pollutants, and nutrients removing (Tanner et al., 2004). Surface water, ground water and soil contamination with ammonia and harmful metal ions even at a few levels is a big issue, and has danger effect to the environment, while the nitrogen as nitrous oxide, nitric oxide, nitrate, nitrite or ammonia is water soluble and can reach to ground and drinking water causing serious problem (Janteng et al., 2007). The utilization of clays as adsorbent in wastewater treatment was increased due to its abundance, low expensive and has a great ability to absorb and remove several forms of pollutants including heavy metals in waters due to the presence of montmorillonite (Ayala et al., 2008). The mechanism of ion exchange process and the amount of pollutants absorbed are strongly dependent on where the clay material comes from, the impurities percentage. Bentonite is considered one of most important clays which have large surface area and negative sign to catch the pollutants ions from surrounding environment (König, 2012). The surface areas and capacities of exchange make it characterized with high sorption capabilities (Babel et al., 2003). Bentonite clay is classified into two type’s sodium Ph ton

and calcium bentonite. The sodium type is volcanic ash origin and generally possesses high swelling, while the other type of calcium bentonite volcanic ash evolved and deposited on fresh water system and low swelling (Al Dwairi et al., 2012). Karapinar and Donat (2009) studied the uptake capacity of bentonite for chromium, copper, zinc and manganese. The obtained results indicate that the adsorption capacity of bentonite for various metal ions is charge density and hydrate ion diameter depends. Therefore, the current study aims to investigate an economically feasible, simple to operate, efficient and sustainable treatment method in order to protect our surface water and also choosing the optimum operating conditions with the possible methods of application for using natural bentonite in the removal of organic and inorganic pollutants (heavy metals, ammonia, chemical oxygen demand, biological oxygen demand, total suspended solid, total nitrogen, total phosphorus and turbidity) from wastewater. Justification of Research In Egypt, water pollution in the different irrigation and drainage channels is a challenging issue. This pollution prevents water managers from recycling the drainage water especially in the era of the Egyptian water scarcity. Therefore, de-pollution and removing whatever pollutants from different waterways are targets for the Egyptian scientific community towards supporting decision makers in facing the various water challenges in Egypt. The current research is considered a break-through in finding a safe, low coast and efficient material available in the Egyptian environment that can reduce the pollution load from the different water ways. This study started with utilizing the natural bentonite in a laboratory scale to evaluate its efficiency for removing hazard contaminants. The research authors are planning to upscale the experiment to be applied in small channel. 2. Experiments 2.1. Preparation and characterization of adsorbent The bentonite clay was obtained from Masr Company for Mineralization and Bentonite, Burg El-Arab, Egypt. The sample was ground in a ball mill and only particles smaller than 0.25 mm, were used for the batch experiments. The mineralogical properties of natural bentonite were determined by X-Ray Powder Diffraction (XRD) using a PAN analytical X-Ray Diffraction equipment model X Pert PRO. The chemical composition was analyzed using X-Ray Fluorescence (XRF) spectroscopy (Axios, sequential WD- XRF spectrometer, PAN 362

