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Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana
Journal of Environmental Management xxx (2016) 1e8
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Research article
Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana Shraddha Khamparia a, *, Dipika Jaspal b a b
Symbiosis Centre for Research and Innovation, Symbiosis International University, Gram:Lavale, Tal Mulshi, Pune 412115, India Symbiosis Institute of Technology, A Constituent of Symbiosis International University, Gram:Lavale, Tal Mulshi, Pune 412115, India
a r t i c l e i n f o
a b s t r a c t
Article history: Received 5 April 2016 Received in revised form 7 June 2016 Accepted 11 September 2016 Available online xxx
The present study aims at exploring the potential of the seeds of a tropical weed, Argemone mexicana (AM), for the removal of a toxic xanthene textile dye, Rhodamine B (RHB), from waste water. Impact of pH, adsorbent dosage, particle size, contact time and dye concentration have been assessed during adsorption. The weed has been well characterized by several latest techniques thereby providing an indepth information of the mechanism during adsorption. About 80% removal has been attained with 0.06 g of adsorbent over the studied system. Thermodynamic and kinetic studies, followed by second order kinetic model, directed towards the endothermic nature of adsorption. The results obtained from batch experiments were modelled using Langmuir and Freundlich isotherm and were analysed on the basis of R2 and six error functions for selection of appropriate model. Langmuir isotherm was found to be best fitted to the experimental data with high values of R2 and lower values of error functions. Adsorption study revealed the affinity of AM seeds for the dye ions present in waste water, introducing a novel adsorbent in field of waste water treatment. © 2016 Elsevier Ltd. All rights reserved.
Keywords: Adsorption Argemone mexicana weed Error functions Langmuir Rhodamine B
1. Introduction Synthetic dyes are considered as the prime contributors towards water pollution. The presence of synthetic dyes in aquatic system, not only deteriorates the clarity of water bodies but also affects the human health directly or indirectly (Robinson et al., 2001). Textile industry being the primary consumer of synthetic dyes, inevitably generates the necessity to treat the textile effluents, before it gets discharged from the source. Some of the dyes are reported to be highly toxic and mutagenic in nature (Wang et al., 2005). Rhodamine B (RHB) is reported to be carcinogenic due to the presence of four N-ethyl linkages on either sides of xanthene ring in its structure (Mohammadi et al., 2010). Ingestion of this dye may result in gastrointestinal disorders with irritation in eyes and skin (Khan et al., 2011). Several physio-chemical, biological and advanced oxidation treatment methods have been employed for the treatment of textile effluents (Gupta et al., 2015a). Amongst different techniques,
* Corresponding author. Symbiosis Centre for Research and Innovation, Symbiosis International University Lavale, Pune, 412115, India. E-mail addresses: [email protected], shraddha.khamparia@ sitpune.edu.in (S. Khamparia), [email protected] (D. Jaspal).
adsorption is a method used since decades (Mittal et al., 2009). The major advantage of adsorption technique lies in its easy application with the higher possibility of using different adsorbents. In view of eco-friendly treatment methods, an urgent need has eventuated to find cost effective and sustainable materials for dye removal. In this regard, the recent contemporary approach of utilization of cheap and waste bio materials during adsorption have been in limelight, replacing the use of costly activated carbon. Different weeds such as Parthenium Hysterophorous (Lata et al., 2008; Bapat and Jaspal, 2016), Water Hyacinth (Lalitha and Sangeetha, 2008), Congon grass (Su et al., 2014) and Narrow leaved Cattail (Inthorn et al., 2004) etc. have been employed after pre-treatment for the removal of dyes from aqueous solution. In an urge to find the sustainable and low cost bio materials for adsorption, an uncharted tropical weed, Argemone mexicana (AM) has been tested in the current research to explore its potential towards decolorization of a cationic toxic textile dye RHB, from textile effluent. AM is a perennial species which can flourish in drought prone regions and is available in abundance. Seeds of AM have been used for adulteration which further drew the attention towards their use as adsorbent. Subsequently, characterization, optimization, equilibrium and kinetic studies were carried out for the adsorbate-adsorbent system.
http://dx.doi.org/10.1016/j.jenvman.2016.09.036 0301-4797/© 2016 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
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liquid was tested for change in pH, and the pHpzc value was determined (Prahas et al., 2008).
2. Materials and method 2.1. Adsorbent and adsorbate
2.3. Batch studies AM weed, commonly known as Mexican prickly poppy abundantly available in and around Sus-Mahalunge area, Pune, Maharashtra, India, was chosen for the adsorption study for the removal of RHB, a cationic xanthene dye. AM seeds closely resemble mustard seeds. The buds were plucked properly and deseeded. Further the seeds were deoiled, grounded and sieved through IS: 460 standard sieve sets to get the desired range of particles of 425e300 mm. (Supplementary material. Table 1). Stock solution of 103 M RHB was prepared with distilled water which was further diluted to the get the desired concentration range of test solutions (1 106 to 10 106 M). The absorption spectrum and concentration of RHB was analysed by a Systronic Double beam spectrophotometer (Model No. 2203) at 554 nm (wavelength of maximum absorption). pH of the solutions were adjusted using 0.1 N HCl and NaOH of analytical grade.
2.2. Characterization of adsorbent Several latest techniques, such as Energy Dispersive X-ray spectroscopy embedded with Scanning electron Microscope (JEOL JSM 6300A), Fourier Transform Infrared spectrophotometry (JASCO 6100 FTIR) and X-Ray Diffraction crystallography (D8 Advance) were employed to detect the elements, surface morphology, functional groups and nature of the adsorbent (AM). Quantification of functional groups was performed by Boehm technique. About 1 g of adsorbent with 20 mL of 0.1 M NaHCO3, 0.05 M Na2CO3, 0.1 M NaOH (for acidic groups) and 0.1 M HCl (for basic groups) was taken in different 100 mL volumetric flask at room temperature for 48 h. Quantification of acidic and basic groups was done by titrating the supernant liquids with respective solutions during acid-base titrations. Both indicators and pH meter were used to determine endpoint of the titration. Considering that NaHCO3 only neutralizes carboxylic groups, Na2CO3 neutralizes carboxylic and lactonic while NaOH neutralizes carboxylic, lactonic and phenolic groups, the difference were calculated giving the quantity of carboxylic, lactones and phenol groups. Basic groups were estimated by back titrating the supernant liquid with strong base (0.1 M NaOH) (Ekpete and Horsfall, 2011). The adsorbent was subjected to proximate analysis (ASTM D 3172-3175 standards) in order to account for moisture, ash, and fixed carbon content. Also the point of zero charge, pHpzc value of the adsorbent was evaluated using pH drift method as carried out by Prahas and co-workers. 0.05 g of adsorbent was taken in a series of 100 mL volumetric flasks having 25 mL of 0.01 N NaOH (electrolyte solution). The pH of the solutions were adjusted from 1 to 10 and which were shaken for 48 h. Afterwards, supernant
Different parameters such as pH, particle size, amount of adsorbent, contact time and concentration were optimized using batch studies. Optimum pH for the adsorption studies was identified by carrying out a series of experiments at pH ranging from 1 to 10. pH adjusted 25 mL of 9 106 M RHB solutions, with 0.04 g of AM, were taken in 100 mL volumetric flasks and shaken for 2 h at 100 rpm in a rotatory shaker. The solutions were then filtered with Whatman no. 41 and analysed spectrophotometrically at 554 nm. Effect of particle size was then tested for three different sizes ranging from 710 to 300 mm. Adsorbent dosage accounting for maximum adsorption was further investigated for 0.02e0.1 g of AM. Contact time studies were carried out at different temperatures to note the time required for attaining equilibrium for the adsorbate-adsorbent system at 30, 40 and 50 C respectively. The study was continued till 5 h and the concentration of solutions was analysed after every 30 min. Study of concentration was done in the range of (1e10 106 M) RHB with optimized pH, particle size and adsorbent dosage. The amount of dye adsorbed (qe) was calculated using following equation in mol g1 (Eq. (1)).
qe ¼
Co Ce V m
(1)
where Co and Ce is the initial and equilibrium concentration of RHB in mol L1, m is the amount of adsorbent in g and V is volume of solution in L. 2.4. Isothermal studies It is important to establish the relationship between the adsorption capacity and nature of adsorption for an adsorbateadsorbent system since it explains the mechanism of adsorption and assists in optimizing the adsorption process. Different isothermal models viz. Langmuir and Freundlich have been tested for the removal of dyes from wastewater (Foo and Hameed, 2010; Rajeshkannan et al., 2011). As per Langmuir, adsorption takes place at homogenous sites of adsorbent (Langmuir, 1918), while Freundlich presumes heterogeneous surface of adsorbent with non-uniform dissemination of heat of adsorption over the surface (Freundlich, 1906). Langmuir and Freundlich isothermal models are represented by Eqs. (2) and (3).
