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Reduced graphene oxide as effective adsorbent for removal of heavy metals in groundwater of Amaravathi River basin, Tamil Nadu

Reduced graphene oxide as effective adsorbent for removal of heavy metals in groundwater of... GEOLOGY, ECOLOGY, AND LANDSCAPES INWASCON https://doi.org/10.1080/24749508.2021.1923273 RESEARCH ARTICLE Reduced graphene oxide as effective adsorbent for removal of heavy metals in groundwater of Amaravathi River basin, Tamil Nadu a b A. Jafar Ahamed and K. Loganathan PG and Research Department of Chemistry, Jamal Mohamed College (Autonomous) Affiliated to Bharathidasan University, Tiruchirappalli, India; Department of Chemistry, Vivekanandha College of Arts and Sciences for Women (Autonomous) Affiliated to Periyar University, Elayampalayam, India ABSTRACT ARTICLE HISTORY Received 12 October 2020 The main aim of the present study was to weigh up and identifies the groundwater quality in the Accepted 24 April 2021 Amaravathi River basin of Karur district. Twenty four samples were collected, processed, and analyzed for various physico-chemical parameters such as pH, electrical conductivity (EC), total KEYWORDS 2+ 2+ dissolved solids (TDS), total hardness (TH), cation such as calcium (Ca ), magnesium (Mg ), Adsorption; Amaravathi + + − − sodium (Na ), and potassium (K ); anion such as bicarbonate (HCO ), chloride (Cl ), sulphate 3 River; graphene oxide; Karur; 2- − (SO ), and fluoride (F ) in the laboratory using the standard methods given by the American nanomaterial 2+ Public Health Association. Specifically, we investigated trace metals like cadmium (Cd ), lead 2+ 2+ 2+ 2+ 2+ 2+ (Pb ), copper (Cu ), zinc (Zn ), manganese (Mn ), nickel (Ni ), and iron (Fe ) using Atomic Absorption Spectrophotometer. Out of 24 samples, Thirumanilayur sample is taken for treatment 2+ 2+ process because all the physico–chemical parameters, and heavy metals Cd and Pb were well above the permissible limits laid by World Health Organizationand Bureau of Indian Standards. Graphene oxide (GO) nanoparticle is taken for treatment process and its adsorption capacity was confirmed by XRD, SEM, FTIR, and EDS techniques. The treated groundwater sample using graphene oxide nanomaterial (60 and 80 mg) show a positive result for reducing the excess 2+ 2+ metal ions (Cd and Pb ), in addition to various water quality parameters. Introduction Karur is a major textile center and has five major product groups, namely bed linens, kitchen linens, Water is the most essential substance for all life on toilet linens, table linens and wall hangings. An earlier earth and a precious resource for human civilization survey in 2011 says that the total number of factories (Shrivastava & Mishra, 2011). There are no other located on the banks of the Amaravathi River is about natural resources that have such an overpowering 515. The dyeing industry consumes totally 3225 liters influence on human lives and plants (Loganathan of water per day for dyeing process. About 14600 m & Jafar Ahamed, 2017; Sultanaa et al., 2017). of coloured effluent with TDS 5000–10,000 mg/L is let Reliable access to clean and affordable water is con- into the Amaravathi River daily (Ahamed et al., 2013). sidered one of the most basic humanitarian goals, st Big factories had even dug tube wells to a depth of and remains a major global challenge for the 21 275 meters and discharged effluents into these wells century. It is well known that nowadays, industrial lead to contamination of groundwater in the area. Soil water use is a major factor of global water crisis due turned infertile, the yield of the crops came down, to drastic increase in population and industries slowly the farmlands became barren and 250 open (Santos et al., 2014). The water usage trends in wells get contaminated. Kidney disorders, cancer and India in the year 2012 show that 13% of the natural abortion are high in the affected villages, revealed by water sources are used for industries. Report by local natives. Owing to zero discharge of effluents, in World Commission on Water revealed that fresh 2011, 459 dyeing units were closed and only 54 fac- water usage will be increased worldwide by around tories were given permission after they installed ETP 60% in the year 2050. For this reason, it is very (Loganathan & Jafar Ahamed, 2017; Suchitra, 2014). important that effective water management activities Asha (1998) has motivated scientists to look at the to protect the water environment problems faced by the general public and farmers who (Thirugnanasambandham et al., 2016). In India, var- use the groundwater for drinking, bathing, washing, ious industries consume large amount of fresh water agriculture, etc. Rajamanickam and Nagan (2010) for their process as well as industries discharge have revealed that the Amaravathi River has been highly polluted wastewater to the nearby ecological converted as drainage for industrial and domestic system (Ahamed & Loganathan, 2012). CONTACT A. Jafar Ahamed agjafar@yahoo.co.in PG and Research Department of Chemistry, Jamal Mohamed College (Autonomous), Tiruchirappalli 620 020, India © 2021 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group on behalf of the International Water, Air & Soil Conservation Society(INWASCON). This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 2 A. J. AHAMED AND K. LOGANATHAN effluents. It is also reported that the water quality enhances active sites (Sharma et al., 2009). Carbon parameters have been well above the permissible limits based nanomaterials, especially carbon aerogels, car- suggested by WHO (1977). Sivakumar et al. (2011) bon nanotubes, graphene, and their composites, repre- quantified that groundwater quality parameters of sent a promising type of adsorbents (Gao et al., 2013) the Amaravathi River basin were crossing the permis- for water and wastewater treatment, and have poten- sible limits due to industrial and textile industrial tial applications for removal of heavy metals and activities. Similar results were reported by Raja and organic contaminants. Venkatesan (2010), that the groundwater in Punnam village of Karur district is highly polluted due to the release of textile industries effluent. Description of the study area Water contains chemical parameters which are The river Amaravathi originates from Naimakad at an above the permissible limit may cause some serious elevation of 2300 m above mean sea level in the damages, which is considered to be polluted. Western Ghats in Idukki region of state Kerala Nowadays, numerous methods have been proposed (Figure 1). Amaravathi River in Karur lies between for efficient removal of pollutants from the waters, north latitudes 11.20° and 12.00° and east longitudes including but not limited to, chemical precipitation, 77.28° and 78.50°. Amaravathi river reach Karur dis- ion exchange, adsorption, membrane filtration and trict near Aravakurichi and joins with Cauvery River electrochemical technologies (Wu et al., 2013). near Thirumakudalur village, and the water flow in the Among these techniques, adsorption offers flexibility river is seasonal from late October to early February in design and operation and, in many cases it will (Ahamed et al., 2015b). Amaravathi River basin and generate high-quality treated effluent (Hua et al., sub-basin (Figure 2(a)) has four different seasons, 2012). The adsorption principle plays a vital role in namely summer season from March to May, south- the treatment of environmental pollution. Adsorption west monsoon commencing from June to early means a process in which the solute species accumu- September, northeast monsoon beginning of October late at an interface. The interface may be gas-solid, to December and winter season starting from January liquid- liquid, liquid-gas and liquid- solid. It is purely to February. The average annual rainfall over the dis- a surface phenomenon, deals with only those species, trict from 1901 to 2011 varies between 620 and which are bound to the surface of the adsorbate. The 745 mm, and in 2012, it was founded