Potentiality of a fruit peel (banana peel) toward abatement of fluoride from synthetic and underground water samples collected from fluoride affected villages of Birbhum district

Potentiality of a fruit peel (banana peel) toward abatement of fluoride from synthetic and... Contamination of underground water with fluoride (F) is a tremendous health hazard. Excessive F (> 1.5 mg/L) in drinking water can cause both dental and skeletal fluorosis. A fixed-bed column experiments were carried out with the operating vari - ables such as different initial F concentrations, bed depths, pH and flow rates. Results revealed that the breakthrough time and exhaustion time decrease with increasing flow rate, decreasing bed depth and increasing influent fluoride concentration. The optimized conditions are: 10 mg/L initial u fl oride concentration; o fl w rate 3.4 mL/min, bed depth 3.5 and pH 5. The bed depth service time model and the Thomas model were applied to the experimental results. Both the models were in good agreement with the experimental data for all the process parameters studied except flow rate, indicating that the models were appropriate for removal of F by natural banana peel dust in fix-bed design. Moreover, column adsorption was reversible and the regeneration was accomplished by pumping of 0.1 M NaOH through the loaded banana peel dust column. On the other hand, field water sample analysis data revealed that 86.5% fluoride can be removed under such optimized conditions. From the experimental results, it may be inferred that natural banana peel dust is an effective adsorbent for defluoridation of water. Keywords Banana peel · Fluoride · Column study · Dental and skeletal fluorosis · Regeneration Introduction in drinking water should not exceed beyond 1.5 mg/L. Many technologies such as precipitation, ion exchange, electrolysis Due to rapid industrialization, huge quantity of pollutants have been developed. However, all the above techniques are discharges in to the environment. Fluorine is one such pol- not cost-effective. These are high maintenance charge and lutant that threatens living organisms, in particular humans not easy to regenerate. But there is another technique, called (Koilraj and Kannan 2013). Fluoride is a strongly electron- adsorption which is an important cost-effective technique egative element, and its presence in drinking water is essen- widely used in most of the developing country for removal tial for human health (Chen et al. 2012). However, excess of fluoride from drinking water (Mondal and Roy 2015). consumption of fluoride can lead to both dental and skeletal Pertinent literature highlighted that many cost-effective fluorosis (Kierdorf et al. 2016; Death et al. 2015). Previ- adsorbents such as sugarcane bagasse, tea waste ash, alu- ous literature (Mohan et al. 2012) demonstrated that more minum impregnated potato plant ash and coconut fiber ash, than 200 million people worldwide are affected by fluoride- lemon leaf dust, banana peel dust, rice husk carbon, tea contaminated drinking water with very high concentration. ash, silica gel, egg shell dust, calcareous soil, coconut fiber, As per the guideline adopted by WHO (2011) and Bureau banana peel have been used for removal of fluoride from of Indian standard (BIS 1991), the concentration of fluoride contaminated drinking water (Ghosh et al. 2016; Mondal et al. 2015; Bhaumok et al. 2013; Mondal et al. 2012a, b, c, d; Bhaumik et al. 2012; Bhaumik and Mondal 2014a, b). But none of the above adsorbents showed excellent removal * Naba Kumar Mondal nkmenvbu@gmail.com performance along with high adsorption capacity. There- fore, it is prime important to synthesize an efficient and cost- Environmental Chemistry Laboratory, Department effective adsorbent for decontamination of fluoride from the of Environmental Science, The University of Burdwan, aqueous medium (Chen et al. 2012). Bardhaman, West Bengal, India Vol.:(0123456789) 1 3 90 Page 2 of 10 Applied Water Science (2018) 8:90 Table 1 Physical characteristics of banana peel Adsorption technique normality processed through batch and column process (Tor et al. 2009). But in batch process, Parameter Values all the operating variables remain constant while one vari- pH 6.59 able changes at a time, and the process is costly and time- Conductivity (mS/cm) 190 consuming. Therefore, column separation process may be Specific gravity 2.66 the suitable one for defluoridation of domestic as well as Bulk density (g/cc) 0.384 community level. In our previous work, we have used the Particle density (g/cc) 0.138 banana peel for removal of fluoride through batch process Porosity (%) 178.26 followed by response surface optimization techniques. Very Moisture content (%) 2.98 recently, we have tried with another variety of banana peel P 5.63 zpc for the same purposes. But, we cannot achieve to reach the Dry matter 89.73 desired level. Crude fiber 10.33 Bananas are a popular fruit consumed worldwide with an Ash 17.94 early production of over 145 million tonnes in 2011. Once BET surface area 23.983 m /g the peel is removed, the fruit can be raw or cooked and peel is generally discarded. On average, banana peel contains 6–9% dry matter of protein and 20–30% fiber. Normally, the ripe banana peels contains 30% free sugar and 15% more The pH of the 0.1 (M) KNO solutions was adjusted by using starch than green banana peels. Moreover, banana peel has 0.05 (N) HNO and 0.1 (N) KOH solutions. After thoroughly many biomolecules such as lignin, cellulose and hemicel- shaking (24 h), the pH of the final solutions was recorded lulose with variety of active functional groups (carboxyl, and a graph was constructed by pH versus ΔpH. hydroxyl, amine, etc.) which suppose to bind the pollutants (Deshmukh et al. 2017; Kumar et al. 2011). Column study The present work is aimed at synthesizing an efficient and economical adsorbent using banana peel toward removal Thomas model of fluoride from water through column study. Finally, the prepared adsorbent was used for removal of fluoride from The Thomas model can be used to predict the breakthrough field samples which was collected from the fluoride affected curve and the maximum adsorption capacity of the banana villages of Birbhum district, West Bengal. peel in a fixed-bed operation. The linearized form of Thomas model can be presented in Eq. (1): Materials and methods C K q X K C t 0 Th 0 Th 0 ln = − (1) C − 1 Q Q Preparation of banana peel dust where X is the amount of sorbent taken in the column (g) The raw waste banana peels (Musa paradisiaca) were col- and Q is the effluent flow rate (mL/min). The kinetic coef- lected from nearby fruits stall of Burdwan town, West Ben- ficient K and the adsorption capacity of the bed q for Th 0 gal. After collection, peels were thoroughly washed with the defluoridation process can be calculated by plotting distilled water followed by washing with de-ionized water ln(C /C − 1) versus t. and dried in hot air oven at 50 °C for 12 h. The dried peels were cut into small pieces and again dried in hot air oven maintaining 60 °C temperatures for 24 h. The dried banana Bed depth service time model (BDST) peels were ground using kitchen grinder to get the desired particle size (200 μm), the powder form of banana peel was It is familiar that BDST model provide a simplest approach and suitable prediction of absorber performance (Al-Degs stored in airtight container, the physico-chemical analysis was done, and the results are depicted in Table 1. et al. 2009). BDST model basically provides a relationship between column bed depth, X and service time t. However, Point of zero charge (pH ) this particular model also focused on the estimation of char- ZPC acteristic parameters such as maximum adsorption capacity Zero point charge of the banana peel was determined by fol- (N ) kinetic constant (K). Moreover, this model considers one valuable assumption that is the adsorption rate is propor- lowing the solid addition method (Mondal 2010). Initially, a series of conical flasks were taken with 50 mL of 0.1 (M) tional to residual capacity of the sorbent and the concentra- tion of the sorbing species. The relationship of service time KNO solutions in each flask along with 0.1 g banana peel. 1 3 Applied Water Science (2018) 8:90 Page 3 of 10 90 with process conditions and operating parameters is given (Systronic 206). The breakthrough curves were constructed as Eq. (2): by Origin software (Version 6.0). C KXN 0 0 ln − 1 = ln exp − 1 − KC t Dental and skeletal fluorosis study (2) C v Primary school children aged between 5–10  years were A linear relationship between bed depth and service time selected from fluoride affected villages of Birbhum district, may be given by Eq. 3 (Al-Degs et al. 2009) West Bengal. Dental fluorosis was examined by a trained N X C 0 0 examiner who held a master degree in dentistry with the help t = − ln − 1 (3) vC KC C 0 0 b of Dean index (Dean 1934). Skeletal fluorosis was assessed