1 1 1 ¼ þ qe Qo bQo Ce
(2)
Table 1 Isothermal parameters and error analysis by different function for RHB-AM adsorption system. Parameters
Langmuir isotherm
Temperature
30 C
Qo (mol g Kf R2 S.E. RMSE
c2 SSE SAE ARE
1
)
Freundlich isotherm 40 C
5
1.33 10 e 0.9495 2.14 107 3.6 107 4.21 107 7.2 1013 1.9 106 13.78
50 C 5
2.26 10 e 0.9332 2.65 107 3.11 107 2.6 107 5.81 1013 1.87 106 11.48
5
3.61 10 e 0.9007 3.23 107 3.47 107 2.8 107 7.22 1013 1.91 106 11.20
30 C
40 C
50 C
e 0.22 0.916 2.36 107 3.74 107 4.15 107 8.48 1013 2.1 106 13.46
e 0.27 0.9085 2.67 107 3.22 107 2.7 107 6.23 1013 1.9 106 11.51
e 0.40 0.9268 3.20 107 3.44 107 2.8 107 7.1 1013 1.9 106 10.90
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
S. Khamparia, D. Jaspal / Journal of Environmental Management xxx (2016) 1e8
1 log qe ¼ log Kf þ log Ce n
(3)
where Qo is maximum adsorption capacity in mol g1, b is the Langmuir constant in L mol1, Kf is the Freundlich constant related to adsorption capacity and n is the constant related to intensity of adsorption associated with heterogeneity factor. The experimental and isothermal predicted data have been compared on the basis of correlation coefficients (R2). Most appropriate isotherm model has been perceived on emulating the results attained by different error analysis functions namely Standard Error (S.E.), Root Mean Square Error (RMSE), Chi square test (c2), Sum of Squared Errors (SSE), Sum of Absolute Errors (SAE) and Average Relative Error (ARE). These error functions have been applied by several researchers in order to corroborate the most suitable isotherm for the studied system (Piccin et al., 2011; et al., 2015). The values for S.E., RMSE, c2, SSE, SAE and ARE Gîlca error functions were calculated using following relations (Eqs. (4)e(9)):
Sdev S:E: ¼ pffiffiffiffi N
(4)
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi u N 2 u 1 X RMSE ¼ t qeexp qemdel N 2 i¼1 PN
c ¼ 2
SSE ¼
i¼1
qeexp qemodel
2
qemodel n X
qemodel qeexp
(5)
n X qe
mdel
DH o DGo
(11)
(12)
T
where b, b1, and b2 are the Langmuir constants at different temperatures i.e. 30, 40 and 50 C respectively, R is the gas constant (8.314 kJ mol1) and T,T1,T2 are the temperatures in Kelvin. Examination of the controlling mechanism for the adsorbateadsorbent system was carried out by testing different kinetic models on the experimental data. In this study, Lagergren's Pseudo first order kinetic model (Periasamy and Namasivayam, 1994) and Pseudo second order proposed by Ho and co-workers (Ho et al., 2002) were applied to test the adsorption rate based on adsorbent capacity for the adsorption process (Eqs. (13) and (14)).
logðqe qt Þ ¼ log qe
k1 t 2:303
t 1 t ¼ þ qt k2 q2e qe
(13)
(14)
where qe is the amount of dye adsorbed at equilibrium in mg g1, qt is the amount of dye adsorbed at any time t in mg g1, and k1 is the pseudo-first-order rate constant of adsorption in min1 and k2 is the pseudo-second-order rate constant of adsorption in g mg1 min1. 3. Results and discussion
2
(7)
qeexp
(8)
i¼1
100 Xqecal qeexp ARE ¼ N qecal
(9)
where Sdev is the standard deviation of the data, N is the no of experimental data points, qeexp and qemdel are the observed adsorption capacity from experiment data and predicted adsorption capacity by the model in mol g1. Isotherm with maximum R2 value and minimum errors was selected as the best fit isotherm model for representing the experimental data. 2.5. Thermodynamic and kinetic studies Adsorption process in the present system deals with the interaction in two phases i.e. solid and liquid. The relative energy of the adsorbate at equilibrium point, during the adsorption process occurs at solid-liquid interface which can be expressed by thermodynamic parameters. Change in Gibb's free energy (DG ), enthalpy (DH ) and entropy (DS ) values allows to determine the feasibility, spontaneity and randomness of the adsorption process. These thermodynamic parameters were evaluated using following relations (Eqs. (10)e(12)):
DGo ¼ RT ln b
DSo ¼
T2 T1 b ln 2 T2 T1 b1
(6)
i¼1
SAE ¼
DHo ¼ R
3
(10)
3.1. Characterization of adsorbent SEM images show rough and flocced surface of the adsorbent which smoothened after adsorption revealing the accumulation of adsorbate over the adsorbent surface (Fig. 1a). Relative smoothening of the adsorbent surface indicated considerable uptake of dye molecules onto the adsorbent surface. Spectrum obtained from EDS, associated with SEM detected the presence of four major elements. AM seeds as per EDS studies contained 97.45% Carbon, 0.10% Sodium, 0.55% Phosphorous and 1.90% Potassium by weight. Shifting, appearance and disappearance of peaks in FTIR spectrum before and after adsorption indicated the adsorption of RHB over AM seeds. A broad band around 3200-3500 cm1 indicated the presence of hydroxyl groups on the adsorbent (Fig. 1b). The XRD pattern of RHB loaded and unloaded AM seeds are shown in Fig. 1c. Presence of broad peaks indicated the amorphousity of the adsorbent, whereas the shift in intensity after adsorption suggested an interaction between adsorbent and adsorbate molecules. It was found that the main peaks corresponded to the crystalline nature of adsorbent while secondary peaks indicated the amorphous nature of the adsorbent. In the XRD analysis of dye loaded samples when compared with unloaded adsorbent samples, the change in percentage of crystalline and amorphous phase was visible indicating adsorption of dye onto adsorbent. Also change in intensity of peaks was attributed to the adsorption of dyes onto the adsorbent. Similar trend was reported by several researchers (Kaur et al., 2012; Wang et al., 2006). Moreover the disappearance and diminishing of some peaks of dye loaded sample confirmed the effective uptake of dye molecules onto the surface of adsorbent (Santhi et al., 2011). Quantification of the functional groups was carried out by Boehm titration. AM seeds exhibited acidic nature (0.1013 mmol g1) with a maximum composition of phenolic compounds. Further proximate analysis
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
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Fig. 1. SEM (a), FTIR (b) and XRD (c) characterization of AM seeds before and after.