as 527.6 mm, plan of nanostructured adsorbents with controlled much less than the states normal average rainfall of functionalities offers new possibilities to tackle the 652.20 mm (Renganathan, 2014), and it is the least low adsorption capacity or efficiency problems around Aravakurichi (622.7 mm) in the western because of their high specific surface areas and region of the district. It progressively increases toward Figure 1. Location of sampling sites on the Amaravathi River basin. GEOLOGY, ECOLOGY, AND LANDSCAPES 3 Figure 2. Map showing the (a) River (b) Geomorphology and Lineament (c) Soil and (d) Geology of the Karur district. eastern parts and reach a maximum around Kulithalai Pungar River drains in the eastern region of the dis- (744.6 mm). The district enjoys a sub-tropical climate, trict. The drainage pattern generally, is dendritic. and the relative humidities generally range from 40 to Except river Cauvery, all the rivers are seasonal and 80%. The average maximum temperature ranges from bring substantial flows during the monsoon time 26.7 to 38.56°C, and the average minimum tempera- (Ahamed & Loganathan, 2012). ture ranged between 18.7 and 29.3°C. The daylight Major part of the district is covered with red soil is heat is oppressive and the temperature attains high the predominant one followed by red loam and thin as 43.9°C and the lowest temperature observed is 13.9° red soil. Red soil is mostly seen in Kulithalai, Kadavur, C (CGWB, 2008). Krishnarayapuram, Thogamalai and Thanthoni Completely the entire area of the Karur district is blocks. Karur block is generally covered by red loam a pediplain. Kadavur and Rangamalai hills occurring (Figure 2(c)). The thin red soils are seen in in the southern part of the district comprise the loose K. Paramathy and Aravakurichi blocks. The major ends of the much denuded Eastern Ghats and rise to economic crops cultivated in this area are jowar heights of over 1031 m above mean sea level. District (22.60%), paddy (16.30%), groundnut (6.90%), sugar possesses several small residual hills represented by cane (6.40%) and banana (5.30%). The total geogra- Ayyarmalai, Thanthonimalai and phical area is 2,89,557 ha of which area employed in Velayuthampalayam hills. General altitude of the cultivation is 1,14,554 ha, 37,264 ha land put into non- area is ranging between 100 m and 200 m above agricultural uses (Ahamed and Loganathan, 2017) and mean sea level. The well-known geomorphic units remaining are engaged in other activities (Table 1). (Figure 2(b)) known in the district are pediments, The available data indicates that an area of about shallow pediments, buried pediments, structural hill 54,709 ha, which is about 18.90% of the total geogra- and alluvial plain (Ahamed et al., 2016). Cauvery River phical area of the district is in irrigated agriculture. drained the major parts of the Karur district. Dug wells accounting for about 59.97% of the total Amaravathi, Kodavanar and Nanganji are the chief area irrigated in the district was the major source of rivers draining the western region of the district and water for irrigation. Tube wells account for about 4 A. J. AHAMED AND K. LOGANATHAN Table 1. The nine-fold lands-use/land-cover statistics for the Materials and methods district. Water sampling and analysis S. No. Classification Area (Ha) 1 Forests 6187 Twenty four groundwater samples were collected from 2 Barren & Uncultivable Lands 2901 3 Land put to non agricultural uses 37264 bore and hand pumps during August (2014), repre- 4 Cultivable Waste 67831 senting the pre-monsoon seasons. Bore wells and hand 5 Permanent Pastures & other grazing lands 10801 pumps for sampling were chosen on the base of an 6 Groves not included in the area sown 1278 7 Current Fallows 4774 industrial unit in addition to diverse land use patterns. 8 Other Fallow Lands 46802 Figure 1 represents the GIS map of the study area 9 Net Area sown 111719 Total 289557 showing sampling locations. During sample collection high density white polyethylene bottles were used. The samples were filled up to the rim and were instantly preserved to avoid exposure to air and were labeled 9.48% of the total area irrigated in the district, while scientifically. The labeled water samples were analyzed tank irrigation accounts only for 1.10%. Comparing for their physico-chemical parameters in the labora- the entire irrigation type, the canal irrigates only tory. At sample collection for handling and preserva- 29.45% area (Ahamed et al., 2015b). tion the American Public Health Association (APHA, 2005) standard procedures were followed to guarantee data quality and reliability. The total dissolved solids Geology and hydrogeology (TDS), hydrogen ion concentration (pH) and electrical The district is underlained entirely by Archaean conductivity (EC) were determined immediately on Crystalline formations with fresh alluvial deposits location by using water quality multi-tester probe taking place along the river and stream courses. (Eutech PC Tester 35), and the major ions were exam- The rigid consolidated crystalline rocks of ined using the standard procedure suggested by the Archaean age symbolize weathered, fractured and American Public Health Association (APHA, 2005). + + Sodium (Na ) and potassium (K ) were determined fissured formations of gneisses, granites, charnock- ites and additional related rocks (Figure 2(d)). by Flame photometer using Systronics make 128. 2+ Deep groundwater occurs beneath phreatic condi- Total hardness (TH), calcium (Ca ), magnesium 2+ − − tions, and the most saturated thickness of the aqui- (Mg ), bicarbonate (HCO ), and chloride (Cl ) fer in rigid rock creation varied between 15 and were analyzed by volumetric methods following 35 m depending upon the topographic circum- Trivedy and Goel (1986) methods and sulphates 2- stances (Ahamed et al., 2015b). Thickness of the (SO ) were estimated by precipitation method using alluvial deposit is estimated to be approximately spectrophotometer. Fluoride ion concentration was 10–12 m. The specific capacity of large diameter estimated by ion selective electrode (Thermo scientific wells tested in crystalline rocks from 31 to 200 Orion 4 star). The accurateness of the results was lpm/m of drawdown. The yield characteristics of performed by calculating the ionic balance errors and wells vary considerably depending on the topo- it was usually within ± 5%. The water samples were graphic set-up, lithology and the degree of weath- filtered using a 0.45 µm Whatman filter paper. The samples were preserved by acidifying to pH ~ 2 with ering. The seasonal fluctuation shows a rise in water level, which ranges from 0.46 to 1.98 m. HNO and kept at a temperature of 4°C until analysis. The piezometric head varied between 3.53 and Prior to any analysis, all the glassware and containers 5.34 m bgl during pre-monsoon and 2.04 to were soaked in deionized distilled water. The determi- 2+ 2+ 2+ 2+ 2+ 2 7.59 m bgl during post-monsoon. The specific nation of metal ions Cd , Pb , Cu , Zn , Mn , Ni +, 2+ capacity in the weathered, partly weathered and and Fe (227, 281.5, 323, 212, 278, 231 and 247.5 nm jointed rocks varies from 31 to 240.5 lpm/m/dd respective wavelength) in water samples were carried and the transmissivity values in weathered, partly out by atomic absorption spectrophotometer (Perkin weathered and jointed rocks vary from 15.5 to Elmer A analyst 400). The limit of detection for Cd was 154 m /day. The optimum yield varied from 45.40 0.0001 and 0.001 ppm for all other elements. The blank readings for all the metals were 0.00 ppm in deionized to 441.60 m /day. The specific capacity in the fis - sured and fractured formation ranges from 6.89 to water with EC value lower than 5 µS/cm. 117.92 lpm/m/dd and the transmissivity values ranges from 11.42 to 669.12 m /day. The specific Treatment process capacity values in the porous formation vary from 135 to 958 lpm/m.dd and the transmissivity values Preparation of graphene oxide ranged from 67.5 to 264.5 m /day. The optimum Graphene oxide was prepared according to the mod- yield