analytical 2005), while the adsorbent was scanned using Electro scanning microscope (ESM) model JEM- 2200FS. 2.2. Preparation and analysis of initial concentrations of pollutants The aqueous solution of ammonia and heavy metals were prepared as following: 2.2.1. The concentrations of ammonia (5 and 10 mg/l) were prepared using crystalline ammonium chloride (Merck brand-NH4Cl). A defined weight was dried at 70°C. The initial concentrations of ammonium ions before and after batch experiment were measured using Ion Chromatography (model Dionex ICS 5000), while pH was measured using an Orion Ross Combination Probe (model 8115BN) with digital meter (model 960). 2.2.2. Metals stock standard of multi element (Al, Ba, Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn, 1000 mg/l Merck Brand), has been used to prepare concentrations of heavy metals (0.5 and 1.0 mg/l) with deionized water and negligible drops of nitric acid. The metals were analyzed using ICP-MS (model Perkin Elmer, NexION 300D) financed by Science and Technology Development Fund (STDF). 2.3. Sewage samples collection and analysis Sewage samples were collected from CLEQM’S septic tank and analyzed for COD, BOD, TSS, TN, TP and turbidity. The samples collection, preservation and analysis regarding all investigated parameters were conducted according to the Standard Methods for the Examination of Water and Wastewater (APHA, 2012). The COD and BOD parameters were determined by Hach DR 3900 and BOD incubator respectively. Total suspended solid was determined gravimetrically. The sewage samples were digested for the determination of TN and TP, while the distillation unit of Kjeldahl model 132D and Hach DR 3900 are used for determination of the mentioned parameters respectively. Turbidity was determined using turbidity meter (model Thermorion AQ 4500). 2.4. The batch experiments 2.4.1. Stage 1: Selecting the optimum conditions of using bentonite to remove ammonia and heavy metals. The adsorption capacity of natural bentonite to uptake ammonium and metal ions from aqueous solution was investigated under various conditions (pH, weight of adsorbent, initial concentrations of pollutants and contact time). Batch adsorption experiments were conducted using different Ph ton

weights of bentonite (0.5, 1.0 and 2.0 g) added to 100 ml of aqueous solutions with varying pollutants initial concentrations. Small volumes (negligible) of sodium hydroxide and hydrochloric acid were added to the aqueous solution to adjust the desired pH (4, 6 and 8). The constant volumes (100 ml) of prepared solution from ammonium chloride and heavy metals were shaking (100 rpm at 25°C) for four hours with various weights of adsorbent to allow the interaction between adsorbent and sorbent. Then the samples were filtered and the concentrations of ammonium ion and different heavy metals ions were measured. 2.4.2. Stage 2: The sewage samples were left to settled down and precipitate the suspended matter for two hours before treatment with bentonite, while the optimum conditions obtained from stage (1) were applied to examine the removal efficiency of bentonite for COD, BOD, TSS, TN, TP and turbidity at different contact time. The removal efficiency of bentonite was calculated by the following equation:

Where, C∘ is the initial concentration of pollutants (mg/l) and Ce is the final concentration of the pollutants after treatment (mg/l). 3. Results and Discussion 3.1. Characterization of natural bentonite The characterization of bentonite by X Ray Diffraction indicates that it consists of minerals (calcium and magnesium), quartz, montmorillonite, kaolinite and dolomite as shown in Table (1) and Figure (1). Quartz mineral has a hexagonal crystal structure made of trigonal crystallized silica (silicon dioxide, SiO2), while the montmorrilonit is a mineral that contains compounds of Al2O3 4Si.H2O. The structures of bentonite composed of a single plate layer occupied between aluminum (Al2O3) and silica (SiO2) plates that can be expand or contract. Kaolinite clay considered the major part of the kaolin clay, consisting of aluminosilicate minerals (Al2O3SiO2H2O). Dolomite is an anhydrous carbonate mineral composed of calcium magnesium carbonate (Naswir and Arita, 2013). The chemical composition of adsorbent was studied by X-Ray Fluorescence (XRF) and presented in Table (2), while Figure (2) shows the electroscaning microscope (ESM) of bentonite sample, which can be observed as a layers arranged above each other. This laminar structure can be representative a structural model of montmorillonite. The model 363

structure presents Al-O and Si-O bonds in octahedral and tetrahedral layer sheets, respectively. This structure is agreed with Ayala et al., (2008) who found that the tetrahedral sheets are Table 1: Mineralogical composition, mass (%) of the natural bentonite. Mineral Name Chemical Formula Quartz Si 3.00 O 6.00 Si 7.80 Al 1.72 Li 0.16 Fe 0.20 Mg 0.28 O Montmorillonite 20.00 Kaolinite Al 2.00 Si 2.00 O 9.00 H 4.00 Dolomite Ca 3.00 Mg 3.00 C 6.00 O 18.00 Table 2: Chemical analysis of bentonite Content Al2O3 SiO2 Fe2O3 CaO K2O TiO2 Trace of other elements (Mn, Cl, Mg, Cr,…….etc)

Composition (%) 22 56 4.77 2.85 1.39 0.12 12.87

Table 3: Removal efficacy of ammonium ions at various pH, initial conc., adsorbent weight and contact time

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Table 4: Removal efficiency of heavy metals (0.5 mg/l) at various pH, adsorbent weight (2g) and contact time Heavy metals adsorption (%) using 2 g of bentonite No.