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
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5
revealed a high carbon content in the adsorbent of about 91.3%. The point of zero charge of the adsorbent was analysed by the final pH vs initial pH plot (Fig. 1d). The pHpzc value of the adsorbent was found to be 4.05 which indicated the nature of charge at adsorbent surface.adsorption of RHB. Point of zero charge of the AM seeds through pH drift method (d). 3.2. Batch studies 3.2.1. Effect of pH pH is the most important parameter in determining the adsorption efficiency since it affects the surface charge properties of the adsorbent and influences the behaviour of adsorbate ions into the solution (Soltani and Entezari, 2013). Uptake of RHB by AM seeds was studied as a function of pH ranging from 1 to 10. Maximum 70% decolorization was obtained at pH 3 at 30 C. Results showed that as pH increased from 3 to 10, dye removal decreased drastically from 70 to 30% (Fig. 2a). Amount of dye adsorbed was also observed to decrease from 75 to 32.346 106 g by varying pH from 3 to 10. Removal of RHB at low pH was also observed by Guo et al., (2005), Mohammadi et al., (2010) and Satapathy et al., (2014) using carbon based on rice husk, palm shell activated carbon and sea nodules respectively. The reason behind adsorption at lower pH was due to the existence of cationic and zwitterionic forms of RHB. The effect can also be explained with zero point charge of adsorbent. When the pH < pHpzc (4.05), the adsorbent surface becomes positively charged and thus attracts the ionic form of RHB dye causing enhanced adsorption at pH lower than pHpzc value (Maurya et al., 2006). Thus due to the availability of some carboxylic anions on RHB in the solution during attainment of equilibrium, adsorption takes place at the positively charged adsorbent surface (Soltani and Entezari, 2013). Also, below pH 3 i.e. optimum pH, the electrostatic repulsion between cationic RHB groups after attainment of equilibrium and charged positive adsorbents leads to a decrease in percentage of adsorption (Li et al., 2010). 3.2.2. Effect of particle size Adsorptive removal of RHB dye was studied for three different particle sizes of AM seeds ranging from 710 to 600, 600e245 and 425-300 mm. Results indicated maximum uptake of dye with 0.04 g of 425e300 mm AM seeds for the studied concentration (9 106 M) of RHB at pH 3. As the particle size range decreased from 710 to 300 mm, adsorption increased from 71.88 to 76.1 106 g. These results were supported by an increase in rate constant with a decrease in half-life period. Higher adsorption with smaller sized particle was due to the accessibility to larger surface area of adsorbent for adsorption to take place (Gupta et al., 2015b). 3.2.3. Effect of adsorbent dosage Effect of adsorbent dosage was investigated for the removal capacity of RHB from aqueous solution at optimum pH 3. The adsorbent dosage for the system was varied from 0.02 to 0.12 g for the same dye concentration (9 106 M) at 30 C. Fig. 2b illustrates the trend of adsorption with variation in adsorbent dosage. Maximum adsorption of RHB was observed as 71.1% for a dosage of 0.06 g/25 mL for AM seeds at studied temperature. The amount adsorbed increased from 70.68 to 76.67 106 g with an increase in adsorbent dosage from 0.02 to 0.06. Increase in adsorption with increase in adsorbent dosage was possibly due to the increase in availability of adsorption sites for the dye ions. On further increasing the adsorbent dosage, adsorption rate remained almost constant with slight decrease till 0.12 g. This decrease in adsorption with an increase in adsorbent dosage after
Fig. 2. Effect of pH (a), adsorbent dosage (b), contact time (c) and dye concentration (d).
certain amount (0.08 g) suggested the adsorption mechanism to be reversible in nature and directed towards the existence of chemical equilibrium between the adsorbent and adsorbate (Ali et al., 2011). A similar shift was observed in the percentage removal which initially increased from 65 to 71% and later decreased to 68.88% with an increase in adsorbent dosage. For further studies 0.06 g of adsorbent was opted as the optimum dosage.
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
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adsorbent with decrease in viscosity of solution (Al-Qodah, 2000). 3.3. Adsorption isotherms
Fig. 3. Experimental and isothermal modelled data for RHB-AM seeds adsorption system.
3.2.4. Effect of contact time Extent of dye uptake was further studied as a function of contact time. The contact time for the adsorption study was varied from 30 to 270 min for 0.06 g/25 mL of 9 106 M RHB solution at pH 3. The concentration of the dye solution was measured periodically after every 30 min. It is evident from Fig. 2c that an equilibrium was attained after 240 min of contact time. On the basis of the results obtained from contact time studies, 240 min was taken as the equilibrium time in kinetic adsorption experiments. The percentage removal increased from 38, 51 and 60 to 71, 72 and 77% at 30, 40 and 50 C respectively. Rapid increase in percentage removal was observed in first 90 min which gradually increased till attainment of equilibrium. As the temperature increased from 30 to 50 C the amount adsorbed increased from 41.93 to 83.86 106 g, suggesting an endothermic nature of adsorption process. Similar trend was observed by Dogan and an et al., 2004). fellow researchers (Dog 3.2.5. Effect of concentration Initial dye concentration in the reaction mixture acts as a driving force for the uptake of adsorbate ions by the adsorbent in batch adsorption process. Study of concentration was carried out by varying the dye concentration from 1e10 106 M RHB at pH 3 with 0.06 g of powdered AM seeds (Fig. 2d). It was noted that as the dye concentration increased, the amount of dye adsorbed increased from 2.396, 5.99, 9.584 to 76.672, 79.068 and 91.048 106 g at 30, 40 and 50 C respectively (Kuo et al., 2008). Obtained results suggested adsorption process to be dependent on the initial adsorbate concentration up to some extent (Rafatullah et al., 2009). Favourability of adsorption process at higher temperature was also evident with increase in dye uptake at higher temperature. The enhancement in adsorption may be due to the increase in rate of diffusion of adsorbate molecules towards
Investigation of Langmuir and Freundlich equilibrium isotherms onto the experimental data obtained at optimum conditions was done to assess the fitness of experimental data to the tested models at 30, 40 and 50 C. A graph of 1/qe versus 1/Ce for the Langmuir isotherm was plotted to determine the isothermal parameters from the slopes (1/Qob) and intercepts (1/Qo) of the obtained graph. Similarly a graph was plotted between log qe versus log Ce to determine the Freundlich isothermal parameters. The linear plot resulted with the straight lines giving slope of 1/n and an intercept of Log Kf. The isothermal parameters obtained from the linear plots are presented in Table 1. Maximum monolayer coverage predicted by Langmuir isotherm model was found to be 3.61 105 mol g1 at 50 C. The values of adsorption intensity, b decreased from 7.07 to 4.46 104 L mol1 with an increase in temperature from 30 to 50 C. Similar trend was reported by Sampranpiboon and coauthors (Sampranpiboon et al., 2014). The values from RL lied from 0.93 to 0.90 at 30e50 C. The calculated values were greater than zero and less than one predicting the favourability of the isotherm to the experimental data. Freundlich constant, 1/n was found to be less than 1 at all the studied temperatures indicating favourability to the isotherm. Kf values related to adsorption capacity, were also found to increase with increase in temperature suggesting favourability of the process at higher temperatures. Fig. 3 compares the fitness of both the isotherms onto the experimental data. Both Langmuir and Freundlich fitted to the experimental data with R2 > 0.9. But on comparing the different error functions and closeness of R2 value to linearity, Langmuir isotherm model was found to be the best fit for the studied system. It was also evident from Table 2, that the experimental data was well described by Langmuir model with lower values of different error functions i.e. S.E, R.M.S.E, c2, SSE, SAE and ARE. Significance of the error functions lies in the fact that lower the magnitude of errors, greater will be the closeness of the modelled data to the experimental data and higher will be the suitability of the model for the system. As the data fitted quite well with the Langmuir isotherm, participation of homogenous active sites of the adsorbent was assumed. 3.4. Adsorption kinetics Adsorption kinetics for the RHB-AM system was evaluated by applying Pseudo first and second order kinetic models. Linear graphs of log qe-qt versus time and t/qt versus time were plotted for the first and second order kinetic models using Eqs. (13) and (14). Rate constant k1 and k2 were tabulated from the slopes of the first
Table 2 Pseudo first and second order kinetic model parameters and error analysis for RHB-AM adsorption system. Parameters
Pseudo 1st order
Temperature
30 C
40 C
50 C
30 C
40 C
50 C
0.0103 e 0.9643 0.0557 0.6310 6.0376 2.78 4.99 10.19
0.0089 e 0.9663 0.0348 0.9669 24.976 6.54 7.67 27.46
0.0081 e 0.9869 0.0325 1.1149 38.485 8.70 8.84 36.54
e 1.73 102 0.9945 0.0701 0.0438 0.0165 0.013 0.29 3.49
e 3.50 102 0.9969 0.0503 0.0461 0.0164 0.014 0.268 2.75
e 3.55 102 0.9957 0.0505 0.0722 0.0378 0.001 0.025 3.71
1
k1 (min ) k2 (g mg min1) R2 S.E. RMSE
c2 SSE SAE ARE
Pseudo 2nd order
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and second order plots respectively (Table 2). Kinetic study revealed that adsorption of RHB increased with an increase in time along with temperature. The rate of adsorption was quick for first 90 min and then the rate gradually increased until equilibrium was attained. Table 2 depicts the pseudo second order rate constant values which increased with increase in temperature showing favourability at higher temperatures. Moreover the values of correlation coefficients were higher than 0.99 and close to unity, affirming the fitness of the pseudo second order kinetic model. Additionally, both the models were compared and a graph was plotted between experimental and predicted qt values with contact time. It was evident from Fig. 4 that pseudo second order model fitted well with the experimental data. The graph indicated that the predicted data by the pseudo second order model was in good agreement with that of experimental values showing better simulation results. Error analysis of the obtained data for both kinetic models were carried out by subjecting to different functions (Table 2). Results confirmed the suitability of Pseudo second order kinetic model for the present system with higher R2 values and minimum S.E., RMSE, c2, SSE, SAE and ARE values on comparison with pseudo first order kinetic model. For better understating of the kinetics, the experimental data was applied to a mathematical treatment given by Boyed and his research team (Boyd et al., 1947). Indepth mechanism of adsorption process undergoing via film or particle diffusion was acquired by performing a linearity test which resulted in straight line passing through origin at 30 C indicating particle diffusion while the lines were away from origin at higher temperatures depicting film diffusion at high temperatures (Supplementary material. Fig. 1). 3.5. Adsorption thermodynamics In order to determine the spontaneity and nature of adsorption process, thermodynamic study was carried out for the RHB-AM system. Thermodynamic parameters were calculated by using equations (Eqs. (10)e(12)) which resulted to negative values of free energy and positive values of enthalpy and entropy for the system. Change in Gibb's free energy was found to be 28.27 kJ mol1 for the system which suggested the process to be spontaneous in nature. Whereas change in enthalpy and entropy was found to be 18.48 kJ mol1 and 149.99 J K1 mol1 respectively. Similar results have been reported by Ho and fellow researchers (Ho et al., 2005) for the removal of a dye using fern tree as a biosorbent. A positive value of enthalpy directed towards the endothermic nature of the adsorption process which was supported by an increase in adsorption at higher temperatures, while positive value of entropy showed the increase in randomness at the adsorbate-adsorbent
Fig. 4. Experimental and kinetic modelled data for RHB-AM seeds adsorption system.