varied from 232.8 to 549.6 m /day ified Hummer’s method that has been reported (Loganathan & Jafar Ahamed, 2017). GEOLOGY, ECOLOGY, AND LANDSCAPES 5 previously (Hummers & Offeman, 1958; Xu et al., were characterized by FESEM (Field emission scan- 2012) using graphite powder procured from sigma ning electron microscopy – ZEISS EVO MA 15). The Aldrich (SP-1 grade 325 mesh). In a typical synthesis, elemental composition of the as-prepared sample was graphite powder (10 g) was added into an 80°C solu- quantified by energy dispersive spectroscopy (EDS) tion of concentrated H SO (20 ml), K S O (4.2 g), using an X-ray detector (THERMO EDS) attached to 2 4 2 2 8 and P O (4.2 g) and the dark blue mixture was stirred the FESEM instrument. Additionally, Fourier trans- 2 5 vigorously and kept at 80°C for 4.5 h. The mixture was form infra–red spectroscopy (FT–IR) analysis was −1 cooled to room temperature, and diluted with 45 ml of carried out in the range of 400–4000 cm (Perkin deionized water. Finally, the solution was transferred Elmer). to a large beaker, and left overnight. The mixture was then carefully filtered and washed with deionized Results and discussion water using 0.22 μm polycarbonate filter until the pH value of the rinse water became neutral. The obtained Groundwater chemistry product was dried at 40°C for 24 hours under vacuum In this study area, pH values ranged between 6.94 and (Ahamed et al., 2015a). 7.81 with the mean value of 7.44 indicating that The pre-oxidized graphite powder was then oxi- groundwater is slightly alkaline in nature. EC varied dized by the Hummer’s method. 2 g of pre-oxidized from 890 µS/cm to 6560 µS/cm with mean of 4532 µS/ graphite powder was added in 46 ml of concentrated cm. TDS showed a wide variation from 798 to H SO of cold (0°C) condition. Then 12 g of KMnO 2 4 4 4546 mg/L with average value of 3867 mg/L. Based was added gradually under stirring and the tempera- on EC value (Langenegger, 1990), groundwater is ture of the mixture was maintained not exceeding 20° classified into saline water (1500–10,000 µS/cm). TH C. Then, it was removed from the ice-bath and the ranged between 445 and 1933 mg/L with mean value mixture was stirred at 35°C for 2 hours. 97 ml of of 1328 mg/L, the excess concentration is due to deionized water was slowly added gradually into the mineral weathering (bivalent cation Ca and Mg). mixture and the diluted suspension was maintained at 2+ 2+ During the analysis, Ca and Mg range from 82 to 98°C for 15 min. Again, 280 ml of deionized water and 591 mg/L and 52 to 116 mg/L, respectively. The excess 5 ml of 30% H O were added into the suspension. 2 2 calcium originated from leaching process of dolomites A brilliant yellow mixture was obtained and the pro- and gypsum, were as magnesium is from cattle feed duct was centrifuged and washed with 10% HCl solu- and fertilizer application. Sodium is responsible for tion to remove the excessive residual metal ions high salinity; it ranged between 674 and 1529 mg/L followed by deionized water to remove the acid until with mean value of 956 mg/L, which derived from the pH of filtrate was neutral. The final dark brown halite due to adsorption on sediments near the river solid product was obtained and dried in vacuum. belt. 93% of samples were in the borderline of potas- Exfoliation was done by sonicating the oxidized gra- sium limit (12 mg/L). phite dispersion for 30 min at 240 W. The prepared Among anions, Cl having excess concentration Graphene Oxide was dried in vacuum for 24 h ranged between 583 and 1619 mg/L, basically chloride (Ahamed et al., 2015a). is found in sewage and course of water passing Carbon nanosheet (graphene oxide) prepared from through natural salt formation in the earth crust. graphite was used for the treatment of groundwater 2- − − SO , F and HCO concentration ranged from 203 4 3 sample collected from Thirumanilayur station. to 264 mg/L, 0.9 to 1.6 mg/L and 226 to 398 mg/L, Equilibrium study (180 min) was carried out by add- respectively. Metal concentration recorded were ing 60 mg and 80 mg of adsorbent into each 100 ml of 2+ 2+ 2+ 2+ 2 ranked in the order Cd > Pb > Zn > Cu > Fe the same sample. The bottles were placed in a rotary + 2+ 2+ > Mn > Ni . Except cadmium and lead all other shaker and agitated for 180 min at a speed of 150 rpm metals are within the limit. to make sure that equilibrium is reached. The content was filtered, analyzed and the values were compared with the same sample before adsorption process and Water treatment process also with WHO (2005) and BIS (2003) standards. A preliminary study on Thirumanilayur sample has been carried out to assess the reduction nature of Characterization techniques graphene oxide using adsorption techniques. The phy- The prepared graphene oxide (GO) nanoparticles sical nature of graphene oxide before treatment has were subjected to XRD analysis. The XRD pattern been investigated using analytical techniques. X-ray was recorded (model: X’PERT PRO PAN analytical) diffraction measurements have been recorded during using Cu Kα radiation (λ = 1.54060 Å) with nickel different steps of preparation of nanocomposites. monochromator in the range of 2θ from 10° to 80°. Figure 3 depicts the XRD studies of the GO materials, The area, size and morphology of the prepared GO which is due to the oxidation process of graphite. The 6 A. J. AHAMED AND K. LOGANATHAN effective oxidation of graphite and the formation of shows a simple nanosheet morphological structure. GO has been compared with the characteristic strong Wave like surface morphology nanosheet is observed and sharp (002) peak at 11.02°. A typical FESEM for the entire reconstructed nanocomposites. The ele- image of the GO is given in Figure 4(a,b) which mental analysis data clearly indicates that graphene is Figure 3. XRD pattern of graphene oxide before treatment (GO) after treatment (60 and 80 mg). Figure 4. (a,b) SEM images of graphene oxide before treatment; (c) SEM images of graphene oxide (60 mg) and (d) SEM images of graphene oxide (80 mg) after treatment. GEOLOGY, ECOLOGY, AND LANDSCAPES 7 Figure 5. (a) EDS analysis of graphene oxide before treatment (b and c) EDS analysis of graphene oxide 60 mg and 80 mg after treatment. Figure 6. (a) FTIR spectra of graphene oxide before treatment; (b & c) FTIR spectra of graphene oxide 60 mg and 80 mg after treatment. 8 A. J. AHAMED AND K. LOGANATHAN 2+ 2+ coordinate with the oxygen atom. EDS profile of gra- when compared with Ca and Mg . The initial con- + + phene oxide C :O is in Figure 5(a). The IR fre- centration of Na and K is 1529 and 14.24 mg/L, after 0.56 0.44 −1 −1 −1, quencies at 3411 cm , 1725 cm , 1038 cm and treatment, it is reduced to 1361 & 10.78 mg/L for −1 1237 cm confirms the presence of many oxygen 60 mg adsorbent and 1278 & 8.16 mg/L for 80 mg containing groups such as OH, C=O, C-O, C-OH, adsorbent. The initial and final concentration of Na respectively in graphene oxide (Figure 6(a)). These and K in the sample was confirmed by Systronics evidences indicate that during the oxidation process Flame photometer 128. The result showed that the of the graphite powder with KMnO in the concen- adsorption of metal ions took place in the binding trated sulphuric acid, the original extended conjugated sites on the surface of the adsorbent in a monolayer π-orbital system of the graphite is destroyed and oxy- mode. gen-containing functional groups are introduced into The anionic species are not much reduced, because carbon skeleton (Ahamed et al., 2015a). The results of of the presence of negative charge on the surface of 2+ the treated sample (Thirumanilayur) show graphene oxide. Among trace elements, Pb is well a conspicuous reduction among water quality para- adsorbed on the GO, since heavy metals in the solu- 2+ meters. The graphene oxide is found to be more effec - tion are positively charged, the metal ion Pb bound tive in removing metals in water samples. The values strongly to graphene oxide. The initial concentration 2+ obtained for raw sample and after the treatment pro- of Pb in raw sample is 