Contact time

1 2 3 4 5 6 7

Aluminium Barium Cadmium Chromium Copper Iron Lead

8

st

pH 4 84.5 83.3 87.3 89.4 84.2 81.2 86.1

2nd hours pH 6 86.2 84.2 88 91.1 87.5 83.4 88.0

pH 8 86.0 84.1 87.8 90.8 87.2 83.1 87.8

75.2

82.3

86.1

85.7

85.2

87.2

78.3

78.0

84.7

pH 4 80.6 78.1 81.6 84.2 73.5 76.1 82.3

1 hour pH 6 83.2 81.7 85.4 86.3 78.6 78.0 84.1

pH 8 82.4 81.0 85.1 86.1 78.2 77.8 83.9

Manganese

72.1

76.5

9

Nickel

83.4

10

Zinc

76.0

pH 4 93.8 90.5 90.9 92.9 91.7 90.5 89.6

3rd hours pH 6 95.1 95.5 97.0 94.4 93.2 91.8 93.5

pH 4 84.0 87.1 88.3 83.0 81.1 81.7 81.5

4th hours pH 6 84.5 88.0 89.6 84.0 83.2 84.4 84.2

pH 8 94.8 95.2 96.5 94.1 93.0 91.3 93.0

pH 8 84.1 87.9 89.2 83.8 82.9 84.4 83.8

86.2

90.7

91.5

91.5

81.2

83.0

82.8

89.5

88.9

91.5

92.2

91.9

74.5

78.2

78.1

87.9

87.2

91.5

93.5

93.0

84.3

86.0

85.8

Table 5: Removal efficiency of heavy metals (0.5 mg/l) at various pH, adsorbent weight (1g) and contact time. Heavy metals adsorption (%) using 1 g of bentonite 1st hour 2nd hours 3rd hours 4th hours No. Contact time pH 4 pH 6 pH 8 pH 4 pH 6 pH 8 pH 4 pH 6 pH 8 pH 4 pH 6 pH 8 1 2 3 4 5 6 7 8 9 10