7
interface. This increase in randomness is attributed to the displacement of the water molecules by the dye ions during the adsorption process over the adsorbent (Vasu, 2008). 4. Conclusion Evaluation of adsorption capacity of Argemone mexicana seeds was done through batch mode studies. SEM, EDS, FTIR, XRD characterization of the adsorbent showed the rough surface with presence of different functional groups favourable for adsorption process. Effect of different parameters during batch studies resulted in maximum removal of RHB at optimum pH 3 with 0.06 g of adsorbent. Higher percentage of removal was attained at equilibrium for the studied concentration. Also the election of the best suited isotherm was made after comparing different error functions such as S.E., RMSE, c2, SAE, SSE and ARE along with correlation coefficients (R2). Langmuir model was found to be the best fit for the experimental data with R2 > 0.9 and minimum values of error functions at all the temperatures studied. Kinetic model supported the results obtained by isothermal analysis following pseudo second order model showing chemisorption during the adsorption process. Thermodynamic model suggested the process to be spontaneous and endothermic in nature with Gibb's free energy as 28.27 kJ mol1. The adsorption studies therefore established Argemone mexicana seeds to be cost effective and efficient adsorbent for removal of textile dye from waste water. Appendix A. Supplementary data Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.jenvman.2016.09.036. References Al-Qodah, Z., 2000. Adsorption of dyes using shale oil ash. Water Res. 34, 4295e4303. http://dx.doi.org/10.1016/S0043-1354(00)00196-2. Ali, S.Z., Athar, M., Salman, M., Din, M.I., 2011. Simultaneous removal of Pb (II), Cd (II) and Cu (II) from aqueous solutions by adsorption on Triticum aestivum-a green approach. Hydrol. Curr. Res. 2 http://dx.doi.org/10.4172/2157-7587.1000118. Bapat, S.A., Jaspal, D.K., 2016. Parthenium hysterophorus: novel adsorbent for the removal of heavy metals and dyes. Global J. Environ. Sci. Manage 2, 135e144. http://dx.doi.org/10.7508/gjesm.2016.02.004. Boyd, G.E., Adamson, A.W., Myers Jr., L.S., 1947. The exchange adsorption of ions from aqueous solutions by organic zeolites. II. Kinetics1. J. Am. Chem. Soc. 69, 2836e2848. € an, M., Alkan, M., Türkyilmaz, A., Ozdemir, Dog Y., 2004. Kinetics and mechanism of removal of methylene blue by adsorption onto perlite. J. Hazard. Mater 109, 141e148. http://dx.doi.org/10.1016/j.jhazmat.2004.03.003. Ekpete, O.A., Horsfall, M.J.N.R., 2011. Preparation and characterization of activated carbon derived from fluted pumpkin stem waste (Telfairia occidentalis Hook F). Res. J. Chem. Sci. 1, 10e17. Foo, K.Y., Hameed, B.H., 2010. Insights into the modeling of adsorption isotherm systems. Chem. Eng. J. 156, 2e10. http://dx.doi.org/10.1016/j.cej.2009.09.013. Freundlich, H.M.F., 1906. Over the adsorption in solution. J. Phys. Chem. 57, 385e470. , E., M neanu, A., Ghiris¸an, A., Ilea, P., 2015. Kinetic modeling and error Gîlca aica analysis for zinc removal on a weak base anion exchange resin. Desalin. Water Treat. 1e9. http://dx.doi.org/10.1080/19443994.2015.1101018. Guo, Y., Zhao, J., Zhang, H., Yang, S., Qi, J., Wang, Z., Xu, H., 2005. Use of rice huskbased porous carbon for adsorption of Rhodamine B from aqueous solutions. Dyes Pigments 66, 123e128. http://dx.doi.org/10.1016/j.dyepig.2004.09.014. Gupta, V.K., Khamparia, S., Tyagi, I., Jaspal, D., Malviya, A., 2015. Decolorization of mixture of dyes: a critical review. Global J. Environ. Sci. Manage 1, 71e94. http://dx.doi.org/10.7508/gjesm.2015.01. Gupta, V., Agarwal, A., Singh, M.K., 2015. Belpatra (aegel marmelos) bark powder as an adsorbent for the color removal of textile dye “torque blue”. Int. J. Sci. Eng. Technol. 4, 56e60. Ho, Y.S., Porter, J.F., McKay, G., 2002. Equilibrium isotherm studies for the sorption of divalent metal ions onto peat: copper, nickel and lead single component systems. Water Air Soil Poll. 141, 1e33. http://dx.doi.org/10.1023/A: 1021304828010. Ho, Y.S., Chiang, T.H., Hsueh, Y.M., 2005. Removal of basic dye from aqueous solution using tree fern as a biosorbent. Process Biochem. 40, 119e124. http://dx.doi.org/ 10.1016/j.procbio.2003.11.035.
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Inthorn, D., Singhtho, S., Thiravetyan, P., Khan, E., 2004. Decolorization of basic, direct and reactive dyes by pre-treated narrow-leaved cattail (Typha angustifolia Linn.). Bioresour. Technol. 94, 299e306. http://dx.doi.org/10.1016/ j.biortech.2004.01.002. Kaur, S., Rani, S., Mahajan, R.K., 2012. Adsorption kinetics for the removal of hazardous dye Congo red by biowaste materials as adsorbents. J. Chem. 2013, 1e12. http://dx.doi.org/10.1155/2013/628582. Khan, T.A., Sharma, S., Ali, I., 2011. Adsorption of Rhodamine B dye from aqueous solution onto acid activated mango (Magnifera indica) leaf powder: equilibrium, kinetic and thermodynamic studies. J. Toxicol. Env. Health Sci. 3, 286e297. Kuo, C.Y., Wu, C.H., Wu, J.Y., 2008. Adsorption of direct dyes from aqueous solutions by carbon nanotubes: determination of equilibrium, kinetics and thermodynamics parameters. J. Colloid Inter. Sci. 327, 308e315. http://dx.doi.org/10.1016/ j.jcis.2008.08.038. Lalitha, P., Sangeetha, S.N., 2008. Experimental investigation of the adsorption of Rhodamine-B from aqueous solution onto activated carbon from water hyacinth. Orient. J. Chem. 24, 983e988. Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass, mica and platinum. J. Am. Chem. Soc. 40, 1361e1403. Lata, H., Mor, S., Garg, V.K., Gupta, R.K., 2008. Removal of a dye from simulated wastewater by adsorption using treated parthenium biomass. J. Hazard. Mater 153, 213e220. http://dx.doi.org/10.1016/j.jhazmat.2007.08.039. Li, L., Liu, S., Zhu, T., 2010. Application of activated carbon derived from scrap tires for adsorption of Rhodamine B. J. Environ. Sci. 22, 1273e1280. http://dx.doi.org/ 10.1016/S1001-0742(09)60250-3. Maurya, N.S., Mittal, A.K., Cornel, P., Rother, E., 2006. Biosorption of dyes using dead macro fungi: effect of dye structure, ionic strength and pH. Bioresour. Technol. 97, 512e521. http://dx.doi.org/10.1016/j.biortech.2005.02.045. Mittal, A., Kaur, D., Malviya, A., Mittal, J., Gupta, V.K., 2009. Adsorption studies on the removal of coloring agent phenol red from wastewater using waste materials as adsorbents. J. Colloid Interf. Sci. 337, 345e354. http://dx.doi.org/10.1016/ j.jcis.2009.05.016. Mohammadi, M., Hassani, A.J., Mohamed, A.R., Najafpour, G.D., 2010. Removal of Rhodamine B from aqueous solution using palm shell-based activated carbon: adsorption and kinetic studies. J. Chem. Eng. Data 55, 5777e5785. http:// dx.doi.org/10.1021/je100730a. Periasamy, K., Namasivayam, C., 1994. Process development for removal and recovery of cadmium from wastewater by a low-cost adsorbent: adsorption rates and equilibrium studies. Ind. Eng. Chem. Res. 33, 317e320. http://dx.doi.org/ 10.1021/ie00026a022. Piccin, J.S., Dotto, G.L., Pinto, L.A.A., 2011. Adsorption isotherms and thermochemical data of FD&C Red n 40 binding by chitosan. Braz. J. Chem. Eng. 28, 295e304.