by clinical symptoms and physical exercise (Susheela and where C is the initial concentration of solute (mg/L), C 0 b Bhatnagar 2002; Shashi et al. 2008). the desired concentration of solute at breakthrough (mg/L), K the adsorption rate constant (L/mg/h), N the adsorption capacity (mg/L), X the bed depth of column (cm), v the lin- Results and discussion ear flow velocity of feed to bed (cm/h), and t the service time of column under above conditions (hrs). Equation (4) can be Adsorbent characterization rewritten in the form of a straight line. T = aX − b Preparation of banana peel dust was subjected to pH (4) ZPC and SEM study for understanding the zero point charge and where ‘a’ is slope of BDST line ( a = ) and the intercept vC surface morphology (HITACHI-S-530, Scanning Electron of this equation represents as Eq. (5): Microscope and ELKO Engineering, accelerating voltage C of 20.0 kV) and surface chemistry of the banana peel was b = ln − 1 (5) assessed by FTIR (BRUKER, Tensor 27). The zero point KC C 0 b charge of the banana peel was recorded as 5.63 (Fig. 1), and Thus, N and K can be evaluated from slope (a) and the 0 from the scanning micrograph it is clear that the surface intercept (b) of the plot of t versus X, respectively. of the banana peel dust is absolutely rough in nature and huge heterogeneity (Fig. 2a). However, after F removal, the surface of banana peel is smooth with less degree of hetero- Column regeneration study geneity (Fig. 2b). The Fourier transformer infrared spectros- copy clearly revealed that it has sharp peaks at 3340, 2890 In order to activate the exhausted column, regeneration −1 and 1741 cm which corresponds the functional groups experiments were conducted by using 0.1 (M) NaOH solu- hydroxyl (–OH), alkyl C–H, and carboxyl (–COOH), respec- tions. The desorption experiments were conducted with tively (Fig. 3). Therefore, it is expected that the functional the flow rate 2 mL/min. After passing 100 mL of 0.1 (M) groups such as –OH and –COOH may interact with fluoride NaOH, the entire column bed was washed with double dis- during adsorption. tilled water. Finally, the regenerated column was then used for the next cycle of column adsorption. The desorption efficiency E was calculated by the fol- lowing Eq. (6) (Zhu et al. 2007) M × 100 E = (6) [(q + M )] 2 where M is desorption fluoride amount (mg) eluted by des- 5.63 orption solution (0.3 M NaOH). q and m are the capacity at exhaustion point (L) and adsorbent dose, respectively, and 0 M is the fluoride amount (mg) retained in the column. -1 Analytical procedure -2 2 46 810 pH Effluent solution was collected at regular interval, and their concentrations were measured (Thermo Orion, 4 star); pH of the experimental solution was measured by using pH meter Fig. 1 ZPC of Banana peel dust 1 3 Initial pH - Final pH 90 Page 4 of 10 Applied Water Science (2018) 8:90 The effect of initial concentration of solution on breakthrough curve Three different initial concentrations (1.5, 10, 35 mg/L) were used in this study. The values were chosen because they were considered to fairly represent fluoride concentration range in most groundwater. The bed mass and flow veloc- ity of the present experiment have been taken as 2 g and 3.4 mL/min, respectively. The breakthrough curves (BTCs) obtained from the experimental investigation of the effect of the initial concentration on fluoride removal are depicted in Fig. 4. From Fig. 4 it is clear that higher the fed concen- tration, the steeper is the breakthrough curve and smaller is the breakthrough time. The adsorbent exhaustion rates (AER) (bed volume (BV) in parenthesis) were computed and found to be 0.046(3.31), 0.023(6.16) and 0.009(15.39) g/L for the initial concentrations of 35, 10 and 1.5 mg/L, respectively (Table 2). As the concentration increase, the driving force for adsorption increases and the active sites are consumed faster. The results also highlighted that both saturation rate and breakthrough time change with changing influent concentration (Goel et al. 2005). This is because, at higher concentration, the active sites of the adsorbent get saturated very quickly (Mondal et al. 2013). The effect of flow rate on breakthrough curve Steeper breakthrough curve was obtained at higher flow rates (Fig. 5). Further it was studied that the steepness of the breakthrough curve reduces with decreasing flow rates Fig. 2 Scanning electron microscopy of banana peel: a before passing fluoride solution (×1500 magnification), b after passing fluoride solu- i.e., increase in breakthrough time. The breaks through tion (×1500 magnification) curves appeared steeper at higher flow rates may be due to faster movement of adsorption zone along the bed aiding its quick saturation (Sulaiman et al. 2009; Tor et al. 2009). Again the variation in the slope of the breakthrough curve Fig. 3 FTIR spectrum of banana peel dust (BPD) 1 3 Applied Water Science (2018) 8:90 Page 5 of 10 90 bed volumes (BV) of water processed at breakthrough curve 0.24 were found to be 6.02, 30.08, and 176.93 L for 1.7, 3.4, and 0.22 8.0 mL/min, respectively (Table 2). The increase in volume 0.20 processed with an increased in velocity can be attributed to reduced influence of external mass transfer resistance 0.18 (Ghribi and Chlendi 2011). The AER values for this respec- 0.16 tive flow rate are 0.029, 0.006 and 0.001 g/mL, respectively. 0.14 0.12 The effect of pH on breakthrough curve 0.10 35 mg/l The breakthrough curves for different pH are shown in 10 mg/l 0.08 1.5 mg/l Fig. 6. The pH of the aqueous solution has been recog- 0.06 nized as one of the most important factors influencing 050 100 150200 250300 350400 450 adsorption kinetics due to its direct inf luence on the sur- time (minute) face properties of the adsorbent (Memon et al. 2008). As shown in Fig. 6, where the value of pH was 5, the value Fig. 4 Breakthrough curve of the effect of different influent con- of C /C reached 0.042 in 30 min. But the breakthrough t 0 centration on fluoride adsorption onto banana peel (v = 3.4  ml/min, curve of the pH 7.0 and 9.0 was not more than 0.045 and Z = 0.9 cm, pH = 5) 0.109 in the different time periods, respectively. With a decrease in pH in the influent, the breakthrough curves and adsorption capacity may be explained on the basis of shifted from left to right, which indicates higher removal mass transfer fundamentals. The reason is that at higher flow of fluoride. It would spend more time reaching the satura- rate the rate of mass transfer increases, i.e., the amount of tion, and the efficiency of biosorption was much higher fluoride adsorbed onto unit bed height (mass transfer zone) (Ma et al. 2008). The F ion binding could be attributed increased with increasing flow rate leading to faster satura- to several mechanisms such as ion exchange, complexa- tion at higher flow rate (Talnikar et al. 2004). The increase tion, electrostatic attraction and precipitation. For banana in adsorption capacity (both up to breakthrough and exhaust) peel, ion exchange has been considered as a main mecha- of banana peel was more pronounced at the flow rate of nism responsible for pollutant sequestering (Sheng et al. 1.7 mL/min, whereas the effect is almost negligible at the 2004). The result suggests that with the decrease in pH, flow rate of 8.0 mL/min. The rate constant, K , increased under experimental condition, the adsorption capacities Th with increasing the flow rate which indicates that the mass increase (Table 2). So the removal of f luoride from aque- transport resistance decreases (Tor et al. 2009). The different ous solution was more efficient at lower initial pH value. Table 2 Summary of pertinent Parameters Service time Adsorption capacity Bed volume pro- AER (g/ml) results at breakthrough point of (min)t (mg/g) q cessed (BV) b b banana peel Adsorbent mass (g)  2 40 0.405 12.03 0.015  4 100 0.429 15.92 0.012  8 250 0.449 19.34 0.009 pH  5.0 30 0.479 9.02 0.020  7.0 60 0.477 18.05 0.010  9.0 300 0.441 90.23 0.002 Different flow (ml/min)  1.7 40 0.495 6.02 0.029  3.4 100 0.477 30.08 0.006  8.0 250 0.466 176.93 0.001 Initial concentration (mg/L)  35.0 30 0.014 3.31 0.046  10.0 60 0.109 6.16 0.023  1.5 150 0.419 15.39 0.009 1 3 c /c t 0 90 Page 6 of 10 Applied Water Science (2018) 8:90 0.12 The effect of different bed depths on the breakthrough curve 0.11 0.10 1.7ml/min Keeping the initial concentration of fluoride, flow rate and 3.4ml/min 0.09 8.0ml/min pH of the solution constant and with varying bed depth, the number of active sites available for sorption and the 0.08 contact time of solute with the adsorbent were determined. 