0.295 mg/L and after treat- cess by varying adsorbent dosage (60 and 80 mg) are ment it is 0.083 and 0.077 mg/L for 60 and 80 mg 2+ compared with standard limits of WHO (2005) and adsorbent. Trace amount of Cd is also adsorbed and BIS (2003) is presented in Table 2. the concentration is observed through an atomic pH of raw water sample is 7.82 and after treatment absorption spectrophotometer. The spectral studies it is 7.90 and 7.98 for 60 and 80 mg adsorbent, respec- evidently depict the reduction process take place in tively. pH is within the permissible limit, but the the water sample. Figure 3, the XRD pattern clearly increase in pH is due to the release of – OH group. indicates that the graphene oxide peak is disappeared Literature (Gao et al., 2013) has revealed that Pb(II) in 11.02° and new amorphous graphene oxide struc- and Cd(II) forms metal hydroxide, when the pH value ture is observed. It shows that the metal ions are is greater than 6.0. Thus, the increase in pH dramati- adsorbed on the surface of carbon nanosheet. The cally increases the adsorption capacities of Pb(II) and FESEM images of treated GO samples (Figure 4(c,d)) Cd(II). The value of the EC in raw sample is 6560 µS/ obviously display the agglomerated flake like morpho- cm, and it is 6193 and 5892 µS/cm after treatment. logical structure. It confirmed the change of surface TDS value ranged between 4292 and 4083 mg/L for 60 uniformity from GO to metal adsorbed GO and 80 mg adsorbent, and it is 4546 mg/L for raw nanosheets. Meanwhile, EDS (Figure 5(b,c)) analysis sample, the reduction of EC and TDS value confirms is evidences that the sodium and lead are predomi- the adsorption take place in the system. There is no nantly adsorbed on the surface of GO nanosheets. notable reduction in hardness, shows that hardness is FTIR spectra of treated GO samples in Figure 6(b,c) 2+ permanent in nature due to divalent cations (Ca and demonstrate the absence of OH, C=O peak at 2+ + + −1 −1 Mg ). Among cations, Na and K were reduced well 3411 cm and 1725 cm which confirms the process Table 2. Treated result for the adsorption process by graphene oxide. WHO BIS Parameters Before adsorption process After adsorption process (60 mg) After adsorption process (80 mg) limit limit pH 7.82 7.90 7.98 7–8.5 6.5–8.5 EC 6560 6193 5892 1000–2000 750–2250 TDS 4546 4292 4083 500 500 TH 1933 1917 1894 300 300 2+ Ca 591 589 585 75 75 2+ Mg 116 109 104 50 50 Na 1529 1361 1278 200 200 K 14.24 10.78 8.16 12 12 HCO 398 386 382 100 200 Cl 1619 1608 1596 200 250 F 1.6 1.5 1.5 1 1 2- SO 264 257 251 200 200 2+ Cd 0.069 0.056 0.052 0.01 0.003 2+ Pb 0.295 0.083 0.077 0.05 0.01 2+ Cu 0.036 0.033 0.032 0.05 2 2+ Zn 0.092 0.090 0.087 5 3 2+ Mn 0.002 bdl* bdl* 0.1 0.4 2+ Ni bdl* bdl* bdl* - 0.02 2+ Fe 0.094 0.082 0.074 0.3 0.3 All the values are expressed in mg/L, except pH and EC in µS/cm, *bdl-below detectable limit GEOLOGY, ECOLOGY, AND LANDSCAPES 9 of adsorption taking place on GO, which is further and-correlation-analysis-of-surface-and-ground-water- of-amaravathi-river-basinkarur-tamilnadu-india.pdf confirmed that, the metal or metal hydroxide (Zhou −1 Ahamed, A. J., & Loganathan, K. (2017). Water quality et al., 2012) peaks appear below 1500 cm . concern in the Amaravathi River basin of Karur District: A view at heavy metal concentration and their interrelationships using geostatistical and multivariate Conclusion and summary analysis. Geology, Ecology and Landscapes, 1(1), 19–36. https://doi.org/10.1080/24749508.2017.1301055 In this present study the dominant cation found in Ahamed, A. J., Loganathan, K., & Jayakumar, R. (2015b). + 2+ 2+ + groundwater is Na followed by Ca , Mg and K . Hydrochemical characteristics and quality assessment of − − 2- The dominant anion is Cl followed by HCO , SO 3 4 groundwater in Amaravathi river basin of Karur district, − 2+ 2+ and F . Among trace elements Cd and Pb were in Tamil Nadu, South India. Sustainable Water Resources Management, 1(3), 273–291. https://doi.org/10.1007/ excess concentration. Analysis identifies both man- s40899-015-0026-3 made activities and geochemical process responsible Ahamed, A. J., Loganathan, K., & Vijayakumar, P. (2013). for groundwater quality in Amaravathi River basin. Bio-chemical investigation of selected water quality para- Reduced graphene oxide is used as adsorbent to meters in Amaravathi River basin, Karur district, reduce excess ion concentration. The parameters like Tamilnadu, India. International Journal of Current + + 2+ 2+ Research, 5(10), 3100–3103. http://journalcra.com/arti EC, TDS, Na , K and metals like Cd and Pb cle/bio-chemical-investigation-selected-water-quality- showed remarkable reduction. The rate of adsorption parameters-amaravathi-river-basin-karur increases when increase in adsorbent dosage. XRD Ahamed, A. J., Vijaya Kumar, P., & Srikesh, G. (2015a). pattern, FESEM and EDS analysis confirmed the Low temperature synthesis and characterization of adsorption process. The groundwater in the rGO-CoO nanocomposite with efficient electrochemi- Amaravathi River Basin is in a critical situation and cal properties. Journal of Environmental Nanotechnology, 4(2), 01–08. https://doi.org/10.13074/ the results of the groundwater quality can be jent.2015.06.152147 employed in future groundwater panning and APHA. (2005). Standard methods for the examination of developments. water and wastewater (21st ed.). American Public Health Association. Asha, K. (1998). A pollution challenge. Frontline, The Acknowledgments Hindu, 15 (13),(June 20-July 3). BIS. (2003). Indian standards specification for drinking water The one of the author Dr. A. Jafar Ahamed is thankful to the 15: 10500. Bureau of Indian Standards. University Grants Commission (UGC), New Delhi for pro- CGWB. (2008). District groundwater brochure, Karur dis- viding Major Research Fund (F. No.41-337/2012) and the trict, Tamil Nadu. Central Ground Water Board. Members of the Management Committee and the Principal Gao, H., Sun, Y., Zhou, J., Xu, R., & Duan, H. (2013). of Jamal Mohamed College for providing necessary Mussel-inspired synthesis of facilities. polydopamine-functionalized graphene hydrogel as reu- sable adsorbents for water purification. ACS Applied Materials & Interfaces, 5(2), 425–432. https://doi.org/10. Disclosure statement 1021/am302500v Hua, M., Zhang, S., Pan, B., Zhang, W., Lv, L., & Zhang, Q. No potential conflict of interest was reported by the (2012). Heavy metal removal from water/wastewater by author(s). nanosized metal oxides: A review. Journal of Hazardous Materials, 211-212, 317–331. https://doi.org/10.1016/j. jhazmat.2011.10.016 Funding Hummers, W. S., & Offeman, R. E. (1958). Preparation of graphite oxide. Journal of American Chemical Society, 80 This work was supported by the University Grants (6), 1339. https://doi.org/10.1021/ja01539a017 Commission (F.No. 41-337/2012). Langenegger, O. (1990). Ground water quality in rural areas of western Africa, UNDP project INT/81/026: 10. 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Engineering Chemistry Research, 51(44), 14390–14398. downtoearth.org.in/content https://doi.org/10.1021/ie301734f Sultanaa, N., Akiba, S., & Ashraf, M. A. (2017). Thermal Zhou, G., Wang, D. W., Yin, L. C., Li, N., Li, F., & comfort and runoff water quality performance on green Cheng, H. M. (2012). Oxygen bridges between NiO roofs in tropical conditions. Geology, Ecology and nanosheets and graphene for improvement of Lithium Landscapes, 1(1), 47–55. https://doi.org/10.1080/ storage. ACS Nano, 6(4), 3214–3223. https://doi.org/10. 24749508.2017.1301058 1021/nn300098m http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Geology Ecology and Landscapes Taylor & Francis

Reduced graphene oxide as effective adsorbent for removal of heavy metals in groundwater of Amaravathi River basin, Tamil Nadu

Geology Ecology and Landscapes , Volume 7 (1): 10 – Jan 2, 2023

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© 2021 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group on behalf of the International Water, Air & Soil Conservation Society(INWASCON).