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Research article
Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana Shraddha Khamparia a, *, Dipika Jaspal b a b
Symbiosis Centre for Research and Innovation, Symbiosis International University, Gram:Lavale, Tal Mulshi, Pune 412115, India Symbiosis Institute of Technology, A Constituent of Symbiosis International University, Gram:Lavale, Tal Mulshi, Pune 412115, India
a r t i c l e i n f o
a b s t r a c t
Article history: Received 5 April 2016 Received in revised form 7 June 2016 Accepted 11 September 2016 Available online xxx
The present study aims at exploring the potential of the seeds of a tropical weed, Argemone mexicana (AM), for the removal of a toxic xanthene textile dye, Rhodamine B (RHB), from waste water. Impact of pH, adsorbent dosage, particle size, contact time and dye concentration have been assessed during adsorption. The weed has been well characterized by several latest techniques thereby providing an indepth information of the mechanism during adsorption. About 80% removal has been attained with 0.06 g of adsorbent over the studied system. Thermodynamic and kinetic studies, followed by second order kinetic model, directed towards the endothermic nature of adsorption. The results obtained from batch experiments were modelled using Langmuir and Freundlich isotherm and were analysed on the basis of R2 and six error functions for selection of appropriate model. Langmuir isotherm was found to be best fitted to the experimental data with high values of R2 and lower values of error functions. Adsorption study revealed the affinity of AM seeds for the dye ions present in waste water, introducing a novel adsorbent in field of waste water treatment. © 2016 Elsevier Ltd. All rights reserved.
Keywords: Adsorption Argemone mexicana weed Error functions Langmuir Rhodamine B
1. Introduction Synthetic dyes are considered as the prime contributors towards water pollution. The presence of synthetic dyes in aquatic system, not only deteriorates the clarity of water bodies but also affects the human health directly or indirectly (Robinson et al., 2001). Textile industry being the primary consumer of synthetic dyes, inevitably generates the necessity to treat the textile effluents, before it gets discharged from the source. Some of the dyes are reported to be highly toxic and mutagenic in nature (Wang et al., 2005). Rhodamine B (RHB) is reported to be carcinogenic due to the presence of four N-ethyl linkages on either sides of xanthene ring in its structure (Mohammadi et al., 2010). Ingestion of this dye may result in gastrointestinal disorders with irritation in eyes and skin (Khan et al., 2011). Several physio-chemical, biological and advanced oxidation treatment methods have been employed for the treatment of textile effluents (Gupta et al., 2015a). Amongst different techniques,
* Corresponding author. Symbiosis Centre for Research and Innovation, Symbiosis International University Lavale, Pune, 412115, India. E-mail addresses: [email protected], shraddha.khamparia@ sitpune.edu.in (S. Khamparia), [email protected] (D. Jaspal).
adsorption is a method used since decades (Mittal et al., 2009). The major advantage of adsorption technique lies in its easy application with the higher possibility of using different adsorbents. In view of eco-friendly treatment methods, an urgent need has eventuated to find cost effective and sustainable materials for dye removal. In this regard, the recent contemporary approach of utilization of cheap and waste bio materials during adsorption have been in limelight, replacing the use of costly activated carbon. Different weeds such as Parthenium Hysterophorous (Lata et al., 2008; Bapat and Jaspal, 2016), Water Hyacinth (Lalitha and Sangeetha, 2008), Congon grass (Su et al., 2014) and Narrow leaved Cattail (Inthorn et al., 2004) etc. have been employed after pre-treatment for the removal of dyes from aqueous solution. In an urge to find the sustainable and low cost bio materials for adsorption, an uncharted tropical weed, Argemone mexicana (AM) has been tested in the current research to explore its potential towards decolorization of a cationic toxic textile dye RHB, from textile effluent. AM is a perennial species which can flourish in drought prone regions and is available in abundance. Seeds of AM have been used for adulteration which further drew the attention towards their use as adsorbent. Subsequently, characterization, optimization, equilibrium and kinetic studies were carried out for the adsorbate-adsorbent system.
http://dx.doi.org/10.1016/j.jenvman.2016.09.036 0301-4797/© 2016 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
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liquid was tested for change in pH, and the pHpzc value was determined (Prahas et al., 2008).
2. Materials and method 2.1. Adsorbent and adsorbate
2.3. Batch studies AM weed, commonly known as Mexican prickly poppy abundantly available in and around Sus-Mahalunge area, Pune, Maharashtra, India, was chosen for the adsorption study for the removal of RHB, a cationic xanthene dye. AM seeds closely resemble mustard seeds. The buds were plucked properly and deseeded. Further the seeds were deoiled, grounded and sieved through IS: 460 standard sieve sets to get the desired range of particles of 425e300 mm. (Supplementary material. Table 1). Stock solution of 103 M RHB was prepared with distilled water which was further diluted to the get the desired concentration range of test solutions (1 106 to 10 106 M). The absorption spectrum and concentration of RHB was analysed by a Systronic Double beam spectrophotometer (Model No. 2203) at 554 nm (wavelength of maximum absorption). pH of the solutions were adjusted using 0.1 N HCl and NaOH of analytical grade.
2.2. Characterization of adsorbent Several latest techniques, such as Energy Dispersive X-ray spectroscopy embedded with Scanning electron Microscope (JEOL JSM 6300A), Fourier Transform Infrared spectrophotometry (JASCO 6100 FTIR) and X-Ray Diffraction crystallography (D8 Advance) were employed to detect the elements, surface morphology, functional groups and nature of the adsorbent (AM). Quantification of functional groups was performed by Boehm technique. About 1 g of adsorbent with 20 mL of 0.1 M NaHCO3, 0.05 M Na2CO3, 0.1 M NaOH (for acidic groups) and 0.1 M HCl (for basic groups) was taken in different 100 mL volumetric flask at room temperature for 48 h. Quantification of acidic and basic groups was done by titrating the supernant liquids with respective solutions during acid-base titrations. Both indicators and pH meter were used to determine endpoint of the titration. Considering that NaHCO3 only neutralizes carboxylic groups, Na2CO3 neutralizes carboxylic and lactonic while NaOH neutralizes carboxylic, lactonic and phenolic groups, the difference were calculated giving the quantity of carboxylic, lactones and phenol groups. Basic groups were estimated by back titrating the supernant liquid with strong base (0.1 M NaOH) (Ekpete and Horsfall, 2011). The adsorbent was subjected to proximate analysis (ASTM D 3172-3175 standards) in order to account for moisture, ash, and fixed carbon content. Also the point of zero charge, pHpzc value of the adsorbent was evaluated using pH drift method as carried out by Prahas and co-workers. 0.05 g of adsorbent was taken in a series of 100 mL volumetric flasks having 25 mL of 0.01 N NaOH (electrolyte solution). The pH of the solutions were adjusted from 1 to 10 and which were shaken for 48 h. Afterwards, supernant
Different parameters such as pH, particle size, amount of adsorbent, contact time and concentration were optimized using batch studies. Optimum pH for the adsorption studies was identified by carrying out a series of experiments at pH ranging from 1 to 10. pH adjusted 25 mL of 9 106 M RHB solutions, with 0.04 g of AM, were taken in 100 mL volumetric flasks and shaken for 2 h at 100 rpm in a rotatory shaker. The solutions were then filtered with Whatman no. 41 and analysed spectrophotometrically at 554 nm. Effect of particle size was then tested for three different sizes ranging from 710 to 300 mm. Adsorbent dosage accounting for maximum adsorption was further investigated for 0.02e0.1 g of AM. Contact time studies were carried out at different temperatures to note the time required for attaining equilibrium for the adsorbate-adsorbent system at 30, 40 and 50 C respectively. The study was continued till 5 h and the concentration of solutions was analysed after every 30 min. Study of concentration was done in the range of (1e10 106 M) RHB with optimized pH, particle size and adsorbent dosage. The amount of dye adsorbed (qe) was calculated using following equation in mol g1 (Eq. (1)).