0.07 Figure 7 shows the BTs obtained upon varying the quan- 0.06 tity of adsorption media between 2, 4 and 8 g. From the 0.05 BTCs, the t and q were determined and are summarized b b in Table 2. From the bed depth study, it was found that as 0.04 the bed height increases, adsorbate had more time to con- 0.03 tact with banana peel dust that resulted in higher removal 050 100 150 200250 300350 400450 efficiency of fluoride ion in column (Fig.  7). So, the higher time(minute) bed depth results in a decrease in the solute concentra- tion in the effluent at the same time. The slope of break - Fig. 5 Breakthrough curve of the effect of different flow rate on fluo- through curve decreased with increasing bed height, which ride adsorption onto banana peel dust (C = 10.0  mg/L, Z = 0.9  cm, resulted in a broadened mass transfer zone. High uptake pH = 5) was observed with highest bed depth 3.7 cm height due to an increase in the surface area of biosorbent, which provided more binding sites for the sorption (Vadivelan 0.12 and Kumar 2005). Almost similar results were reported by Paudyal et al. (2013) and Mondal et al. (2013) for F 0.10 pH5 removal by dried orange juice residue and sugarcane char- pH7 coal. The different bed volumes (BV) of water processed at pH9 breakthrough curve were found to be 12.03, 15.92, 19.34 0.08 L, and the AER value was found to be 0.0145, 0.0117, 0.0094 g/mL for 2, 4 and 8 g of banana peel dust adsor- 0.06 bent, respectively. 0.04 0.02 050 100 150200 250 300350 400 450 time (minute) 0.20 Fig. 6 Breakthrough curve of the effect of different pH on fluoride adsorption onto banana peel dust (v = 3.4  ml/min, C = 10.0  mg/L, Z = 2 g) 0.15 The AER for different pH are 0.0196, 0.098, 0.020 g/mL, respectively. There are many reasons which may be attrib- uted toward the f luoride adsorption behavior of the sorb- 0.9cm ent relative to solution pH. At lower pH, the surface of 1.7cm 3.5cm banana peel may get positively charged, which enhances the negatively charged f luoride ion through electrostatic 0.10 force of attraction (Han et  al. 2007). Almost similar results reported by Paudyal et al. (2013) for removal of 050100 150200 250 300350 400450 F using a fixed-bed column packed with Zr (IV) loaded time (minute) dried orange juice residue. Fig. 7 Breakthrough curve of the effect of different bed depth on fluoride adsorption onto banana peel dust (v = 3.4  ml/min, C = 10.0 mg/L, pH = 5) 1 3 c /c c /c t 0 t 0 ct/c0 Applied Water Science (2018) 8:90 Page 7 of 10 90 Table 3 Calculated constants 2 pH Z (cm) v (ml/min) C (mg/L) K (ml/min/mg) q (mg/g) R 0 th 0 of Thomas model at different conditions using linear 5 3.5 3.4 10 55.12 98.26 0.999 regression analysis 7 3.5 3.4 10 55.12 98.26 0.999 9 3.5 3.4 10 55.12 98.26 0.999 5 0.9 3.4 10 7.80 3.76 0.996 5 1.7 3.4 10 7.80 1.88 0.996 5 3.5 3.4 10 7.80 0.94 0.996 5 3.5 1.7 10 12.61 29.81 0.775 5 3.5 3.4 10 25.22 59.61 0.775 5 3.5 8.0 10 59.34 140.27 0.775 5 3.5 1.7 1.5 43.58 8.15 0.996 5 3.5 1.7 10 6.54 8.15 0.996 5 3.5 1.7 35 1.87 8.15 0.996 Fig. 8 BDST model at break- BDST model Banana peel through curve in fixed-bed column for F adsorption by 3.5 banana peel 2.5 y = 0.0123x + 0.4333 R² = 0.9994 1.5 0.5 050 100 150 200 250 300 service time (minute) Table 4 Calculated constants of BDST model for the adsorption of Table 5 Column regeneration parameters for NBP column fluoride by banana peel dust using linear regression analysis Regeneration cycle Percentage of desorption Q E (%) E D C /C a (min/cm) b (min) K (l/mg/min) N (mg/l) R (mg/g) (%) t 0 a 0 0.0101 0.0123 0.4333 0.005 0.4182 0.9994 1 84 2.091 2 72 1.321 = 10.0 mg/L, v = 3.4 ml/min 3 54 0.694 Adsorption operation constant–initial fluoride concentration: 8  ml/ min; Z = 0.9  cm; pH = 5; C = 10  mg/L. Desorption condition—des- Modeling of breakthrough curve orption solution 0.1 M NaOH, solution flow rate 2 ml/min The entire experimental column study has been fitted with scaled up to other flow rates without further experimental Thomas model, results revealed that all the operating vari- runs. ables are well acquainted with Thomas model, and goodness of the fit of the model (R ) is very high except variation of flow rate (Table  3). A plot of service time (t) versus bed Regeneration study depth (X) at a flow rate of 3.4 mL/min is shown in Fig.  8. The equation of the linear relationship was obtained with After regeneration of the exhausted column, it has been R above 0.999. This indicated the validity of the BDST found that desorption gradually decreases from first to sec- model for present column system. The calculated adsorption ond and second to third cycles. The calculated column des- capacity (N ) and the rate constant (K) are 0.418 mg/L and −3 orption parameters are listed in Table 5. From Table 5, it 5 × 10 L/mg/min, respectively (Table 4). The advantage of is clear that E value decreases with consecutive cycles of the BDST model is that any experimental test can be reliably 1 3 Bed depth (cm) 90 Page 8 of 10 Applied Water Science (2018) 8:90 desorption (Tor et al. 2009). This is probably due to the loss Table 6 Physico-chemical characteristics of ground water of adsorption capability of banana peel dust column. Parameters Values Conductivity (μS/cm) 113 ± 2.07 Defluoridation from field sample Hardness (mg/L, CaCO ) 178 ± 3.11 Chlorine (mg/L) 12.3 ± 0.71 Forty three (43) tube well water samples were collected from Nitrate (mg/L) 9.3 ± 0.06 the severally fluoride affected villages of Birbhum district, Sulfate (mg/L) 0.81 ± 0.013 West Bengal. The children aged between 5 and 10 years Fluoride (mg/L) 9.89 ± 0.33 were selected for understanding the status of dental and pH 7.9 skeletal fluorosis (Fig.  9). From the data (data not shown), it is clear that about 63% boys and 48% girls were severally Mean ± SD affected by dental fluorosis (Fig.  9). However, 18% boys and 12% of girls were affected by skeletal fluorosis (Fig.  9). the adsorption capacity of banana peel increased with The physico-chemical analysis of the field samples is pre- sented in Table 6. From Table 6 it is found that the highest decreasing medium pH. Column study revealed the best fluoride removal conditions as: 10 mg/L initial fluoride fluoride level in the affected areas is 9.89 mg/L. Moreover, for field sample defluoridation study, highest fluoride con- concentration; flow rate 3.4  ml/min, bed depth 3.5 and pH 5. The study results were best fitted with both Thomas taining tube well water (9.89 mg/L) was selected and it was recorded that about 86.5% removal can be achieved through and BDST models. Moreover, Thomas equation indicated that the increase in bed height caused an increase in the standardized column study (v = 3.4 mL/min, C = 9.89, pH = 5, Z = 3.7 cm). mass transport resistance and axial dispersion, which was confirmed from the K values. The exhausted banana peel Th dust can be regenerated by 0.1 M NaOH and reused with minimal loss of efficiency for three adsorption–desorption Conclusions cycles. Finally, best optimized conditions were applied for defluoridation of the field sample, and 86.5% removal was Present finding highlights the removal of fluoride from both synthetic and field samples using banana peel dust achieved. Therefore, it can be conclude that the use of banana peel as an adsorbent for fluoride removal is poten- through column study. The surface morphology of the banana peel dust was assessed by SEM study, and the tially cost-effective and may provide an alternative method for fluoride removal from contaminated water. active functional group was evaluated by FTIR study (Table  7). Fluoride adsorption results highlighted that Fig. 9 Children affected by skletal and dental fluorosis in the study area 1 3 Applied Water Science (2018) 8:90 Page 9 of 10 90 Table 7 Comparative evaluation Adsorbent pH Adsorption capac- References of adsorption capacities of ity (mg/g) various biosorbents for fluoride removal 1. Acid and alkali treated Tamarindous 2–10 – Ramanjaneyulu et al. (2013) indica fruit shall 2. Acid treated Banana peel 2–12 1.34 Mohammad and Majumder (2014) 3. Untreated Tamarind fruit corner 1–8 4.14 Sivasankar et al. (2012) 4. Mousabi (Citrus limetta) peel 7.0 1.915 Singh and Majumder (2015) 5. Ground nut (Arachishypogaea) 7.0 1.15 Singh and Majumder (2015) 6. Untreated sweet lemon peel 2–12 0.744 Mohammad and Majumder (2014) 7. Untreated Banana peel (BPD-1) 2–10 17.43 Bhaumik and Mondal (2014b) 8. Algal Biosorbent Spirogyra sp. 2.0 1.272 Mohan et al. (2007) 9. Leaf biomass powder sample 2.0 Jamode et al.(2004) 10. Treated coffee husk 2.0 0.416 Getachew et al. (2015) 11. Guava seeds – 116.5 Sánchez-Sánchez et al. (2013) 12. Banana peel 5.0 8.15 Present work Acknowledgement The authors are grateful to Dr. Rajarshi Ghosh, Chen H, Yan M, Yang X et al (2012) Spatial distribution and temporal Assistant Professor, Department of Chemistry, Burdwan University, variation of high fluoride contents in groundwater and prevalence Burdwan, West Bengal, India, for recording FTIR data and they also of fluorosis in humans in Yuanmou County, Southwest China. extend their gratitude to Dr. Srikanta Chakraborty, Incharge of SEM, J Hazard Mater 235:201–209. https ://doi.or g/10.1016/j.jhazm USIC, University of Burdwan, West Bengal, India, for SEM study. at.2012.07.042 Dean HT (1934) Classification of mottled enamel diagnosis. J Am Dent Assoc 21:1421–1426 Compliance with ethical standards Death C, Coulson G, Kierdorf U, Kierdorf H, Morris WK, Hufschmid J (2015) Dental fluorosis and skeletal fluoride content as biomark - Conflict of interest Authors declare that they have no conflict of inter - ers of excess fluoride exposure in marsupials. Sci Total Environ est for publishing the present manuscript. 