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Abstract

GEOLOGY, ECOLOGY, AND LANDSCAPES INWASCON https://doi.org/10.1080/24749508.2021.1923273 RESEARCH ARTICLE Reduced graphene oxide as effective adsorbent for removal of heavy metals in groundwater of Amaravathi River basin, Tamil Nadu a b A. Jafar Ahamed and K. Loganathan PG and Research Department of Chemistry, Jamal Mohamed College (Autonomous) Affiliated to Bharathidasan University, Tiruchirappalli, India; Department of Chemistry, Vivekanandha College of Arts and Sciences for Women (Autonomous) Affiliated to Periyar University, Elayampalayam, India ABSTRACT ARTICLE HISTORY Received 12 October 2020 The main aim of the present study was to weigh up and identifies the groundwater quality in the Accepted 24 April 2021 Amaravathi River basin of Karur district. Twenty four samples were collected, processed, and analyzed for various physico-chemical parameters such as pH, electrical conductivity (EC), total KEYWORDS 2+ 2+ dissolved solids (TDS), total hardness (TH), cation such as calcium (Ca ), magnesium (Mg ), Adsorption; Amaravathi + + − − sodium (Na ), and potassium (K ); anion such as bicarbonate (HCO ), chloride (Cl ), sulphate 3 River; graphene oxide; Karur; 2- − (SO ), and fluoride (F ) in the laboratory using the standard methods given by the American nanomaterial 2+ Public Health Association. Specifically, we investigated trace metals like cadmium (Cd ), lead 2+ 2+ 2+ 2+ 2+ 2+ (Pb ), copper (Cu ), zinc (Zn ), manganese (Mn ), nickel (Ni ), and iron (Fe ) using Atomic Absorption Spectrophotometer. Out of 24 samples, Thirumanilayur sample is taken for treatment 2+ 2+ process because all the physico–chemical parameters, and heavy metals Cd and Pb were well above the permissible limits laid by World Health Organizationand Bureau of Indian Standards. Graphene oxide (GO) nanoparticle is taken for treatment process and its adsorption capacity was confirmed by XRD, SEM, FTIR, and EDS techniques. The treated groundwater sample using graphene oxide nanomaterial (60 and 80 mg) show a positive result for reducing the excess 2+ 2+ metal ions (Cd and Pb ), in addition to various water quality parameters. Introduction Karur is a major textile center and has five major product groups, namely bed linens, kitchen linens, Water is the most essential substance for all life on toilet linens, table linens and wall hangings. An earlier earth and a precious resource for human civilization survey in 2011 says that the total number of factories (Shrivastava & Mishra, 2011). There are no other located on the banks of the Amaravathi River is about natural resources that have such an overpowering 515. The dyeing industry consumes totally 3225 liters influence on human lives and plants (Loganathan of water per day for dyeing process. About 14600 m & Jafar Ahamed, 2017; Sultanaa et al., 2017). of coloured effluent with TDS 5000–10,000 mg/L is let Reliable access to clean and affordable water is con- into the Amaravathi River daily (Ahamed et al., 2013). sidered one of the most basic humanitarian goals, st Big factories had even dug tube wells to a depth of and remains a major global challenge for the 21 275 meters and discharged effluents into these wells century. It is well known that nowadays, industrial lead to contamination of groundwater in the area. Soil water use is a major factor of global water crisis due turned infertile, the yield of the crops came down, to drastic increase in population and industries slowly the farmlands became barren and 250 open (Santos et al., 2014). The water usage trends in wells get contaminated. Kidney disorders, cancer and India in the year 2012 show that 13% of the natural abortion are high in the affected villages, revealed by water sources are used for industries. Report by local natives. Owing to zero discharge of effluents, in World Commission on Water revealed that fresh 2011, 459 dyeing units were closed and only 54 fac- water usage will be increased worldwide by around tories were given permission after they installed ETP 60% in the year 2050. For this reason, it is very (Loganathan & Jafar Ahamed, 2017; Suchitra, 2014). important that effective water management activities Asha (1998) has motivated scientists to look at the to protect the water environment problems faced by the general public and farmers who (Thirugnanasambandham et al., 2016). In India, var- use the groundwater for drinking, bathing, washing, ious industries consume large amount of fresh water agriculture, etc. Rajamanickam and Nagan (2010) for their process as well as industries discharge have revealed that the Amaravathi River has been highly polluted wastewater to the nearby ecological converted as drainage for industrial and domestic system (Ahamed & Loganathan, 2012). CONTACT A. Jafar Ahamed agjafar@yahoo.co.in PG and Research Department of Chemistry, Jamal Mohamed College (Autonomous), Tiruchirappalli 620 020, India © 2021 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group on behalf of the International Water, Air & Soil Conservation Society(INWASCON). This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. 2 A. J. AHAMED AND K. LOGANATHAN effluents. It is also reported that the water quality enhances active sites (Sharma et al., 2009). Carbon parameters have been well above the permissible limits based nanomaterials, especially carbon aerogels, car- suggested by WHO (1977). Sivakumar et al. (2011) bon nanotubes, graphene, and their composites, repre- quantified that groundwater quality parameters of sent a promising type of adsorbents (Gao et al., 2013) the Amaravathi River basin were crossing the permis- for water and wastewater treatment, and have poten- sible limits due to industrial and textile industrial tial applications for removal of heavy metals and activities. Similar results were reported by Raja and organic contaminants. Venkatesan (2010), that the groundwater in Punnam village of Karur district is highly polluted due to the release of textile industries effluent. Description of the study area Water contains chemical parameters which are The river Amaravathi originates from Naimakad at an above the permissible limit may cause some serious elevation of 2300 m above mean sea level in the damages, which is considered to be polluted. Western Ghats in Idukki region of state Kerala Nowadays, numerous methods have been proposed (Figure 1). Amaravathi River in Karur lies between for efficient removal of pollutants from the waters, north latitudes 11.20° and 12.00° and east longitudes including but not limited to, chemical precipitation, 77.28° and 78.50°. Amaravathi river reach Karur dis- ion exchange, adsorption, membrane filtration and trict near Aravakurichi and joins with Cauvery River electrochemical technologies (Wu et al., 2013). near Thirumakudalur village, and the water flow in the Among these techniques, adsorption offers flexibility river is seasonal from late October to early February in design and operation and, in many cases it will (Ahamed et al., 2015b). Amaravathi River basin and generate high-quality treated effluent (Hua et al., sub-basin (Figure 2(a)) has four different seasons, 2012). The adsorption principle plays a vital role in namely summer season from March to May, south- the treatment of environmental pollution. Adsorption west monsoon commencing from June to early means a process in which the solute species accumu- September, northeast monsoon beginning of October late at an interface. The interface may be gas-solid, to December and winter season starting from January liquid- liquid, liquid-gas and liquid- solid. It is purely to February. The average annual rainfall over the dis- a surface phenomenon, deals with only those species, trict from 1901 to 2011 varies between 620 and which are bound to