qe ¼
Co Ce V m
(1)
where Co and Ce is the initial and equilibrium concentration of RHB in mol L1, m is the amount of adsorbent in g and V is volume of solution in L. 2.4. Isothermal studies It is important to establish the relationship between the adsorption capacity and nature of adsorption for an adsorbateadsorbent system since it explains the mechanism of adsorption and assists in optimizing the adsorption process. Different isothermal models viz. Langmuir and Freundlich have been tested for the removal of dyes from wastewater (Foo and Hameed, 2010; Rajeshkannan et al., 2011). As per Langmuir, adsorption takes place at homogenous sites of adsorbent (Langmuir, 1918), while Freundlich presumes heterogeneous surface of adsorbent with non-uniform dissemination of heat of adsorption over the surface (Freundlich, 1906). Langmuir and Freundlich isothermal models are represented by Eqs. (2) and (3).
1 1 1 ¼ þ qe Qo bQo Ce
(2)
Table 1 Isothermal parameters and error analysis by different function for RHB-AM adsorption system. Parameters
Langmuir isotherm
Temperature
30 C
Qo (mol g Kf R2 S.E. RMSE
c2 SSE SAE ARE
1
)
Freundlich isotherm 40 C
5
1.33 10 e 0.9495 2.14 107 3.6 107 4.21 107 7.2 1013 1.9 106 13.78
50 C 5
2.26 10 e 0.9332 2.65 107 3.11 107 2.6 107 5.81 1013 1.87 106 11.48
5
3.61 10 e 0.9007 3.23 107 3.47 107 2.8 107 7.22 1013 1.91 106 11.20
30 C
40 C
50 C
e 0.22 0.916 2.36 107 3.74 107 4.15 107 8.48 1013 2.1 106 13.46
e 0.27 0.9085 2.67 107 3.22 107 2.7 107 6.23 1013 1.9 106 11.51
e 0.40 0.9268 3.20 107 3.44 107 2.8 107 7.1 1013 1.9 106 10.90
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
S. Khamparia, D. Jaspal / Journal of Environmental Management xxx (2016) 1e8
1 log qe ¼ log Kf þ log Ce n
(3)
where Qo is maximum adsorption capacity in mol g1, b is the Langmuir constant in L mol1, Kf is the Freundlich constant related to adsorption capacity and n is the constant related to intensity of adsorption associated with heterogeneity factor. The experimental and isothermal predicted data have been compared on the basis of correlation coefficients (R2). Most appropriate isotherm model has been perceived on emulating the results attained by different error analysis functions namely Standard Error (S.E.), Root Mean Square Error (RMSE), Chi square test (c2), Sum of Squared Errors (SSE), Sum of Absolute Errors (SAE) and Average Relative Error (ARE). These error functions have been applied by several researchers in order to corroborate the most suitable isotherm for the studied system (Piccin et al., 2011; et al., 2015). The values for S.E., RMSE, c2, SSE, SAE and ARE Gîlca error functions were calculated using following relations (Eqs. (4)e(9)):
Sdev S:E: ¼ pffiffiffiffi N
(4)
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi u N 2 u 1 X RMSE ¼ t qeexp qemdel N 2 i¼1 PN
c ¼ 2
SSE ¼
i¼1
qeexp qemodel
2
qemodel n X
qemodel qeexp
(5)
n X qe
mdel
DH o DGo
(11)
(12)
T
where b, b1, and b2 are the Langmuir constants at different temperatures i.e. 30, 40 and 50 C respectively, R is the gas constant (8.314 kJ mol1) and T,T1,T2 are the temperatures in Kelvin. Examination of the controlling mechanism for the adsorbateadsorbent system was carried out by testing different kinetic models on the experimental data. In this study, Lagergren's Pseudo first order kinetic model (Periasamy and Namasivayam, 1994) and Pseudo second order proposed by Ho and co-workers (Ho et al., 2002) were applied to test the adsorption rate based on adsorbent capacity for the adsorption process (Eqs. (13) and (14)).
logðqe qt Þ ¼ log qe
k1 t 2:303
t 1 t ¼ þ qt k2 q2e qe
(13)
(14)
where qe is the amount of dye adsorbed at equilibrium in mg g1, qt is the amount of dye adsorbed at any time t in mg g1, and k1 is the pseudo-first-order rate constant of adsorption in min1 and k2 is the pseudo-second-order rate constant of adsorption in g mg1 min1. 3. Results and discussion
2
(7)
qeexp
(8)
i¼1
100 Xqecal qeexp ARE ¼ N qecal
(9)
where Sdev is the standard deviation of the data, N is the no of experimental data points, qeexp and qemdel are the observed adsorption capacity from experiment data and predicted adsorption capacity by the model in mol g1. Isotherm with maximum R2 value and minimum errors was selected as the best fit isotherm model for representing the experimental data. 2.5. Thermodynamic and kinetic studies Adsorption process in the present system deals with the interaction in two phases i.e. solid and liquid. The relative energy of the adsorbate at equilibrium point, during the adsorption process occurs at solid-liquid interface which can be expressed by thermodynamic parameters. Change in Gibb's free energy (DG ), enthalpy (DH ) and entropy (DS ) values allows to determine the feasibility, spontaneity and randomness of the adsorption process. These thermodynamic parameters were evaluated using following relations (Eqs. (10)e(12)):
DGo ¼ RT ln b
DSo ¼
T2 T1 b ln 2 T2 T1 b1
(6)
i¼1
SAE ¼
DHo ¼ R
3
(10)
3.1. Characterization of adsorbent SEM images show rough and flocced surface of the adsorbent which smoothened after adsorption revealing the accumulation of adsorbate over the adsorbent surface (Fig. 1a). Relative smoothening of the adsorbent surface indicated considerable uptake of dye molecules onto the adsorbent surface. Spectrum obtained from EDS, associated with SEM detected the presence of four major elements. AM seeds as per EDS studies contained 97.45% Carbon, 0.10% Sodium, 0.55% Phosphorous and 1.90% Potassium by weight. Shifting, appearance and disappearance of peaks in FTIR spectrum before and after adsorption indicated the adsorption of RHB over AM seeds. A broad band around 3200-3500 cm1 indicated the presence of hydroxyl groups on the adsorbent (Fig. 1b). The XRD pattern of RHB loaded and unloaded AM seeds are shown in Fig. 1c. Presence of broad peaks indicated the amorphousity of the adsorbent, whereas the shift in intensity after adsorption suggested an interaction between adsorbent and adsorbate molecules. It was found that the main peaks corresponded to the crystalline nature of adsorbent while secondary peaks indicated the amorphous nature of the adsorbent. In the XRD analysis of dye loaded samples when compared with unloaded adsorbent samples, the change in percentage of crystalline and amorphous phase was visible indicating adsorption of dye onto adsorbent. Also change in intensity of peaks was attributed to the adsorption of dyes onto the adsorbent. Similar trend was reported by several researchers (Kaur et al., 2012; Wang et al., 2006). Moreover the disappearance and diminishing of some peaks of dye loaded sample confirmed the effective uptake of dye molecules onto the surface of adsorbent (Santhi et al., 2011). Quantification of the functional groups was carried out by Boehm titration. AM seeds exhibited acidic nature (0.1013 mmol g1) with a maximum composition of phenolic compounds. Further proximate analysis
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
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Fig. 1. SEM (a), FTIR (b) and XRD (c) characterization of AM seeds before and after.