533:528–541 Deshmukh PD, Khadse GK, Shinde VM, Labhasetwar P (2017) Cad- Open Access This article is distributed under the terms of the Crea- mium removal from aqueous solutions using dried banana peels tive Commons Attribution 4.0 International License (http://creat iveco as an adsorbent: kinetics and equilibrium modeling. J Bioremediat mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- Biodegrad 8:395. https ://doi.org/10.4172/2155-6199.10003 95 tion, and reproduction in any medium, provided you give appropriate Getachew T, Hussen A, Rao VM (2015) Defluoridation of water by credit to the original author(s) and the source, provide a link to the activated carbon prepared from banana (Musa paradisiaca) peel Creative Commons license, and indicate if changes were made. and coffee (Coffea arabica) husk. Int J Environ Sci Technol 12:1857–1866 Ghosh SB, Bhaumik R, Mondal NK (2016) Optimization study of adsorption parameters for removal of fluoride using aluminium- impregnated potato plant ash by response surface methodology. References Clean Technol Environ Policy 18:1069–1083 Ghribi A, Chlendi M (2011) Modeling of fixed bed adsorption: applica- tion to the adsorption of an organic dye. Asian J Text 1:161–171 Al-Degs YS, Khraisheh MAM, Allen SJ, Ahmad MN (2009) Adsorp- Goel J, Kadirvelu K, Rajagopal C, Garg VK (2005) Removal of lead tion characteristics of reactive dyes in columns of activated car- (II) by adsorption using treated granular activated carbon: batch bon. J Hazard Mater 165:944–949 and column studies. J Hazard Mater B 125:211–220 Bhaumik R, Mondal NK (2014a) Adsorption of fluoride from aqueous Han R, Wang Y, Yu W, Zou W, Shi J, Liu H (2007) Biosorption of solution by a new low-cost adsorbent: thermally and chemically methylene blue from aqueous solution by rice husk in a fixedbed activated coconut fibre dust. Clean Techn Environ Policy. https:// column. J Hazard Mater 141:713–718 doi.org/10.1007/s1009 8-015-0937-6 Jamode AV, Sapkal VS, Jamode VS (2004) Defluoridation of water Bhaumik R, Mondal NK (2014b) Optimizing adsorption of fluoride using inexpensive adsorbents. J Indian Inst Sci 84:163–171 from water by modified banana peel dust using response surface Kierdorf H, Rhede D, Death C, Hufschmid J, Kierdorf U (2016) Recon- modelling approach. Appl Water Sci. ht tps : //doi .org /10.10 07/ structing temporal variation of fluoride uptake in eastern grey kan- s1320 1-014-0211-9 garoos (Macropus giganteus) from a high-fluoride area by analysis Bhaumik R, Mondal NK, Das B, Roy P, Pal KC, Das C, Banerjee A, of fluoride distribution in dentine. Environ Pollut 211:74–80 Dutta JK (2012) Eggshell powder as an adsorbent for removal of Koilraj P, Kannan S (2013) Aqueous fluoride removal using ZnCr lay - fluoride from aqueous solution: equilibrium, kinetic and thermo- ered double hyroxides and their polymeric composites: batch and dynamic studies. Eur J Chem 9(3):1457–1480 column studies. Chem Eng J 234:406–415 Bhaumik R, Mondal NK, Chattoraj S, Datta JK (2013) Application Kumar J, Balomajumder C, Mondal P (2011) Application of agro- of response surface methodology for optimization of fluoride based biomasses for zinc removal from wastewater-a review. removal mechanism by newely developed biomaterial. Am J Anal Clean Soil Air Water 39:641–652 Chem 4:404–419 1 3 90 Page 10 of 10 Applied Water Science (2018) 8:90 Ma W, Ya F, Wang R, Zhao YQ (2008) Fluoride removal from drinking Ramanjaneyulu V, Jaipal M, Yasovardhan N, Sharada S (2013) Kinetic water by adsorption using bone char as a biosorbent. Int J Environ studies on removal of fluoride from drinking water by using Technol Manag 9:59–69 tamarind shell and pipal leaf powder. Inter J Emerg Trends Eng Memon JR, Memon SQ, Bhanger MI, Memon GZ, El-Turki A, Allen Develop 5(3):146–155 GC (2008) Characterization of banana peel by scanning electron Sánchez-Sánchez HA, Cortés-Martínez R, Alfaro-CuevasVillanueva R microscopy and FT-IR spectroscopy and its use for cadmium (2013) Fluoride removal from aqueous solutions by mechanically removal. Colloids Surf B 66:260–265 modified guava seeds. Int J Sci Basic Appl Res 11(1):159–172 Mohammad A, Majumder CB (2014) Removal of fluoride from syn- Shashi A, Kumar M, Bhardwaj M (2008) Incidence of skeletal deformi- thetic waste water by using bioadsorbents. Int J Res Eng Technol ties in endemic fluorosis. Trop Dr 38:231–233 3(4):776–785 Sheng PX, Ting Y, Chen JP, Hong L (2004) Sorption of lead, copper, Mohan SV, Ramanaiah SV, Rajkumar B, Sarma PN (2007) Removal cadmium, zinc and nickel by marine algal biomass: characteriza- of fluoride from aqueous phase by biosorption onto algal biosorb- tion of biosorptive capacity and investigation of mechanisms. J ent Spirogyra sp.-IO2: sorption mechanism elucidation. J Hazard Colloid Interface Sci 275:131–141 Mater 141:465–474 Singh T, Majumder CB (2015) Kinetics for removal of fluoride from Mohan D, Sharma R, Singh VK, Steele P, Pittman CU (2012) Fluo- aqueous solution through adsorption from mousambi peel, ride removal from water using biochar, a green waste, low-cost ground nut shell and neem leaves. Inter J Sol Sci Engin Technol adsorbent: equilibrium uptake and sorption dynamics modeling. 3(4):879–883 Ind Eng Chem Res 51:900–914 Sivasankar V, Rajkumar S, Murugesh S, Darchen A (2012) Tamarind Mondal MK (2010) Removal of Pb(II) from aqueous solution by (Tamarindus indica) fruit shell carbon: a calcium-rich promising adsorption using activated tea waste. Korean J Chem Eng adsorbent for fluoride removal from groundwater. J Hazard Mater 27(1):144–151 225–226:164–172 Mondal NK, Roy S (2015) Optimization study of adsorption parameters Sulaiman A, Gupta AK, Basheer AB (2009) A fixed bed sorption for removal of phenol on gastropod shell dust using response sur- system for defluoridation of ground water. J Urban Environ Eng face methodology. Clean Technol Environ Policy 18(2):429–447 3(1):17–22 Mondal NK, Das B, Bhaumik R, Bour T, Roy P (2012a) Calcareous Susheela AK, Bhatnagar M (2002) Reversal of fluoride induced cell soil as a promising adsorbent to remove fluoride from aqueous injury through elimination of fluoride and consumption of diet solution: equilibrium, kinetic and thermodynamic study. J Modern rich in essential nutrients and antioxidants. Mol Cell Biochem Chem Technol 3(3):1–21 234(235):335–340 Mondal NK, Bhaumik R, Bour T, Das B, Roy P, Datta JK (2012b) Talnikar VD, Pant KK, Shukla NP (2004) A field study and continu- Studies on defluoridation of water by tea ash: an unconventional ous removal of fluoride in a packed column. J Environ Sci Eng biosorbent. Chem Sci Trans 1(2):239–256 46(4):289–292 Mondal NK, Bhaumik R, Banerjee A, Datta JK, Baur T (2012c) A Tor A, Danaoglua N, Arslan G, Cengeloglu Y (2009) Removal of fluo - comparative study on the batch performance of fluoride adsorp- ride from water by using granular red mud: batch and column tion by activated silica gel and activated rice husk ash. Int J Envi- studies. J Hazard Mater 164:271–278 ron Sci 2(3):1643–1661 Vadivelan V, Kumar KV (2005) Equilibrium, kinetics, mechanism, and Mondal NK, Das B, Bhaumik R, Bour T, Roy P (2012d) Calcareous process design for the sorption of methylene blue onto rice husk. soil as a promising adsorbent to remove fluoride from aqueous J Colloid Interf Sci 286:90–100 solution: equilibrium, kinetic and thermodynamic study. J Mod WHO (2011) Guideline for drinking-water quality, 4th edn. World Chem Technol 3(3):1–21 Health Organization, Geneva Mondal NK, Bhaumik R, Roy P, Das B, Datta JK (2013) Investiga- Zhu C, Lian Z, Wang Y, Shan X (2007) Removal of cadmium from tion on fixed bed column performance of fluoride adsorption by aqueous solutions by adsorption on granular red mud (GRM). Sep sugarcane charcoal. J Environ Biol 34:1059–1064 Purif Technol 57:161–169 Mondal NK, Bhaumik R, Datta JK (2015) Removal of fluoride by alu - minum impregnated coconut fiber from synthetic fluoride solution Publisher’s Note Springer Nature remains neutral with regard to and natural water. Alexan Eng J 54(4):1273–1284 jurisdictional claims in published maps and institutional affiliations. Paudyal H, Pangeni B, Inoue K, Kawakita H, Ohto K, Alam S (2013) Adsorptive removal of fluoride from aqueous medium using a fixed bed column packed with Zr(IV) loaded dried orange juice residue. Biores Technol 146:713–720 1 3 http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Applied Water Science Springer Journals

Potentiality of a fruit peel (banana peel) toward abatement of fluoride from synthetic and underground water samples collected from fluoride affected villages of Birbhum district