the surface of the adsorbate. The 745 mm, and in 2012, it was founded as 527.6 mm, plan of nanostructured adsorbents with controlled much less than the states normal average rainfall of functionalities offers new possibilities to tackle the 652.20 mm (Renganathan, 2014), and it is the least low adsorption capacity or efficiency problems around Aravakurichi (622.7 mm) in the western because of their high specific surface areas and region of the district. It progressively increases toward Figure 1. Location of sampling sites on the Amaravathi River basin. GEOLOGY, ECOLOGY, AND LANDSCAPES 3 Figure 2. Map showing the (a) River (b) Geomorphology and Lineament (c) Soil and (d) Geology of the Karur district. eastern parts and reach a maximum around Kulithalai Pungar River drains in the eastern region of the dis- (744.6 mm). The district enjoys a sub-tropical climate, trict. The drainage pattern generally, is dendritic. and the relative humidities generally range from 40 to Except river Cauvery, all the rivers are seasonal and 80%. The average maximum temperature ranges from bring substantial flows during the monsoon time 26.7 to 38.56°C, and the average minimum tempera- (Ahamed & Loganathan, 2012). ture ranged between 18.7 and 29.3°C. The daylight Major part of the district is covered with red soil is heat is oppressive and the temperature attains high the predominant one followed by red loam and thin as 43.9°C and the lowest temperature observed is 13.9° red soil. Red soil is mostly seen in Kulithalai, Kadavur, C (CGWB, 2008). Krishnarayapuram, Thogamalai and Thanthoni Completely the entire area of the Karur district is blocks. Karur block is generally covered by red loam a pediplain. Kadavur and Rangamalai hills occurring (Figure 2(c)). The thin red soils are seen in in the southern part of the district comprise the loose K. Paramathy and Aravakurichi blocks. The major ends of the much denuded Eastern Ghats and rise to economic crops cultivated in this area are jowar heights of over 1031 m above mean sea level. District (22.60%), paddy (16.30%), groundnut (6.90%), sugar possesses several small residual hills represented by cane (6.40%) and banana (5.30%). The total geogra- Ayyarmalai, Thanthonimalai and phical area is 2,89,557 ha of which area employed in Velayuthampalayam hills. General altitude of the cultivation is 1,14,554 ha, 37,264 ha land put into non- area is ranging between 100 m and 200 m above agricultural uses (Ahamed and Loganathan, 2017) and mean sea level. The well-known geomorphic units remaining are engaged in other activities (Table 1). (Figure 2(b)) known in the district are pediments, The available data indicates that an area of about shallow pediments, buried pediments, structural hill 54,709 ha, which is about 18.90% of the total geogra- and alluvial plain (Ahamed et al., 2016). Cauvery River phical area of the district is in irrigated agriculture. drained the major parts of the Karur district. Dug wells accounting for about 59.97% of the total Amaravathi, Kodavanar and Nanganji are the chief area irrigated in the district was the major source of rivers draining the western region of the district and water for irrigation. Tube wells account for about 4 A. J. AHAMED AND K. LOGANATHAN Table 1. The nine-fold lands-use/land-cover statistics for the Materials and methods district. Water sampling and analysis S. No. Classification Area (Ha) 1 Forests 6187 Twenty four groundwater samples were collected from 2 Barren & Uncultivable Lands 2901 3 Land put to non agricultural uses 37264 bore and hand pumps during August (2014), repre- 4 Cultivable Waste 67831 senting the pre-monsoon seasons. Bore wells and hand 5 Permanent Pastures & other grazing lands 10801 pumps for sampling were chosen on the base of an 6 Groves not included in the area sown 1278 7 Current Fallows 4774 industrial unit in addition to diverse land use patterns. 8 Other Fallow Lands 46802 Figure 1 represents the GIS map of the study area 9 Net Area sown 111719 Total 289557 showing sampling locations. During sample collection high density white polyethylene bottles were used. The samples were filled up to the rim and were instantly preserved to avoid exposure to air and were labeled 9.48% of the total area irrigated in the district, while scientifically. The labeled water samples were analyzed tank irrigation accounts only for 1.10%. Comparing for their physico-chemical parameters in the labora- the entire irrigation type, the canal irrigates only tory. At sample collection for handling and preserva- 29.45% area (Ahamed et al., 2015b). tion the American Public Health Association (APHA, 2005) standard procedures were followed to guarantee data quality and reliability. The total dissolved solids Geology and hydrogeology (TDS), hydrogen ion concentration (pH) and electrical The district is underlained entirely by Archaean conductivity (EC) were determined immediately on Crystalline formations with fresh alluvial deposits location by using water quality multi-tester probe taking place along the river and stream courses. (Eutech PC Tester 35), and the major ions were exam- The rigid consolidated crystalline rocks of ined using the standard procedure suggested by the Archaean age symbolize weathered, fractured and American Public Health Association (APHA, 2005). + + Sodium (Na ) and potassium (K ) were determined fissured formations of gneisses, granites, charnock- ites and additional related rocks (Figure 2(d)). by Flame photometer using Systronics make 128. 2+ Deep groundwater occurs beneath phreatic condi- Total hardness (TH), calcium (Ca ), magnesium 2+ − − tions, and the most saturated thickness of the aqui- (Mg ), bicarbonate (HCO ), and chloride (Cl ) fer in rigid rock creation varied between 15 and were analyzed by volumetric methods following 35 m depending upon the topographic circum- Trivedy and Goel (1986) methods and sulphates 2- stances (Ahamed et al., 2015b). Thickness of the (SO ) were estimated by precipitation method using alluvial deposit is estimated to be approximately spectrophotometer. Fluoride ion concentration was 10–12 m. The specific capacity of large diameter estimated by ion selective electrode (Thermo scientific wells tested in crystalline rocks from 31 to 200 Orion 4 star). The accurateness of the results was lpm/m of drawdown. The yield characteristics of performed by calculating the ionic balance errors and wells vary considerably depending on the topo- it was usually within ± 5%. The water samples were graphic set-up, lithology and the degree of weath- filtered using a 0.45 µm Whatman filter paper. The samples were preserved by acidifying to pH ~ 2 with ering. The seasonal fluctuation shows a rise in water level, which ranges from 0.46 to 1.98 m. HNO and kept at a temperature of 4°C until analysis. The piezometric head varied between 3.53 and Prior to any analysis, all the glassware and containers 5.34 m bgl during pre-monsoon and 2.04 to were soaked in deionized distilled water. The determi- 2+ 2+ 2+ 2+ 2+ 2 7.59 m bgl during post-monsoon. The specific nation of metal ions Cd , Pb , Cu , Zn , Mn , Ni +, 2+ capacity in the weathered, partly weathered and and Fe (227, 281.5, 323, 212, 278, 231 and 247.5 nm jointed rocks varies from 31 to 240.5 lpm/m/dd respective wavelength) in water samples were carried and the transmissivity values in weathered, partly out by atomic absorption spectrophotometer (Perkin weathered and jointed rocks vary from 15.5 to Elmer A analyst 400). The limit of detection for Cd was 154 m /day. The optimum yield varied from 45.40 0.0001 and 0.001 ppm for all other elements. The blank readings for all the metals were 0.00 ppm in deionized to 441.60 m /day. The specific capacity in the fis - sured and fractured formation ranges from 6.89 to water with EC value lower than 5 