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
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revealed a high carbon content in the adsorbent of about 91.3%. The point of zero charge of the adsorbent was analysed by the final pH vs initial pH plot (Fig. 1d). The pHpzc value of the adsorbent was found to be 4.05 which indicated the nature of charge at adsorbent surface.adsorption of RHB. Point of zero charge of the AM seeds through pH drift method (d). 3.2. Batch studies 3.2.1. Effect of pH pH is the most important parameter in determining the adsorption efficiency since it affects the surface charge properties of the adsorbent and influences the behaviour of adsorbate ions into the solution (Soltani and Entezari, 2013). Uptake of RHB by AM seeds was studied as a function of pH ranging from 1 to 10. Maximum 70% decolorization was obtained at pH 3 at 30 C. Results showed that as pH increased from 3 to 10, dye removal decreased drastically from 70 to 30% (Fig. 2a). Amount of dye adsorbed was also observed to decrease from 75 to 32.346 106 g by varying pH from 3 to 10. Removal of RHB at low pH was also observed by Guo et al., (2005), Mohammadi et al., (2010) and Satapathy et al., (2014) using carbon based on rice husk, palm shell activated carbon and sea nodules respectively. The reason behind adsorption at lower pH was due to the existence of cationic and zwitterionic forms of RHB. The effect can also be explained with zero point charge of adsorbent. When the pH < pHpzc (4.05), the adsorbent surface becomes positively charged and thus attracts the ionic form of RHB dye causing enhanced adsorption at pH lower than pHpzc value (Maurya et al., 2006). Thus due to the availability of some carboxylic anions on RHB in the solution during attainment of equilibrium, adsorption takes place at the positively charged adsorbent surface (Soltani and Entezari, 2013). Also, below pH 3 i.e. optimum pH, the electrostatic repulsion between cationic RHB groups after attainment of equilibrium and charged positive adsorbents leads to a decrease in percentage of adsorption (Li et al., 2010). 3.2.2. Effect of particle size Adsorptive removal of RHB dye was studied for three different particle sizes of AM seeds ranging from 710 to 600, 600e245 and 425-300 mm. Results indicated maximum uptake of dye with 0.04 g of 425e300 mm AM seeds for the studied concentration (9 106 M) of RHB at pH 3. As the particle size range decreased from 710 to 300 mm, adsorption increased from 71.88 to 76.1 106 g. These results were supported by an increase in rate constant with a decrease in half-life period. Higher adsorption with smaller sized particle was due to the accessibility to larger surface area of adsorbent for adsorption to take place (Gupta et al., 2015b). 3.2.3. Effect of adsorbent dosage Effect of adsorbent dosage was investigated for the removal capacity of RHB from aqueous solution at optimum pH 3. The adsorbent dosage for the system was varied from 0.02 to 0.12 g for the same dye concentration (9 106 M) at 30 C. Fig. 2b illustrates the trend of adsorption with variation in adsorbent dosage. Maximum adsorption of RHB was observed as 71.1% for a dosage of 0.06 g/25 mL for AM seeds at studied temperature. The amount adsorbed increased from 70.68 to 76.67 106 g with an increase in adsorbent dosage from 0.02 to 0.06. Increase in adsorption with increase in adsorbent dosage was possibly due to the increase in availability of adsorption sites for the dye ions. On further increasing the adsorbent dosage, adsorption rate remained almost constant with slight decrease till 0.12 g. This decrease in adsorption with an increase in adsorbent dosage after
Fig. 2. Effect of pH (a), adsorbent dosage (b), contact time (c) and dye concentration (d).
certain amount (0.08 g) suggested the adsorption mechanism to be reversible in nature and directed towards the existence of chemical equilibrium between the adsorbent and adsorbate (Ali et al., 2011). A similar shift was observed in the percentage removal which initially increased from 65 to 71% and later decreased to 68.88% with an increase in adsorbent dosage. For further studies 0.06 g of adsorbent was opted as the optimum dosage.
Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036
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adsorbent with decrease in viscosity of solution (Al-Qodah, 2000). 3.3. Adsorption isotherms
Fig. 3. Experimental and isothermal modelled data for RHB-AM seeds adsorption system.
3.2.4. Effect of contact time Extent of dye uptake was further studied as a function of contact time. The contact time for the adsorption study was varied from 30 to 270 min for 0.06 g/25 mL of 9 106 M RHB solution at pH 3. The concentration of the dye solution was measured periodically after every 30 min. It is evident from Fig. 2c that an equilibrium was attained after 240 min of contact time. On the basis of the results obtained from contact time studies, 240 min was taken as the equilibrium time in kinetic adsorption experiments. The percentage removal increased from 38, 51 and 60 to 71, 72 and 77% at 30, 40 and 50 C respectively. Rapid increase in percentage removal was observed in first 90 min which gradually increased till attainment of equilibrium. As the temperature increased from 30 to 50 C the amount adsorbed increased from 41.93 to 83.86 106 g, suggesting an endothermic nature of adsorption process. Similar trend was observed by Dogan and an et al., 2004). fellow researchers (Dog 3.2.5. Effect of concentration Initial dye concentration in the reaction mixture acts as a driving force for the uptake of adsorbate ions by the adsorbent in batch adsorption process. Study of concentration was carried out by varying the dye concentration from 1e10 106 M RHB at pH 3 with 0.06 g of powdered AM seeds (Fig. 2d). It was noted that as the dye concentration increased, the amount of dye adsorbed increased from 2.396, 5.99, 9.584 to 76.672, 79.068 and 91.048 106 g at 30, 40 and 50 C respectively (Kuo et al., 2008). Obtained results suggested adsorption process to be dependent on the initial adsorbate concentration up to some extent (Rafatullah et al., 2009). Favourability of adsorption process at higher temperature was also evident with increase in dye uptake at higher temperature. The enhancement in adsorption may be due to the increase in rate of diffusion of adsorbate molecules towards
Investigation of Langmuir and Freundlich equilibrium isotherms onto the experimental data obtained at optimum conditions was done to assess the fitness of experimental data to the tested models at 30, 40 and 50 C. A graph of 1/qe versus 1/Ce for the Langmuir isotherm was plotted to determine the isothermal parameters from the slopes (1/Qob) and intercepts (1/Qo) of the obtained graph. Similarly a graph was plotted between log qe versus log Ce to determine the Freundlich isothermal parameters. The linear plot resulted with the straight lines giving slope of 1/n and an intercept of Log Kf. The isothermal parameters obtained from the linear plots are presented in Table 1. Maximum monolayer coverage predicted by Langmuir isotherm model was found to be 3.61 105 mol g1 at 50 C. The values of adsorption intensity, b decreased from 7.07 to 4.46 104 L mol1 with an increase in temperature from 30 to 50 C. Similar trend was reported by Sampranpiboon and coauthors (Sampranpiboon et al., 2014). The values from RL lied from 0.93 to 0.90 at 30e50 C. The calculated values were greater than zero and less than one predicting the favourability of the isotherm to the experimental data. Freundlich constant, 1/n was found to be less than 1 at all the studied temperatures indicating favourability to the isotherm. Kf values related to adsorption capacity, were also found to increase with increase in temperature suggesting favourability of the process at higher temperatures. Fig. 3 compares the fitness of both the isotherms onto the experimental data. Both Langmuir and Freundlich fitted to the experimental data with R2 > 0.9. But on comparing the different error functions and closeness of R2 value to linearity, Langmuir isotherm model was found to be the best fit for the studied system. It was also evident from Table 2, that the experimental data was well described by Langmuir model with lower values of different error functions i.e. S.E, R.M.S.E, c2, SSE, SAE and ARE. Significance of the error functions lies in the fact that lower the magnitude of errors, greater will be the closeness of the modelled data to the experimental data and higher will be the suitability of the model for the system. As the data fitted quite well with the Langmuir isotherm, participation of homogenous active sites of the adsorbent was assumed. 3.4. Adsorption kinetics Adsorption kinetics for the RHB-AM system was evaluated by applying Pseudo first and second order kinetic models. Linear graphs of log qe-qt versus time and t/qt versus time were plotted for the first and second order kinetic models using Eqs. (13) and (14). Rate constant k1 and k2 were tabulated from the slopes of the first