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Earth Sciences; Hydrogeology; Water Industry/Water Technologies; Industrial and Production Engineering; Waste Water Technology / Water Pollution Control / Water Management / Aquatic Pollution; Nanotechnology; Private International Law, International & Foreign Law, Comparative Law
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Abstract

Contamination of underground water with fluoride (F) is a tremendous health hazard. Excessive F (> 1.5 mg/L) in drinking water can cause both dental and skeletal fluorosis. A fixed-bed column experiments were carried out with the operating vari - ables such as different initial F concentrations, bed depths, pH and flow rates. Results revealed that the breakthrough time and exhaustion time decrease with increasing flow rate, decreasing bed depth and increasing influent fluoride concentration. The optimized conditions are: 10 mg/L initial u fl oride concentration; o fl w rate 3.4 mL/min, bed depth 3.5 and pH 5. The bed depth service time model and the Thomas model were applied to the experimental results. Both the models were in good agreement with the experimental data for all the process parameters studied except flow rate, indicating that the models were appropriate for removal of F by natural banana peel dust in fix-bed design. Moreover, column adsorption was reversible and the regeneration was accomplished by pumping of 0.1 M NaOH through the loaded banana peel dust column. On the other hand, field water sample analysis data revealed that 86.5% fluoride can be removed under such optimized conditions. From the experimental results, it may be inferred that natural banana peel dust is an effective adsorbent for defluoridation of water. Keywords Banana peel · Fluoride · Column study · Dental and skeletal fluorosis · Regeneration Introduction in drinking water should not exceed beyond 1.5 mg/L. Many technologies such as precipitation, ion exchange, electrolysis Due to rapid industrialization, huge quantity of pollutants have been developed. However, all the above techniques are discharges in to the environment. Fluorine is one such pol- not cost-effective. These are high maintenance charge and lutant that threatens living organisms, in particular humans not easy to regenerate. But there is another technique, called (Koilraj and Kannan 2013). Fluoride is a strongly electron- adsorption which is an important cost-effective technique egative element, and its presence in drinking water is essen- widely used in most of the developing country for removal tial for human health (Chen et al. 2012). However, excess of fluoride from drinking water (Mondal and Roy 2015). consumption of fluoride can lead to both dental and skeletal Pertinent literature highlighted that many cost-effective fluorosis (Kierdorf et al. 2016; Death et al. 2015). Previ- adsorbents such as sugarcane bagasse, tea waste ash, alu- ous literature (Mohan et al. 2012) demonstrated that more minum impregnated potato plant ash and coconut fiber ash, than 200 million people worldwide are affected by fluoride- lemon leaf dust, banana peel dust, rice husk carbon, tea contaminated drinking water with very high concentration. ash, silica gel, egg shell dust, calcareous soil, coconut fiber, As per the guideline adopted by WHO (2011) and Bureau banana peel have been used for removal of fluoride from of Indian standard (BIS 1991), the concentration of fluoride contaminated drinking water (Ghosh et al. 2016; Mondal et al. 2015; Bhaumok et al. 2013; Mondal et al. 2012a, b, c, d; Bhaumik et al. 2012; Bhaumik and Mondal 2014a, b). But none of the above adsorbents showed excellent removal * Naba Kumar Mondal nkmenvbu@gmail.com performance along with high adsorption capacity. There- fore, it is prime important to synthesize an efficient and cost- Environmental Chemistry Laboratory, Department effective adsorbent for decontamination of fluoride from the of Environmental Science, The University of Burdwan, aqueous medium (Chen et al. 2012). Bardhaman, West Bengal, India Vol.:(0123456789) 1 3 90 Page 2 of 10 Applied Water Science (2018) 8:90 Table 1 Physical characteristics of banana peel Adsorption technique normality processed through batch and column process (Tor et al. 2009). But in batch process, Parameter Values all the operating variables remain constant while one vari- pH 6.59 able changes at a time, and the process is costly and time- Conductivity (mS/cm) 190 consuming. Therefore, column separation process may be Specific gravity 2.66 the suitable one for defluoridation of domestic as well as Bulk density (g/cc) 0.384 community level. In our previous work, we have used the Particle density (g/cc) 0.138 banana peel for removal of fluoride through batch process Porosity (%) 178.26 followed by response surface optimization techniques. Very Moisture content (%) 2.98 recently, we have tried with another variety of banana peel P 5.63 zpc for the same purposes. But, we cannot achieve to reach the Dry matter 89.73 desired level. Crude fiber 10.33 Bananas are a popular fruit consumed worldwide with an Ash 17.94 early production of over 145 million tonnes in 2011. Once BET surface area 23.983 m /g the peel is removed, the fruit can be raw or cooked and peel is generally discarded. On average, banana peel contains 6–9% dry matter of protein and 20–30% fiber. Normally, the ripe banana peels contains 30% free sugar and 15% more The pH of the 0.1 (M) KNO solutions was adjusted by using starch than green banana peels. Moreover, banana peel has 0.05 (N) HNO and 0.1 (N) KOH solutions. After thoroughly many biomolecules such as lignin, cellulose and hemicel- shaking (24 h), the pH of the final solutions was recorded lulose with variety of active functional groups (carboxyl, and a graph was constructed by pH versus ΔpH. hydroxyl, amine, etc.) which suppose to bind the pollutants (Deshmukh et al. 2017; Kumar et al. 2011). Column study The present work is aimed at synthesizing an efficient and economical adsorbent using banana peel toward removal Thomas model of fluoride from water through column study. Finally, the prepared adsorbent was used for removal of fluoride from The Thomas model can be used to predict the breakthrough field samples which was collected from the fluoride affected curve and the maximum adsorption capacity of the banana villages of Birbhum district, West Bengal. peel in a fixed-bed operation. The linearized form of Thomas model can be presented in Eq. (1): Materials and methods C K q X K C t 0 Th 0 Th 0 ln = − (1) C − 1 Q Q Preparation of banana peel dust where X is the amount of sorbent taken in the column (g) The raw waste banana peels (Musa paradisiaca) were col- and Q is the effluent flow rate (mL/min). The kinetic coef- lected from nearby fruits stall of Burdwan town, West Ben- ficient K and the adsorption capacity of the bed q for Th 0 gal. After collection, peels were thoroughly washed with the defluoridation process can be calculated by plotting distilled water followed by washing with de-ionized water ln(C /C − 1) versus t. and dried in hot air oven at 50 °C for 12 h. The dried peels were cut into small pieces and again dried in hot air oven maintaining 60 °C temperatures for 24 h. The dried banana Bed depth service time model (BDST) peels were ground using kitchen grinder to get the desired particle size (200 μm), the powder form of banana peel was It is familiar that BDST model provide a simplest approach and suitable prediction of absorber performance (Al-Degs stored in airtight container, the physico-chemical analysis was done, and the results are depicted in Table 1. et al. 2009). BDST model basically provides a relationship between column bed depth, X and service time t. However, Point of zero charge (pH ) this particular model also focused on the estimation of char- ZPC acteristic parameters such as maximum adsorption capacity Zero point charge of the banana peel was determined by fol- (N ) kinetic constant (K). Moreover, this model considers one valuable assumption that is the adsorption rate is propor- lowing the solid addition method (Mondal 2010). Initially, a series of conical flasks were taken with 50 mL of 0.1 (M) tional to residual capacity of the sorbent and the concentra- tion of the sorbing species. The relationship of service time KNO solutions in each flask along with 0.1 g banana peel. 1 3 Applied Water Science (2018) 8:90 Page 3 of 10 90 with process conditions and operating parameters is given (Systronic 206). The breakthrough curves were constructed as Eq. (2): by Origin software (Version 6.0). C KXN 0 0 ln − 1 = ln exp − 1 − KC t Dental and skeletal fluorosis study (2) C v Primary school children aged between 5–10  years were A linear relationship between bed depth and service time selected from fluoride affected villages of Birbhum district, may be given by Eq. 3 (Al-Degs et al. 2009) West Bengal. Dental fluorosis was examined by a trained N X C 0 0 examiner who held a master degree