Aluminium Barium Cadmium Chromium Copper Iron Lead Manganese Nickel Zinc

71.8 73.5 75.9 71.9 73.7 77.9 70.5 72.7 72.5 76.4

75.3 74.5 76.8 73.0 80.5 79.3 72.0 74.6 75.6 77.2

74.9 74.1 76.2 72.8 79.8 79.0 71.8 73.9 74.9 76.8

80.6 78.3 79.1 76.7 80.3 82.1 75.3 75.1 78.4 79.2

81.7 79.6 83.2 77.6 82.8 87.0 76.2 78.4 80.7 80.4

81.2 79.0 83.0 77.2 82.0 86.7 76.1 78.2 80.2 80.1

87.3 86.5 85.9 81.9 84.7 84.7 83.3 79.7 82.5 83.6

88.2 88.1 89.3 83.4 89.5 89.8 84.0 80.8 84.4 86.1

87.9 81.5 88.9 82.8 89.2 89.5 83.7 80.3 84.0 85.7

76.1 75.1 73.4 75.4 74.4 71.3 72.6 72.4 71.1 74.5

77.6 77.7 76.9 78.3 76.6 73.7 73.7 73.6 72.5 76.7

Table 6: Removal efficiency of heavy metals (0.5 mg/l) at various pH, adsorbent weight (0.5g) and contact time. Heavy metals adsorption (%) using 1 g of bentonite 1st hour 2nd hours 3rd hours 4th hours No. Contact time pH 4 pH 6 pH 8 pH 4 pH 6 pH 8 pH 4 pH 6 pH 8 pH 4 pH 6 1 Aluminium 71.6 73.4 73.1 75.8 76.6 76.3 77.8 81.8 81.2 72.3 74.2 2 Barium 73.5 76.8 75.3 78.2 79.3 78.7 80.4 81.3 80.8 76.8 77.0 3 Cadmium 74.7 76.6 76.1 81.9 83.4 82.9 84.9 88.4 87.6 73.1 75.4 4 Chromium 78.2 79.4 78.8 80.3 81.0 80.6 82.7 84.7 84.1 73.1 75.3 5 Copper 71.2 73.5 72.4 75.2 76.3 74.6 81.3 82.8 81.8 75.4 76.8 6 Iron 73.1 75.2 74.7 76.7 77.8 76.4 82.6 84.7 83.7 75.8 76.3 7 Lead 70.8 72.4 75.7 76.8 78.4 77.2 80.7 83.2 82.6 74.1 76.6 8 Manganese 72.4 75.5 74.8 76.2 77.3 75.8 82.6 84.7 84.1 72.4 74.3 9 Nickel 72.2 73.7 73.1 75.6 78.6 77.3 81.2 84.6 83.8 72.4 74.6 10 Zinc 73.7 75.7 74.3 76.7 78.4 77.8 83.4 85.4 83.8 73.8 75.4

77.1 76.9 75.8 78.1 75.8 73.2 73.3 73.2 72.2 76.3

pH 8 74.1 77.0 74.9 72.8 75.4 74.7 75.9 71.6 73.1 73.7

Table 7: The chemical analysis of CLEQM’S septic tank for the tested parameters No.

Parameters

Unit

Results

1

Chemical Oxygen Demand (COD)

mg/l

63

2

Biological Oxygen Demand (BOD)

mg/l

42

3

Total Suspended Solids (TSS)

mg/l

62

4

Total Nitrogen (TN)

mg/l

96.7

5

Total Phosphorus (TP)

mg/l

2.23

6

Turbidity

NTU

42

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Figure 1: spectrum XRD of bentonit Counts 80

2

60

40

20

0 10

20

30

40

50

Position [°2Theta] (Copper (Cu))

Figure 2: ESM of bentonite.

Figure 3: Removal efficiency of COD and BOD against contact time using 2g of bentonite 100

Removal % Removal %

85

70 55

COD

40

BOD

25 1 Hour 2 Hours 3 Hours 4 Hours Contact time

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Figure 4: Removal efficiency of TSS and turbidity against contact time using 2g of bentonite 100

70

55 40

Removal %

Removal %

85

TSS

Turbidity

25 1 Hour 2 Hours 3 Hours 4 Hours Contact time

Figure 5: Removal efficiency of TN and TP against contact time using 2g of bentonite

80 60

40

Removal %

Removal %

100

20

TN

TP

0 1 Hour 2 Hours 3 Hours 4 Hours Contact time

forming the hexagonal cavities which play an important role during adsorption process. On the other hand, siloxane bonds located at its edges and external surfaces allow removal of pollutants in solution, carried out mainly by cation exchange and by complexation with oxygenated groups. This construction allows to understanding of the mechanisms involved during adsorption of pollutants. 3.2 Batch Study (Stage 1) There are many factors effect on sorption of toxic materials by clays such as pH of solution, weight of adsorbent, initial concentrations of pollutants, temperature and contact time. The removal efficiency of natural bentonite towards different organic and inorganic pollutants was studied under the previous conditions except temperature. 3.2.1. Effect of pH The adsorption of ammonium and metal ions from solution is strongly dependent on the pH due to its influence the metal ions solubility (White et al., 2005). The effect of pH was investigated with various initial concentrations of ammonia and heavy metals at 25 °C. The uptake of ammonia and heavy metals Ph ton