µS/cm. 117.92 lpm/m/dd and the transmissivity values ranges from 11.42 to 669.12 m /day. The specific Treatment process capacity values in the porous formation vary from 135 to 958 lpm/m.dd and the transmissivity values Preparation of graphene oxide ranged from 67.5 to 264.5 m /day. The optimum Graphene oxide was prepared according to the mod- yield varied from 232.8 to 549.6 m /day ified Hummer’s method that has been reported (Loganathan & Jafar Ahamed, 2017). GEOLOGY, ECOLOGY, AND LANDSCAPES 5 previously (Hummers & Offeman, 1958; Xu et al., were characterized by FESEM (Field emission scan- 2012) using graphite powder procured from sigma ning electron microscopy – ZEISS EVO MA 15). The Aldrich (SP-1 grade 325 mesh). In a typical synthesis, elemental composition of the as-prepared sample was graphite powder (10 g) was added into an 80°C solu- quantified by energy dispersive spectroscopy (EDS) tion of concentrated H SO (20 ml), K S O (4.2 g), using an X-ray detector (THERMO EDS) attached to 2 4 2 2 8 and P O (4.2 g) and the dark blue mixture was stirred the FESEM instrument. Additionally, Fourier trans- 2 5 vigorously and kept at 80°C for 4.5 h. The mixture was form infra–red spectroscopy (FT–IR) analysis was −1 cooled to room temperature, and diluted with 45 ml of carried out in the range of 400–4000 cm (Perkin deionized water. Finally, the solution was transferred Elmer). to a large beaker, and left overnight. The mixture was then carefully filtered and washed with deionized Results and discussion water using 0.22 μm polycarbonate filter until the pH value of the rinse water became neutral. The obtained Groundwater chemistry product was dried at 40°C for 24 hours under vacuum In this study area, pH values ranged between 6.94 and (Ahamed et al., 2015a). 7.81 with the mean value of 7.44 indicating that The pre-oxidized graphite powder was then oxi- groundwater is slightly alkaline in nature. EC varied dized by the Hummer’s method. 2 g of pre-oxidized from 890 µS/cm to 6560 µS/cm with mean of 4532 µS/ graphite powder was added in 46 ml of concentrated cm. TDS showed a wide variation from 798 to H SO of cold (0°C) condition. Then 12 g of KMnO 2 4 4 4546 mg/L with average value of 3867 mg/L. Based was added gradually under stirring and the tempera- on EC value (Langenegger, 1990), groundwater is ture of the mixture was maintained not exceeding 20° classified into saline water (1500–10,000 µS/cm). TH C. Then, it was removed from the ice-bath and the ranged between 445 and 1933 mg/L with mean value mixture was stirred at 35°C for 2 hours. 97 ml of of 1328 mg/L, the excess concentration is due to deionized water was slowly added gradually into the mineral weathering (bivalent cation Ca and Mg). mixture and the diluted suspension was maintained at 2+ 2+ During the analysis, Ca and Mg range from 82 to 98°C for 15 min. Again, 280 ml of deionized water and 591 mg/L and 52 to 116 mg/L, respectively. The excess 5 ml of 30% H O were added into the suspension. 2 2 calcium originated from leaching process of dolomites A brilliant yellow mixture was obtained and the pro- and gypsum, were as magnesium is from cattle feed duct was centrifuged and washed with 10% HCl solu- and fertilizer application. Sodium is responsible for tion to remove the excessive residual metal ions high salinity; it ranged between 674 and 1529 mg/L followed by deionized water to remove the acid until with mean value of 956 mg/L, which derived from the pH of filtrate was neutral. The final dark brown halite due to adsorption on sediments near the river solid product was obtained and dried in vacuum. belt. 93% of samples were in the borderline of potas- Exfoliation was done by sonicating the oxidized gra- sium limit (12 mg/L). phite dispersion for 30 min at 240 W. The prepared Among anions, Cl having excess concentration Graphene Oxide was dried in vacuum for 24 h ranged between 583 and 1619 mg/L, basically chloride (Ahamed et al., 2015a). is found in sewage and course of water passing Carbon nanosheet (graphene oxide) prepared from through natural salt formation in the earth crust. graphite was used for the treatment of groundwater 2- − − SO , F and HCO concentration ranged from 203 4 3 sample collected from Thirumanilayur station. to 264 mg/L, 0.9 to 1.6 mg/L and 226 to 398 mg/L, Equilibrium study (180 min) was carried out by add- respectively. Metal concentration recorded were ing 60 mg and 80 mg of adsorbent into each 100 ml of 2+ 2+ 2+ 2+ 2 ranked in the order Cd > Pb > Zn > Cu > Fe the same sample. The bottles were placed in a rotary + 2+ 2+ > Mn > Ni . Except cadmium and lead all other shaker and agitated for 180 min at a speed of 150 rpm metals are within the limit. to make sure that equilibrium is reached. The content was filtered, analyzed and the values were compared with the same sample before adsorption process and Water treatment process also with WHO (2005) and BIS (2003) standards. A preliminary study on Thirumanilayur sample has been carried out to assess the reduction nature of Characterization techniques graphene oxide using adsorption techniques. The phy- The prepared graphene oxide (GO) nanoparticles sical nature of graphene oxide before treatment has were subjected to XRD analysis. The XRD pattern been investigated using analytical techniques. X-ray was recorded (model: X’PERT PRO PAN analytical) diffraction measurements have been recorded during using Cu Kα radiation (λ = 1.54060 Å) with nickel different steps of preparation of nanocomposites. monochromator in the range of 2θ from 10° to 80°. Figure 3 depicts the XRD studies of the GO materials, The area, size and morphology of the prepared GO which is due to the oxidation process of graphite. The 6 A. J. AHAMED AND K. LOGANATHAN effective oxidation of graphite and the formation of shows a simple nanosheet morphological structure. GO has been compared with the characteristic strong Wave like surface morphology nanosheet is observed and sharp (002) peak at 11.02°. A typical FESEM for the entire reconstructed nanocomposites. The ele- image of the GO is given in Figure 4(a,b) which mental analysis data clearly indicates that graphene is Figure 3. XRD pattern of graphene oxide before treatment (GO) after treatment (60 and 80 mg). Figure 4. (a,b) SEM images of graphene oxide before treatment; (c) SEM images of graphene oxide (60 mg) and (d) SEM images of graphene oxide (80 mg) after treatment. GEOLOGY, ECOLOGY, AND LANDSCAPES 7 Figure 5. (a) EDS analysis of graphene oxide before treatment (b and c) EDS analysis of graphene oxide 60 mg and 80 mg after treatment. Figure 6. (a) FTIR spectra of graphene oxide before treatment; (b & c) FTIR spectra of graphene oxide 60 mg and 80 mg after treatment. 