in dentistry with the help t = − ln − 1 (3) vC KC C 0 0 b of Dean index (Dean 1934). Skeletal fluorosis was assessed by clinical symptoms and physical exercise (Susheela and where C is the initial concentration of solute (mg/L), C 0 b Bhatnagar 2002; Shashi et al. 2008). the desired concentration of solute at breakthrough (mg/L), K the adsorption rate constant (L/mg/h), N the adsorption capacity (mg/L), X the bed depth of column (cm), v the lin- Results and discussion ear flow velocity of feed to bed (cm/h), and t the service time of column under above conditions (hrs). Equation (4) can be Adsorbent characterization rewritten in the form of a straight line. T = aX − b Preparation of banana peel dust was subjected to pH (4) ZPC and SEM study for understanding the zero point charge and where ‘a’ is slope of BDST line ( a = ) and the intercept vC surface morphology (HITACHI-S-530, Scanning Electron of this equation represents as Eq. (5): Microscope and ELKO Engineering, accelerating voltage C of 20.0 kV) and surface chemistry of the banana peel was b = ln − 1 (5) assessed by FTIR (BRUKER, Tensor 27). The zero point KC C 0 b charge of the banana peel was recorded as 5.63 (Fig. 1), and Thus, N and K can be evaluated from slope (a) and the 0 from the scanning micrograph it is clear that the surface intercept (b) of the plot of t versus X, respectively. of the banana peel dust is absolutely rough in nature and huge heterogeneity (Fig. 2a). However, after F removal, the surface of banana peel is smooth with less degree of hetero- Column regeneration study geneity (Fig. 2b). The Fourier transformer infrared spectros- copy clearly revealed that it has sharp peaks at 3340, 2890 In order to activate the exhausted column, regeneration −1 and 1741 cm which corresponds the functional groups experiments were conducted by using 0.1 (M) NaOH solu- hydroxyl (–OH), alkyl C–H, and carboxyl (–COOH), respec- tions. The desorption experiments were conducted with tively (Fig. 3). Therefore, it is expected that the functional the flow rate 2 mL/min. After passing 100 mL of 0.1 (M) groups such as –OH and –COOH may interact with fluoride NaOH, the entire column bed was washed with double dis- during adsorption. tilled water. Finally, the regenerated column was then used for the next cycle of column adsorption. The desorption efficiency E was calculated by the fol- lowing Eq. (6) (Zhu et al. 2007) M × 100 E = (6) [(q + M )] 2 where M is desorption fluoride amount (mg) eluted by des- 5.63 orption solution (0.3 M NaOH). q and m are the capacity at exhaustion point (L) and adsorbent dose, respectively, and 0 M is the fluoride amount (mg) retained in the column. -1 Analytical procedure -2 2 46 810 pH Effluent solution was collected at regular interval, and their concentrations were measured (Thermo Orion, 4 star); pH of the experimental solution was measured by using pH meter Fig. 1 ZPC of Banana peel dust 1 3 Initial pH - Final pH 90 Page 4 of 10 Applied Water Science (2018) 8:90 The effect of initial concentration of solution on breakthrough curve Three different initial concentrations (1.5, 10, 35 mg/L) were used in this study. The values were chosen because they were considered to fairly represent fluoride concentration range in most groundwater. The bed mass and flow veloc- ity of the present experiment have been taken as 2 g and 3.4 mL/min, respectively. The breakthrough curves (BTCs) obtained from the experimental investigation of the effect of the initial concentration on fluoride removal are depicted in Fig. 4. From Fig. 4 it is clear that higher the fed concen- tration, the steeper is the breakthrough curve and smaller is the breakthrough time. The adsorbent exhaustion rates (AER) (bed volume (BV) in parenthesis) were computed and found to be 0.046(3.31), 0.023(6.16) and 0.009(15.39) g/L for the initial concentrations of 35, 10 and 1.5 mg/L, respectively (Table 2). As the concentration increase, the driving force for adsorption increases and the active sites are consumed faster. The results also highlighted that both saturation rate and breakthrough time change with changing influent concentration (Goel et al. 2005). This is because, at higher concentration, the active sites of the adsorbent get saturated very quickly (Mondal et al. 2013). The effect of flow rate on breakthrough curve Steeper breakthrough curve was obtained at higher flow rates (Fig. 5). Further it was studied that the steepness of the breakthrough curve reduces with decreasing flow rates Fig. 2 Scanning electron microscopy of banana peel: a before passing fluoride solution (×1500 magnification), b after passing fluoride solu- i.e., increase in breakthrough time. The breaks through tion (×1500 magnification) curves appeared steeper at higher flow rates may be due to faster movement of adsorption zone along the bed aiding its quick saturation (Sulaiman et al. 2009; Tor et al. 2009). Again the variation in the slope of the breakthrough curve Fig. 3 FTIR spectrum of banana peel dust (BPD) 1 3 Applied Water Science (2018) 8:90 Page 5 of 10 90 bed volumes (BV) of water processed at breakthrough curve 0.24 were found to be 6.02, 30.08, and 176.93 L for 1.7, 3.4, and 0.22 8.0 mL/min, respectively (Table 2). The increase in volume 0.20 processed with an increased in velocity can be attributed to reduced influence of external mass transfer resistance 0.18 (Ghribi and Chlendi 2011). The AER values for this respec- 0.16 tive flow rate are 0.029, 0.006 and 0.001 g/mL, respectively. 0.14 0.12 The effect of pH on breakthrough curve 0.10 35 mg/l The breakthrough curves for different pH are shown in 10 mg/l 0.08 1.5 mg/l Fig. 6. The pH of the aqueous solution has been recog- 0.06 nized as one of the most important factors influencing 050 100 150200 250300 350400 450 adsorption kinetics due to its direct inf luence on the sur- time (minute) face properties of the adsorbent (Memon et al. 2008). As shown in Fig. 6, where the value of pH was 5, the value Fig. 4 Breakthrough curve of the effect of different influent con- of C /C reached 0.042 in 30 min. But the breakthrough t 0 centration on fluoride adsorption onto banana peel (v = 3.4  ml/min, curve of the pH 7.0 and 9.0 was not more than 0.045 and Z = 0.9 cm, pH = 5) 0.109 in the different time periods, respectively. With a decrease in pH in the influent, the breakthrough curves and adsorption capacity may be explained on the basis of shifted from left to right, which indicates higher removal mass transfer fundamentals. The reason is that at higher flow of fluoride. It would spend more time reaching the satura- rate the rate of mass transfer increases, i.e., the amount of tion, and the efficiency of biosorption was much higher fluoride adsorbed onto unit bed height (mass transfer zone) (Ma et al. 2008). The F ion binding could be attributed increased with increasing flow rate leading to faster satura- to several mechanisms such as ion exchange, complexa- tion at higher flow rate (Talnikar et al. 2004). The increase tion, electrostatic attraction and precipitation. For banana in adsorption capacity (both up to breakthrough and exhaust) peel, ion exchange has been considered as a main mecha- of banana peel was more pronounced at the flow rate of nism responsible for pollutant sequestering (Sheng et al. 1.7 mL/min, whereas the effect is almost negligible at the 2004). The result suggests that with the decrease in pH, flow rate of 8.0 mL/min. The rate constant, K , increased under experimental condition, the adsorption capacities Th with increasing the flow rate which indicates that the mass increase (Table 2). So the removal of f luoride from aque- transport resistance decreases (Tor et al. 2009). The different ous solution was more efficient at lower initial pH value. Table 2 Summary of pertinent Parameters Service time Adsorption capacity Bed volume pro- AER (g/ml) results at breakthrough point of (min)t (mg/g) q cessed (BV) b b banana peel Adsorbent mass (g)  2 40 0.405 12.03 0.015  4 100 0.429 15.92 0.012  8 250 0.449 19.34 0.009 pH  5.0 30 0.479 9.02 0.020  7.0 60 0.477 18.05 0.010  9.0 300 0.441 90.23 0.002 Different flow (ml/min)  1.7 40 0.495 6.02 0.029  3.4 100 0.477 30.08 0.006  8.0 250 0.466 176.93 0.001 Initial concentration (mg/L)  35.0 30 0.014 3.31 0.046  10.0 60 0.109 6.16 0.023  1.5 150 0.419 15.39 0.009 1 3 c /c t 0 90 Page 6 of 10 Applied Water Science (2018) 8:90 0.12 The effect of different bed depths on the breakthrough curve 0.11 0.10 1.7ml/min Keeping the initial concentration of fluoride, flow rate and 3.4ml/min 0.09 8.0ml/min pH of the solution constant and with varying bed depth, the number of active sites available for sorption and the 0.08 contact time of solute with the adsorbent were determined. 