by natural bentonite as a function of pH are presented in Tables (3-6). It was observed that the sorption of the metal and ammonium ions decreased at low pH. That is due to the competition between positive charge ions (pollutants) and hydrogen ions with negative sites on the clay (Horsfall et al., 2006). Regarding the obtained results, ammonium and heavy metals ions adsorption increased with increasing pH (Tables 3-6). This behavior agrees with the results of heavy metals adsorption by lucia and Gilvanise (2009). The results support the observation that increasing bentonite solution system pH led, initially, to increase the net negative surface charge on bentonite where, ammonium and heavy metals ions are adsorbed. This can be due to the deprotonation of the most active surfaces of bentonite as a result of surface hydrolysis with increase in pH from 4 to 6. 3.2.2. Effect of initial concentrations of pollutants. The obtained data indicate that the sorption capacity of natural bentonite to ammonium and metal ions is affected by their initial concentrations as presented in Tables (3–6). The adsorption of bentonite was increased as the initial 367

concentrations of pollutants decreased at 25ºC. The results of the current study were agreed with Tito et al., 2011. They reported that the adsorption of natural bentonite to various metal ions was increased by decreasing the initial concentrations of pollutants. 3.2.3. Effect of Clay dosage The current study was performed using different weights of natural bentonite clay (0.5, 1.0 and 2.0 g). The results of ammonium and metal ions removal is presented in Tables (3-6). The obtained results revealed the adsorption values for the investigated parameters were increased by increasing the weight of bentonite. The results of the current study is agreed with the data obtained by Varank et al., (2014). 3.2.4. Effect of contact time During the batch experiment the effect of contact time was also studied. The results are shown in Tables (3-6). The data revealed that percentage of ammonium ions and various adsorbed metal ions increased by increasing contact time. This was due to at the beginning of experiment the adsorption capacity increased due to all sites on the clay were empty and pollutants concentration was high, however by time the sorption sites reduced leads to decreased adsorption rate. The obtained data are match with that found in the experiment of Yu et al., (2000); Sheng et al., (2009) and Mousavi et al., (2010). They found the adsorption rate was high at the first hour and starts gradually decrease by increasing time. The results revealed the optimum contact time for ammonium ions and heavy metals removal is at 120 and 240 minutes respectively, then the uptake rate decreased with increasing contact time. 3.3. Applied study (Stage 2). The applied study was performed using sewage samples collected from CLEQM’S septic tank. The chemical analysis was presented in Table (7). The selected optimum conditions obtained from stage (1) were applied at various contact time to investigate the removal efficiency of bentonite for COD, BOD, TSS, TN, TP and turbidity. The results revealed that the maximum removal efficiency was recorded for TN (91.3 %) and the minimum value was recorded for TP (69%). The results revealed that the adsorption capacity of the selected parameters increased with increasing contact time as shown in Figures (3-5) This is due to the adsorption capacity was increased rapidly at the beginning of study, but it was slowed in the later stages until reaching equilibrium because pollutants form layer on the surface, which prevents more adsorption to bentonite. This

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circumstance is in agreement with the results obtained by Janteng et al., (2007). Conclusion 1-Bentonite clay is low cost, environmentally safe and potentially efficient for pollutants removal from wastewater such as ammonia, heavy metals, COD, BOD, TSS, TN, TP and turbidity parameters. 2- It was found that adsorption capacity of studied pollutants is affected by the pH of solution, weight of adsorbent, the initial concentrations of contaminants and contact time. Research Highlights 1- This study aims to use natural bentonite as an effective material for wastewater treatment from some inorganic and organic pollutants. 2- Natural bentonite can be potentially efficient for pollutants removal due to its peculiar structure which has many sites of cations that are interchangeable for pollutants. 3- The removal capacity is depending on the pH of solution, weight of adsorbent, the initial concentration of contaminants and contact time. 4- The results revealed that the percentage of removal efficiency were 58, 97, 88, 90, 76, 91, 69, 90 % for ammonium ions (NH4+), heavy metals, COD, BOD, TSS, TN, TP and turbidity respectively. Limitations The current study represents one of most effective ways of using natural adsorbent for wastewater treatment. This research utilized the natural bentonite in a laboratory experiments and proved to be very efficient according to the results presented. Therefore, the current research is limited until now for laboratory experimentation. The authors plan to extend their research to a laboratory flume with a flowing water to measure the efficiency of natural bentonite in removing the different pollutants in a small scale channels as well as the other parameters such as the contact time, optimum water flow velocity, amount of bentonite needed compared to the water flow, and any side effects that might be witnessed. Recommendations 1-Bentonite can be used on large scale represented on water flume to investigate if it useful to demonstrates this module at water drainage. 2- This study recommended that the wastewater must be settled before treatment with bentonite to 368