Table 2 Pseudo first and second order kinetic model parameters and error analysis for RHB-AM adsorption system. Parameters
Pseudo 1st order
Temperature
30 C
40 C
50 C
30 C
40 C
50 C
0.0103 e 0.9643 0.0557 0.6310 6.0376 2.78 4.99 10.19
0.0089 e 0.9663 0.0348 0.9669 24.976 6.54 7.67 27.46
0.0081 e 0.9869 0.0325 1.1149 38.485 8.70 8.84 36.54
e 1.73 102 0.9945 0.0701 0.0438 0.0165 0.013 0.29 3.49
e 3.50 102 0.9969 0.0503 0.0461 0.0164 0.014 0.268 2.75
e 3.55 102 0.9957 0.0505 0.0722 0.0378 0.001 0.025 3.71
1
k1 (min ) k2 (g mg min1) R2 S.E. RMSE
c2 SSE SAE ARE
Pseudo 2nd order
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and second order plots respectively (Table 2). Kinetic study revealed that adsorption of RHB increased with an increase in time along with temperature. The rate of adsorption was quick for first 90 min and then the rate gradually increased until equilibrium was attained. Table 2 depicts the pseudo second order rate constant values which increased with increase in temperature showing favourability at higher temperatures. Moreover the values of correlation coefficients were higher than 0.99 and close to unity, affirming the fitness of the pseudo second order kinetic model. Additionally, both the models were compared and a graph was plotted between experimental and predicted qt values with contact time. It was evident from Fig. 4 that pseudo second order model fitted well with the experimental data. The graph indicated that the predicted data by the pseudo second order model was in good agreement with that of experimental values showing better simulation results. Error analysis of the obtained data for both kinetic models were carried out by subjecting to different functions (Table 2). Results confirmed the suitability of Pseudo second order kinetic model for the present system with higher R2 values and minimum S.E., RMSE, c2, SSE, SAE and ARE values on comparison with pseudo first order kinetic model. For better understating of the kinetics, the experimental data was applied to a mathematical treatment given by Boyed and his research team (Boyd et al., 1947). Indepth mechanism of adsorption process undergoing via film or particle diffusion was acquired by performing a linearity test which resulted in straight line passing through origin at 30 C indicating particle diffusion while the lines were away from origin at higher temperatures depicting film diffusion at high temperatures (Supplementary material. Fig. 1). 3.5. Adsorption thermodynamics In order to determine the spontaneity and nature of adsorption process, thermodynamic study was carried out for the RHB-AM system. Thermodynamic parameters were calculated by using equations (Eqs. (10)e(12)) which resulted to negative values of free energy and positive values of enthalpy and entropy for the system. Change in Gibb's free energy was found to be 28.27 kJ mol1 for the system which suggested the process to be spontaneous in nature. Whereas change in enthalpy and entropy was found to be 18.48 kJ mol1 and 149.99 J K1 mol1 respectively. Similar results have been reported by Ho and fellow researchers (Ho et al., 2005) for the removal of a dye using fern tree as a biosorbent. A positive value of enthalpy directed towards the endothermic nature of the adsorption process which was supported by an increase in adsorption at higher temperatures, while positive value of entropy showed the increase in randomness at the adsorbate-adsorbent
Fig. 4. Experimental and kinetic modelled data for RHB-AM seeds adsorption system.
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interface. This increase in randomness is attributed to the displacement of the water molecules by the dye ions during the adsorption process over the adsorbent (Vasu, 2008). 4. Conclusion Evaluation of adsorption capacity of Argemone mexicana seeds was done through batch mode studies. SEM, EDS, FTIR, XRD characterization of the adsorbent showed the rough surface with presence of different functional groups favourable for adsorption process. Effect of different parameters during batch studies resulted in maximum removal of RHB at optimum pH 3 with 0.06 g of adsorbent. Higher percentage of removal was attained at equilibrium for the studied concentration. Also the election of the best suited isotherm was made after comparing different error functions such as S.E., RMSE, c2, SAE, SSE and ARE along with correlation coefficients (R2). Langmuir model was found to be the best fit for the experimental data with R2 > 0.9 and minimum values of error functions at all the temperatures studied. Kinetic model supported the results obtained by isothermal analysis following pseudo second order model showing chemisorption during the adsorption process. Thermodynamic model suggested the process to be spontaneous and endothermic in nature with Gibb's free energy as 28.27 kJ mol1. The adsorption studies therefore established Argemone mexicana seeds to be cost effective and efficient adsorbent for removal of textile dye from waste water. Appendix A. Supplementary data Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.jenvman.2016.09.036. References Al-Qodah, Z., 2000. Adsorption of dyes using shale oil ash. Water Res. 34, 4295e4303. http://dx.doi.org/10.1016/S0043-1354(00)00196-2. Ali, S.Z., Athar, M., Salman, M., Din, M.I., 2011. Simultaneous removal of Pb (II), Cd (II) and Cu (II) from aqueous solutions by adsorption on Triticum aestivum-a green approach. Hydrol. Curr. Res. 2 http://dx.doi.org/10.4172/2157-7587.1000118. Bapat, S.A., Jaspal, D.K., 2016. Parthenium hysterophorus: novel adsorbent for the removal of heavy metals and dyes. Global J. Environ. Sci. Manage 2, 135e144. http://dx.doi.org/10.7508/gjesm.2016.02.004. Boyd, G.E., Adamson, A.W., Myers Jr., L.S., 1947. The exchange adsorption of ions from aqueous solutions by organic zeolites. II. Kinetics1. J. Am. Chem. Soc. 69, 2836e2848. € an, M., Alkan, M., Türkyilmaz, A., Ozdemir, Dog Y., 2004. Kinetics and mechanism of removal of methylene blue by adsorption onto perlite. J. Hazard. Mater 109, 141e148. http://dx.doi.org/10.1016/j.jhazmat.2004.03.003. Ekpete, O.A., Horsfall, M.J.N.R., 2011. Preparation and characterization of activated carbon derived from fluted pumpkin stem waste (Telfairia occidentalis Hook F). Res. J. Chem. Sci. 1, 10e17. Foo, K.Y., Hameed, B.H., 2010. Insights into the modeling of adsorption isotherm systems. Chem. Eng. J. 156, 2e10. http://dx.doi.org/10.1016/j.cej.2009.09.013. Freundlich, H.M.F., 1906. Over the adsorption in solution. J. Phys. Chem. 57, 385e470. , E., M neanu, A., Ghiris¸an, A., Ilea, P., 2015. Kinetic modeling and error Gîlca aica analysis for zinc removal on a weak base anion exchange resin. Desalin. Water Treat. 1e9. http://dx.doi.org/10.1080/19443994.2015.1101018. Guo, Y., Zhao, J., Zhang, H., Yang, S., Qi, J., Wang, Z., Xu, H., 2005. Use of rice huskbased porous carbon for adsorption of Rhodamine B from aqueous solutions. Dyes Pigments 66, 123e128. http://dx.doi.org/10.1016/j.dyepig.2004.09.014. Gupta, V.K., Khamparia, S., Tyagi, I., Jaspal, D., Malviya, A., 2015. Decolorization of mixture of dyes: a critical review. Global J. Environ. Sci. Manage 1, 71e94. http://dx.doi.org/10.7508/gjesm.2015.01. Gupta, V., Agarwal, A., Singh, M.K., 2015. Belpatra (aegel marmelos) bark powder as an adsorbent for the color removal of textile dye “torque blue”. Int. J. Sci. Eng. Technol. 4, 56e60. Ho, Y.S., Porter, J.F., McKay, G., 2002. Equilibrium isotherm studies for the sorption of divalent metal ions onto peat: copper, nickel and lead single component systems. Water Air Soil Poll. 141, 1e33. http://dx.doi.org/10.1023/A: 1021304828010. Ho, Y.S., Chiang, T.H., Hsueh, Y.M., 2005. Removal of basic dye from aqueous solution using tree fern as a biosorbent. Process Biochem. 40, 119e124. http://dx.doi.org/ 10.1016/j.procbio.2003.11.035.
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Please cite this article in press as: Khamparia, S., Jaspal, D., Investigation of adsorption of Rhodamine B onto a natural adsorbent Argemone mexicana, Journal of Environmental Management (2016), http://dx.doi.org/10.1016/j.jenvman.2016.09.036