0.07 Figure 7 shows the BTs obtained upon varying the quan- 0.06 tity of adsorption media between 2, 4 and 8 g. From the 0.05 BTCs, the t and q were determined and are summarized b b in Table 2. From the bed depth study, it was found that as 0.04 the bed height increases, adsorbate had more time to con- 0.03 tact with banana peel dust that resulted in higher removal 050 100 150 200250 300350 400450 efficiency of fluoride ion in column (Fig.  7). So, the higher time(minute) bed depth results in a decrease in the solute concentra- tion in the effluent at the same time. The slope of break - Fig. 5 Breakthrough curve of the effect of different flow rate on fluo- through curve decreased with increasing bed height, which ride adsorption onto banana peel dust (C = 10.0  mg/L, Z = 0.9  cm, resulted in a broadened mass transfer zone. High uptake pH = 5) was observed with highest bed depth 3.7 cm height due to an increase in the surface area of biosorbent, which provided more binding sites for the sorption (Vadivelan 0.12 and Kumar 2005). Almost similar results were reported by Paudyal et al. (2013) and Mondal et al. (2013) for F 0.10 pH5 removal by dried orange juice residue and sugarcane char- pH7 coal. The different bed volumes (BV) of water processed at pH9 breakthrough curve were found to be 12.03, 15.92, 19.34 0.08 L, and the AER value was found to be 0.0145, 0.0117, 0.0094 g/mL for 2, 4 and 8 g of banana peel dust adsor- 0.06 bent, respectively. 0.04 0.02 050 100 150200 250 300350 400 450 time (minute) 0.20 Fig. 6 Breakthrough curve of the effect of different pH on fluoride adsorption onto banana peel dust (v = 3.4  ml/min, C = 10.0  mg/L, Z = 2 g) 0.15 The AER for different pH are 0.0196, 0.098, 0.020 g/mL, respectively. There are many reasons which may be attrib- uted toward the f luoride adsorption behavior of the sorb- 0.9cm ent relative to solution pH. At lower pH, the surface of 1.7cm 3.5cm banana peel may get positively charged, which enhances the negatively charged f luoride ion through electrostatic 0.10 force of attraction (Han et  al. 2007). Almost similar results reported by Paudyal et al. (2013) for removal of 050100 150200 250 300350 400450 F using a fixed-bed column packed with Zr (IV) loaded time (minute) dried orange juice residue. Fig. 7 Breakthrough curve of the effect of different bed depth on fluoride adsorption onto banana peel dust (v = 3.4  ml/min, C = 10.0 mg/L, pH = 5) 1 3 c /c c /c t 0 t 0 ct/c0 Applied Water Science (2018) 8:90 Page 7 of 10 90 Table 3 Calculated constants 2 pH Z (cm) v (ml/min) C (mg/L) K (ml/min/mg) q (mg/g) R 0 th 0 of Thomas model at different conditions using linear 5 3.5 3.4 10 55.12 98.26 0.999 regression analysis 7 3.5 3.4 10 55.12 98.26 0.999 9 3.5 3.4 10 55.12 98.26 0.999 5 0.9 3.4 10 7.80 3.76 0.996 5 1.7 3.4 10 7.80 1.88 0.996 5 3.5 3.4 10 7.80 0.94 0.996 5 3.5 1.7 10 12.61 29.81 0.775 5 3.5 3.4 10 25.22 59.61 0.775 5 3.5 8.0 10 59.34 140.27 0.775 5 3.5 1.7 1.5 43.58 8.15 0.996 5 3.5 1.7 10 6.54 8.15 0.996 5 3.5 1.7 35 1.87 8.15 0.996 Fig. 8 BDST model at break- BDST model Banana peel through curve in fixed-bed column for F adsorption by 3.5 banana peel 2.5 y = 0.0123x + 0.4333 R² = 0.9994 1.5 0.5 050 100 150 200 250 300 service time (minute) Table 4 Calculated constants of BDST model for the adsorption of Table 5 Column regeneration parameters for NBP column fluoride by banana peel dust using linear regression analysis Regeneration cycle Percentage of desorption Q E (%) E D C /C a (min/cm) b (min) K (l/mg/min) N (mg/l) R (mg/g) (%) t 0 a 0 0.0101 0.0123 0.4333 0.005 0.4182 0.9994 1 84 2.091 2 72 1.321 = 10.0 mg/L, v = 3.4 ml/min 3 54 0.694 Adsorption operation constant–initial fluoride concentration: 8  ml/ min; Z = 0.9  cm; pH = 5; C = 10  mg/L. Desorption condition—des- Modeling of breakthrough curve orption solution 0.1 M NaOH, solution flow rate 2 ml/min The entire experimental column study has been fitted with scaled up to other flow rates without further experimental Thomas model, results revealed that all the operating vari- runs. ables are well acquainted with Thomas model, and goodness of the fit of the model (R ) is very high except variation of flow rate (Table  3). A plot of service time (t) versus bed Regeneration study depth (X) at a flow rate of 3.4 mL/min is shown in Fig.  8. The equation of the linear relationship was obtained with After regeneration of the exhausted column, it has been R above 0.999. This indicated the validity of the BDST found that desorption gradually decreases from first to sec- model for present column system. The calculated adsorption ond and second to third cycles. The calculated column des- capacity (N ) and the rate constant (K) are 0.418 mg/L and −3 orption parameters are listed in Table 5. From Table 5, it 5 × 10 L/mg/min, respectively (Table 4). The advantage of is clear that E value decreases with consecutive cycles of the BDST model is that any experimental test can be reliably 1 3 Bed depth (cm) 90 Page 8 of 10 Applied Water Science (2018) 8:90 desorption (Tor et al. 2009). This is probably due to the loss Table 6 Physico-chemical characteristics of ground water of adsorption capability of banana peel dust column. Parameters Values Conductivity (μS/cm) 113 ± 2.07 Defluoridation from field sample Hardness (mg/L, CaCO ) 178 ± 3.11 Chlorine (mg/L) 12.3 ± 0.71 Forty three (43) tube well water samples were collected from Nitrate (mg/L) 9.3 ± 0.06 the severally fluoride affected villages of Birbhum district, Sulfate (mg/L) 0.81 ± 0.013 West Bengal. The children aged between 5 and 10 years Fluoride (mg/L) 9.89 ± 0.33 were selected for understanding the status of dental and pH 7.9 skeletal fluorosis (Fig.  9). From the data (data not shown), it is clear that about 63% boys and 48% girls were severally Mean ± SD affected by dental fluorosis (Fig.  9). However, 18% boys and 12% of girls were affected by skeletal fluorosis (Fig.  9). the adsorption capacity of banana peel increased with The physico-chemical analysis of the field samples is pre- sented in Table 6. From Table 6 it is found that the highest decreasing medium pH. Column study revealed the best fluoride removal conditions as: 10 mg/L initial fluoride fluoride level in the affected areas is 9.89 mg/L. Moreover, for field sample defluoridation study, highest fluoride con- concentration; flow rate 3.4  ml/min, bed depth 3.5 and pH 5. The study results were best fitted with both Thomas taining tube well water (9.89 mg/L) was selected and it was recorded that about 86.5% removal can be achieved through and BDST models. Moreover, Thomas equation indicated that the increase in bed height caused an increase in the standardized column study (v = 3.4 mL/min, C = 9.89, pH = 5, Z = 3.7 cm). mass transport resistance and axial dispersion, which was confirmed from the K values. The exhausted banana peel Th dust can be regenerated by 0.1 M NaOH and reused with minimal loss of efficiency for three adsorption–desorption Conclusions cycles. Finally, best optimized conditions were applied for defluoridation of the field sample, and 86.5% removal was Present finding highlights the removal of fluoride from both synthetic and field samples using banana peel dust achieved. Therefore, it can be conclude that the use of banana peel as an adsorbent for fluoride removal is poten- through column study. The surface morphology of the banana peel dust was assessed by SEM study, and the tially cost-effective and may provide an alternative method for fluoride removal from contaminated water. active functional group was evaluated by FTIR study (Table  7). Fluoride adsorption results highlighted that Fig. 9 Children affected by skletal and dental fluorosis in the study area 1 3 Applied Water Science (2018) 8:90 Page 9 of 10 90 Table 7 Comparative evaluation Adsorbent pH Adsorption capac- References of adsorption capacities of ity (mg/g) various biosorbents for fluoride removal 1. Acid and alkali treated Tamarindous 2–10 – Ramanjaneyulu et al. (2013) indica fruit shall 2. Acid treated Banana peel 2–12 1.34 Mohammad and Majumder (2014) 3. Untreated Tamarind fruit corner 1–8 4.14 Sivasankar et al. (2012) 4. Mousabi (Citrus limetta) peel 7.0 1.915 Singh and Majumder (2015) 5. Ground nut (Arachishypogaea) 7.0 1.15 Singh and Majumder (2015) 6. Untreated sweet lemon peel 2–12 0.744 Mohammad and Majumder (2014) 7. Untreated Banana peel (BPD-1) 2–10 17.43 Bhaumik and Mondal (2014b) 8. Algal Biosorbent Spirogyra sp. 2.0 1.272 Mohan et al. (2007) 9. Leaf biomass powder sample 2.0 Jamode et al.(2004) 10. Treated coffee husk 2.0 0.416 Getachew et al. (2015) 11. Guava seeds – 116.5 Sánchez-Sánchez et al. (2013) 12. Banana peel 5.0 8.15 Present work Acknowledgement The authors are grateful to Dr. Rajarshi Ghosh, Chen H, Yan M, Yang X et al (2012) Spatial distribution and temporal Assistant Professor, Department of Chemistry, Burdwan University, variation of high fluoride contents in groundwater and prevalence Burdwan, West Bengal, India, for recording FTIR data and they also of fluorosis in humans in Yuanmou County, Southwest China. extend their gratitude to Dr. Srikanta Chakraborty, Incharge of SEM, J Hazard Mater 235:201–209. https ://doi.or g/10.1016/j.jhazm USIC, University of Burdwan, West Bengal, India, for SEM study. at.2012.07.042 Dean HT (1934) Classification of mottled enamel diagnosis. J Am Dent Assoc 21:1421–1426 Compliance with ethical standards Death C, Coulson G, Kierdorf U, Kierdorf H, Morris WK, Hufschmid J (2015) Dental fluorosis and skeletal fluoride content as biomark - Conflict of interest Authors declare that they have no conflict of inter - ers of excess fluoride exposure in marsupials. Sci Total Environ est for publishing the present manuscript. 