8 A. J. AHAMED AND K. LOGANATHAN 2+ 2+ coordinate with the oxygen atom. EDS profile of gra- when compared with Ca and Mg . The initial con- + + phene oxide C :O is in Figure 5(a). The IR fre- centration of Na and K is 1529 and 14.24 mg/L, after 0.56 0.44 −1 −1 −1, quencies at 3411 cm , 1725 cm , 1038 cm and treatment, it is reduced to 1361 & 10.78 mg/L for −1 1237 cm confirms the presence of many oxygen 60 mg adsorbent and 1278 & 8.16 mg/L for 80 mg containing groups such as OH, C=O, C-O, C-OH, adsorbent. The initial and final concentration of Na respectively in graphene oxide (Figure 6(a)). These and K in the sample was confirmed by Systronics evidences indicate that during the oxidation process Flame photometer 128. The result showed that the of the graphite powder with KMnO in the concen- adsorption of metal ions took place in the binding trated sulphuric acid, the original extended conjugated sites on the surface of the adsorbent in a monolayer π-orbital system of the graphite is destroyed and oxy- mode. gen-containing functional groups are introduced into The anionic species are not much reduced, because carbon skeleton (Ahamed et al., 2015a). The results of of the presence of negative charge on the surface of 2+ the treated sample (Thirumanilayur) show graphene oxide. Among trace elements, Pb is well a conspicuous reduction among water quality para- adsorbed on the GO, since heavy metals in the solu- 2+ meters. The graphene oxide is found to be more effec - tion are positively charged, the metal ion Pb bound tive in removing metals in water samples. The values strongly to graphene oxide. The initial concentration 2+ obtained for raw sample and after the treatment pro- of Pb in raw sample is 0.295 mg/L and after treat- cess by varying adsorbent dosage (60 and 80 mg) are ment it is 0.083 and 0.077 mg/L for 60 and 80 mg 2+ compared with standard limits of WHO (2005) and adsorbent. Trace amount of Cd is also adsorbed and BIS (2003) is presented in Table 2. the concentration is observed through an atomic pH of raw water sample is 7.82 and after treatment absorption spectrophotometer. The spectral studies it is 7.90 and 7.98 for 60 and 80 mg adsorbent, respec- evidently depict the reduction process take place in tively. pH is within the permissible limit, but the the water sample. Figure 3, the XRD pattern clearly increase in pH is due to the release of – OH group. indicates that the graphene oxide peak is disappeared Literature (Gao et al., 2013) has revealed that Pb(II) in 11.02° and new amorphous graphene oxide struc- and Cd(II) forms metal hydroxide, when the pH value ture is observed. It shows that the metal ions are is greater than 6.0. Thus, the increase in pH dramati- adsorbed on the surface of carbon nanosheet. The cally increases the adsorption capacities of Pb(II) and FESEM images of treated GO samples (Figure 4(c,d)) Cd(II). The value of the EC in raw sample is 6560 µS/ obviously display the agglomerated flake like morpho- cm, and it is 6193 and 5892 µS/cm after treatment. logical structure. It confirmed the change of surface TDS value ranged between 4292 and 4083 mg/L for 60 uniformity from GO to metal adsorbed GO and 80 mg adsorbent, and it is 4546 mg/L for raw nanosheets. Meanwhile, EDS (Figure 5(b,c)) analysis sample, the reduction of EC and TDS value confirms is evidences that the sodium and lead are predomi- the adsorption take place in the system. There is no nantly adsorbed on the surface of GO nanosheets. notable reduction in hardness, shows that hardness is FTIR spectra of treated GO samples in Figure 6(b,c) 2+ permanent in nature due to divalent cations (Ca and demonstrate the absence of OH, C=O peak at 2+ + + −1 −1 Mg ). Among cations, Na and K were reduced well 3411 cm and 1725 cm which confirms the process Table 2. Treated result for the adsorption process by graphene oxide. WHO BIS Parameters Before adsorption process After adsorption process (60 mg) After adsorption process (80 mg) limit limit pH 7.82 7.90 7.98 7–8.5 6.5–8.5 EC 6560 6193 5892 1000–2000 750–2250 TDS 4546 4292 4083 500 500 TH 1933 1917 1894 300 300 2+ Ca 591 589 585 75 75 2+ Mg 116 109 104 50 50 Na 1529 1361 1278 200 200 K 14.24 10.78 8.16 12 12 HCO 398 386 382 100 200 Cl 1619 1608 1596 200 250 F 1.6 1.5 1.5 1 1 2- SO 264 257 251 200 200 2+ Cd 0.069 0.056 0.052 0.01 0.003 2+ Pb 0.295 0.083 0.077 0.05 0.01 2+ Cu 0.036 0.033 0.032 0.05 2 2+ Zn 0.092 0.090 0.087 5 3 2+ Mn 0.002 bdl* bdl* 0.1 0.4 2+ Ni bdl* bdl* bdl* - 0.02 2+ Fe 0.094 0.082 0.074 0.3 0.3 All the values are expressed in mg/L, except pH and EC in µS/cm, *bdl-below detectable limit GEOLOGY, ECOLOGY, AND LANDSCAPES 9 of adsorption taking place on GO, which is further and-correlation-analysis-of-surface-and-ground-water- of-amaravathi-river-basinkarur-tamilnadu-india.pdf confirmed that, the metal or metal hydroxide (Zhou −1 Ahamed, A. J., & Loganathan, K. (2017). Water quality et al., 2012) peaks appear below 1500 cm . concern in the Amaravathi River basin of Karur District: A view at heavy metal concentration and their interrelationships using geostatistical and multivariate Conclusion and summary analysis. Geology, Ecology and Landscapes, 1(1), 19–36. https://doi.org/10.1080/24749508.2017.1301055 In this present study the dominant cation found in Ahamed, A. J., Loganathan, K., & Jayakumar, R. (2015b). + 2+ 2+ + groundwater is Na followed by Ca , Mg and K . Hydrochemical characteristics and quality assessment of − − 2- The dominant anion is Cl followed by HCO , SO 3 4 groundwater in Amaravathi river basin of Karur district, − 2+ 2+ and F . Among trace elements Cd and Pb were in Tamil Nadu, South India. Sustainable Water Resources Management, 1(3), 273–291. https://doi.org/10.1007/ excess concentration. Analysis identifies both man- s40899-015-0026-3 made activities and geochemical process responsible Ahamed, A. J., Loganathan, K., & Vijayakumar, P. (2013). for groundwater quality in Amaravathi River basin. Bio-chemical investigation of selected water quality para- Reduced graphene oxide is used as adsorbent to meters in Amaravathi River basin, Karur district, reduce excess ion concentration. The parameters like Tamilnadu, India. International Journal of Current + + 2+ 2+ Research, 5(10), 3100–3103. http://journalcra.com/arti EC, TDS, Na , K and metals like Cd and Pb cle/bio-chemical-investigation-selected-water-quality- showed remarkable reduction. The rate of adsorption parameters-amaravathi-river-basin-karur increases when increase in adsorbent dosage. XRD Ahamed, A. J., Vijaya Kumar, P., & Srikesh, G. (2015a). pattern, FESEM and EDS analysis confirmed the Low temperature synthesis and characterization of adsorption process. The groundwater in the rGO-CoO nanocomposite with efficient electrochemi- Amaravathi River Basin is in a critical situation and cal properties. Journal of Environmental Nanotechnology, 4(2), 01–08. https://doi.org/10.13074/ the results of the groundwater quality can be jent.2015.06.152147 employed in future groundwater panning and APHA. (2005). Standard methods for the examination of developments. water and wastewater (21st ed.). American Public Health Association. Asha, K. (1998). A pollution challenge. Frontline, The Acknowledgments Hindu, 15 (13),(June 20-July 3). BIS. (2003). Indian standards specification for drinking water The one of the author Dr. A. Jafar Ahamed is thankful to the 15: 10500. Bureau of Indian Standards. University Grants Commission (UGC), New Delhi for pro- CGWB. (2008). District groundwater brochure, Karur dis- viding Major Research Fund (F. No.41-337/2012) and the trict, Tamil Nadu. Central Ground Water Board. Members of the Management Committee and the Principal Gao, H., Sun, Y., Zhou, J., Xu, R., & Duan, H. (2013). of Jamal Mohamed College for providing necessary Mussel-inspired synthesis of facilities. polydopamine-functionalized graphene hydrogel as reu- sable adsorbents for water purification. ACS Applied Materials & Interfaces, 5(2), 425–432. https://doi.org/10. Disclosure statement 1021/am302500v Hua, M., Zhang, S., Pan, B., Zhang, W., Lv, L., & Zhang, Q. No potential conflict of interest was reported by the (2012). Heavy metal removal from water/wastewater by author(s). nanosized metal oxides: A review. Journal of Hazardous Materials, 211-212, 317–331. https://doi.org/10.1016/j. jhazmat.2011.10.016 Funding Hummers, W. S., & Offeman, R. E. (1958). Preparation of graphite oxide. Journal of American Chemical Society, 80 This work was supported by the University Grants (6), 1339. https://doi.org/10.1021/ja01539a017 Commission (F.No. 41-337/2012). Langenegger, O. (1990). Ground water quality in rural areas of western Africa, UNDP project INT/81/026: 10. 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Journal

Geology Ecology and LandscapesTaylor & Francis

Published: Jan 2, 2023

Keywords: Adsorption; Amaravathi River; graphene oxide; Karur; nanomaterial

References