reduce the suspended matter and increase the removal efficiency COD, BOD, TSS, TN, TP and turbidity. Author's Contributions and Competing Interest The authors in the current study are in team work and aiming to use low cost and safe environmentally materials on wastewater treatment to overcome the water scarcity due to increasing of population in Egypt. References Al Dwairi R., Al-Rawajfeh A., 2012. Removal of cobalt and nickel from wastewater by using Jordan low-cost zeolite and bentonite. Journal of Chemical Technology and Metallurgy 47, 69-76. APHA (American Public Health Association), 2012. Standard methods for examination of water and wastewater, 22th Ed. Washington, D C. Ayala J., Vega J.L., Alvarez R., Loredo J., 2008. Retention of heavy metal ions in bentonites from Grau Region (Northern Peru). Environmental Geology 2008; 53:1323–1330. Babel S., Kurniawan T. A., 2003. Low-cost adsorbents for heavy metals uptake from contaminated water: a review. Journal of hazardous materials 97(1): 219-243. Easton D. F., Pooley K. A., Dunning A. M., Pharoah P. D., Thompson D., Ballinger D. G., Struewing J. P., Morrison J., Field H., Luben R., 2007. Genome-wide association study identifies novel breast cancer susceptibility loci. Nature 447(7148): 1087-1093. Horsfall M., Abia A.,Spiff A., 2006. Kinetic studies on the adsorption of Cd 2+, Cu 2+ and Zn 2+ ions from aqueous solutions by cassava (Manihot sculenta Cranz) tuber bark waste. Bioresource technology 97(2): 283291. Janteng A., Halim S. A., Darus M., 2007. Hankel determinant for starlike and convex functions. International Journal of Mathematical Analysis, 1(13): 619-625. Karapinar N., Donat, R., 2009. Adsorption behaviour of Cu 2+ and Cd 2+ onto natural bentonite. Desalination 249(1): 123-129. König J. A., 2012. Shakedown of elastic-plastic structures, Elsevier. Lucia H. G. C., Gilvanise A. T., 2011. Cadmium and copper adsorption on bentonite: effects of pH and particle size. Revista Ciência Agronômica 48(308): 178182.

Naswir M., Arita S., 2013. Characterization of Bentonite by XRD and SEM-EDS andUse to Increase PH and Color Removal, Fe and Organic Substances in Peat Water. Journal of Clean Energy Technologies, 1(4), 313317. Novoselov K. S., Geim A. K., Morozov S. V., Jiang D., Zhang Y., Dubonos S. V., Grigorieva I. V., Firsov, A. A., 2004. Electric field effect in atomically thin carbon films. science 306(5696): 666-669. Papayannis, A., Mamouri R., Remoundaki E., Bourliva A., Tsaknakis G., Amiridis V., Kokkalis P., Veselovskii I., Kolgotin A., Samara C., 2010. Optical, microphysical and chemical properties of Saharan dust aerosols using a multi-wavelength Raman lidar, in situ sensors and modeling. Proc. of the 25th International Laser Radar Conference, St. Petersburg. Sheng G., Wang S., Hu J., Lu Y., Li J., Dong Y., Wang X., 2009. Adsorption of Pb (II) on diatomite as affected via aqueous solution chemistry and temperature. Colloids and Surfaces A: Physicochemical and Engineering Aspects 339(1): 159-166. Tahir A. A., Wijayantha K. U., Saremi-Yarahmadi S., Mazhar M., McKee V., 2009. Nanostructured α-Fe2O3 thin films for photoelectrochemical hydrogen generation. Chemistry of Materials 21(16): 3763-3772. Tanner S. M., Li Z., Bisson R., Acar C., Öner C., Öner R., Çetin M., Abdelaal M. A., Ismail E. A., Lissens W., 2004. Genetically heterogeneous selective intestinal malabsorption of vitamin B12: founder effects, consanguinity, and high clinical awareness explain aggregations in Scandinavia and the Middle East. Human mutation 23(4): 327-333. Tito G. A., Chaves L. H, Guerra H. O., Soares F.A., 2011. Uso de bentonita na remediação de solos contaminados com zinco: Efeito na produção de feijão. Revista Brasileira Engenharia Agrícola e Ambiental 15: 917-923. Varank G., Demir A., Bilgili M. S., Top, S., Sekman, E., Yazici, S., Erkan, H. S., 2014. Equilibrium and kinetic studies on the removal of heavy metal ions with natural low-cost adsorbents. Environment Protection Engineering 40(3): 43--61. White C. M., Smith D. H., Jones K. L., Goodman A. L., Jikich S. A., LaCount R. B., DuBose S. B., Ozdemir E., Morsi B. I., Schroeder K. T., 2005. Sequestration of carbon dioxide in coal with enhanced coalbed methane recovery a review. Energy & Fuels 19(3): 659-724. Yu B., Zhang Y., Shukla A., Shukla S. S. Dorris K. L., 2000. The removal of heavy metal from aqueous solutions by sawdust adsorption removal of copper. Journal of Hazardous Materials 80(1): 33-42.