533:528–541 Deshmukh PD, Khadse GK, Shinde VM, Labhasetwar P (2017) Cad- Open Access This article is distributed under the terms of the Crea- mium removal from aqueous solutions using dried banana peels tive Commons Attribution 4.0 International License (http://creat iveco as an adsorbent: kinetics and equilibrium modeling. J Bioremediat mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- Biodegrad 8:395. https ://doi.org/10.4172/2155-6199.10003 95 tion, and reproduction in any medium, provided you give appropriate Getachew T, Hussen A, Rao VM (2015) Defluoridation of water by credit to the original author(s) and the source, provide a link to the activated carbon prepared from banana (Musa paradisiaca) peel Creative Commons license, and indicate if changes were made. and coffee (Coffea arabica) husk. Int J Environ Sci Technol 12:1857–1866 Ghosh SB, Bhaumik R, Mondal NK (2016) Optimization study of adsorption parameters for removal of fluoride using aluminium- impregnated potato plant ash by response surface methodology. References Clean Technol Environ Policy 18:1069–1083 Ghribi A, Chlendi M (2011) Modeling of fixed bed adsorption: applica- tion to the adsorption of an organic dye. Asian J Text 1:161–171 Al-Degs YS, Khraisheh MAM, Allen SJ, Ahmad MN (2009) Adsorp- Goel J, Kadirvelu K, Rajagopal C, Garg VK (2005) Removal of lead tion characteristics of reactive dyes in columns of activated car- (II) by adsorption using treated granular activated carbon: batch bon. J Hazard Mater 165:944–949 and column studies. J Hazard Mater B 125:211–220 Bhaumik R, Mondal NK (2014a) Adsorption of fluoride from aqueous Han R, Wang Y, Yu W, Zou W, Shi J, Liu H (2007) Biosorption of solution by a new low-cost adsorbent: thermally and chemically methylene blue from aqueous solution by rice husk in a fixedbed activated coconut fibre dust. Clean Techn Environ Policy. https:// column. J Hazard Mater 141:713–718 doi.org/10.1007/s1009 8-015-0937-6 Jamode AV, Sapkal VS, Jamode VS (2004) Defluoridation of water Bhaumik R, Mondal NK (2014b) Optimizing adsorption of fluoride using inexpensive adsorbents. J Indian Inst Sci 84:163–171 from water by modified banana peel dust using response surface Kierdorf H, Rhede D, Death C, Hufschmid J, Kierdorf U (2016) Recon- modelling approach. Appl Water Sci. ht tps : //doi .org /10.10 07/ structing temporal variation of fluoride uptake in eastern grey kan- s1320 1-014-0211-9 garoos (Macropus giganteus) from a high-fluoride area by analysis Bhaumik R, Mondal NK, Das B, Roy P, Pal KC, Das C, Banerjee A, of fluoride distribution in dentine. Environ Pollut 211:74–80 Dutta JK (2012) Eggshell powder as an adsorbent for removal of Koilraj P, Kannan S (2013) Aqueous fluoride removal using ZnCr lay - fluoride from aqueous solution: equilibrium, kinetic and thermo- ered double hyroxides and their polymeric composites: batch and dynamic studies. Eur J Chem 9(3):1457–1480 column studies. Chem Eng J 234:406–415 Bhaumik R, Mondal NK, Chattoraj S, Datta JK (2013) Application Kumar J, Balomajumder C, Mondal P (2011) Application of agro- of response surface methodology for optimization of fluoride based biomasses for zinc removal from wastewater-a review. removal mechanism by newely developed biomaterial. Am J Anal Clean Soil Air Water 39:641–652 Chem 4:404–419 1 3 90 Page 10 of 10 Applied Water Science (2018) 8:90 Ma W, Ya F, Wang R, Zhao YQ (2008) Fluoride removal from drinking Ramanjaneyulu V, Jaipal M, Yasovardhan N, Sharada S (2013) Kinetic water by adsorption using bone char as a biosorbent. Int J Environ studies on removal of fluoride from drinking water by using Technol Manag 9:59–69 tamarind shell and pipal leaf powder. Inter J Emerg Trends Eng Memon JR, Memon SQ, Bhanger MI, Memon GZ, El-Turki A, Allen Develop 5(3):146–155 GC (2008) Characterization of banana peel by scanning electron Sánchez-Sánchez HA, Cortés-Martínez R, Alfaro-CuevasVillanueva R microscopy and FT-IR spectroscopy and its use for cadmium (2013) Fluoride removal from aqueous solutions by mechanically removal. Colloids Surf B 66:260–265 modified guava seeds. Int J Sci Basic Appl Res 11(1):159–172 Mohammad A, Majumder CB (2014) Removal of fluoride from syn- Shashi A, Kumar M, Bhardwaj M (2008) Incidence of skeletal deformi- thetic waste water by using bioadsorbents. Int J Res Eng Technol ties in endemic fluorosis. Trop Dr 38:231–233 3(4):776–785 Sheng PX, Ting Y, Chen JP, Hong L (2004) Sorption of lead, copper, Mohan SV, Ramanaiah SV, Rajkumar B, Sarma PN (2007) Removal cadmium, zinc and nickel by marine algal biomass: characteriza- of fluoride from aqueous phase by biosorption onto algal biosorb- tion of biosorptive capacity and investigation of mechanisms. J ent Spirogyra sp.-IO2: sorption mechanism elucidation. J Hazard Colloid Interface Sci 275:131–141 Mater 141:465–474 Singh T, Majumder CB (2015) Kinetics for removal of fluoride from Mohan D, Sharma R, Singh VK, Steele P, Pittman CU (2012) Fluo- aqueous solution through adsorption from mousambi peel, ride removal from water using biochar, a green waste, low-cost ground nut shell and neem leaves. Inter J Sol Sci Engin Technol adsorbent: equilibrium uptake and sorption dynamics modeling. 3(4):879–883 Ind Eng Chem Res 51:900–914 Sivasankar V, Rajkumar S, Murugesh S, Darchen A (2012) Tamarind Mondal MK (2010) Removal of Pb(II) from aqueous solution by (Tamarindus indica) fruit shell carbon: a calcium-rich promising adsorption using activated tea waste. Korean J Chem Eng adsorbent for fluoride removal from groundwater. J Hazard Mater 27(1):144–151 225–226:164–172 Mondal NK, Roy S (2015) Optimization study of adsorption parameters Sulaiman A, Gupta AK, Basheer AB (2009) A fixed bed sorption for removal of phenol on gastropod shell dust using response sur- system for defluoridation of ground water. J Urban Environ Eng face methodology. Clean Technol Environ Policy 18(2):429–447 3(1):17–22 Mondal NK, Das B, Bhaumik R, Bour T, Roy P (2012a) Calcareous Susheela AK, Bhatnagar M (2002) Reversal of fluoride induced cell soil as a promising adsorbent to remove fluoride from aqueous injury through elimination of fluoride and consumption of diet solution: equilibrium, kinetic and thermodynamic study. J Modern rich in essential nutrients and antioxidants. Mol Cell Biochem Chem Technol 3(3):1–21 234(235):335–340 Mondal NK, Bhaumik R, Bour T, Das B, Roy P, Datta JK (2012b) Talnikar VD, Pant KK, Shukla NP (2004) A field study and continu- Studies on defluoridation of water by tea ash: an unconventional ous removal of fluoride in a packed column. J Environ Sci Eng biosorbent. Chem Sci Trans 1(2):239–256 46(4):289–292 Mondal NK, Bhaumik R, Banerjee A, Datta JK, Baur T (2012c) A Tor A, Danaoglua N, Arslan G, Cengeloglu Y (2009) Removal of fluo - comparative study on the batch performance of fluoride adsorp- ride from water by using granular red mud: batch and column tion by activated silica gel and activated rice husk ash. Int J Envi- studies. J Hazard Mater 164:271–278 ron Sci 2(3):1643–1661 Vadivelan V, Kumar KV (2005) Equilibrium, kinetics, mechanism, and Mondal NK, Das B, Bhaumik R, Bour T, Roy P (2012d) Calcareous process design for the sorption of methylene blue onto rice husk. soil as a promising adsorbent to remove fluoride from aqueous J Colloid Interf Sci 286:90–100 solution: equilibrium, kinetic and thermodynamic study. J Mod WHO (2011) Guideline for drinking-water quality, 4th edn. World Chem Technol 3(3):1–21 Health Organization, Geneva Mondal NK, Bhaumik R, Roy P, Das B, Datta JK (2013) Investiga- Zhu C, Lian Z, Wang Y, Shan X (2007) Removal of cadmium from tion on fixed bed column performance of fluoride adsorption by aqueous solutions by adsorption on granular red mud (GRM). Sep sugarcane charcoal. J Environ Biol 34:1059–1064 Purif Technol 57:161–169 Mondal NK, Bhaumik R, Datta JK (2015) Removal of fluoride by alu - minum impregnated coconut fiber from synthetic fluoride solution Publisher’s Note Springer Nature remains neutral with regard to and natural water. Alexan Eng J 54(4):1273–1284 jurisdictional claims in published maps and institutional affiliations. Paudyal H, Pangeni B, Inoue K, Kawakita H, Ohto K, Alam S (2013) Adsorptive removal of fluoride from aqueous medium using a fixed bed column packed with Zr(IV) loaded dried orange juice residue. Biores Technol 146:713–720 1 3

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Applied Water ScienceSpringer Journals

Published: May 29, 2018

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