Mousavi H., Hosseynifar A., Jahed V., Dehghani S., 2010. Removal of lead from aqueous solution using waste tire rubber ash as an adsorbent. Brazilian Journal of Chemical Engineering 27(1): 79-87.

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Author’s Information-

Prof. Dr. Maha Mahmoud Ali is a professor in analytiacal and environmental chemistry. Currently, she is a deputy director and operation manger in the Central Laboratory for Environmental Quality Monitoring (CLEQM), national Water Research Center (NWRC), Egypt. Since 1998, she was worked in CLEQM as a Head of Inorganic Chemistry Department and also as a Head of Aquatic Environmental Research Unit. During this period the Inorganic department, under her supervision, holds an accreditation from the Canadian Association for Laboratory Accreditation (CALA) according to ISO/IEC 17025. She was worked from 1982-1998 in Channeel Maintenance Research Institute (CMRI) where she was started as a laboratory specialist in water quality, fish culture and its artificial re-production till she holded a director of Delta Breading Station (DBS). Since 1982-2015 her experiences focused on the application of analytical chemistry in monitoring, analyzing and treatments of environmetal pollution source. She paticibtates in several project on national (eg. EEAA, MWRI, STDF, etc.) and international scale (ICLARM, DEPTSWAP, UNDP, GEF, Jica, etc.). She published 33 papers in national and international journals. She had resived 3 AWRDS titled Prof. Dr. Mostafa Kamal Tolba’s award for the best researches in the field of ‘“Protecting the Aquatic Environment from Pollution” at 2003, 2005 and 2009.

Dr. ElSayed ElBastamy ElSayed is a researcher at National Water Research Center, the Central Laboratory for Environmental Quality Monitoring (CLEQM) from 2003 till now. I had worked as a chemist in Laboratories of "Water Resources and Sustainable Development in the South Valley" project, Toshka Egypt from 2004 till 2008. Twining project (European Commission Decision) for water quality management and chemical & Ph ton

biological methods for water monitoring. PI of JICA project, the Project of Sustainable Systems for Food and Bio-energy Production with WaterSaving Irrigation in the Egyptian Nile Basin Faculty of Agriculture, Cairo University & Japan International Cooperation Agency), until now. PI of JICA project (Water reuse in Kafr ElShikh governorate), from 2009 till March 2015.PI researcher during Constriction of Suez Electricity Power Station on Suez Gulf, until now, the impact of using the sea water in electricity production in the ecosystem of Suez Gulf.

For publications/ Enquiries/ Copyrights: Email: [email protected]

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16 hours ago - the current study is agreed with the data obtained by Varank .... recovery a review. Energy ... a laboratory specialist in water quality, fish culture.

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