Synthesized bioadsorbent from fish scale for chromium (III) removal

Journal Pre-proof Synthesized Bioadsorbent from Fish Scale for Chromium (III) Removal Firomsa Teshale, R. Karthikeyan, Omprakash Sahu

PII:

S0968-4328(19)30297-5

DOI:

https://doi.org/10.1016/j.micron.2019.102817

Reference:

JMIC 102817

To appear in:

Micron

Received Date:

14 September 2019

Revised Date:

24 December 2019

Accepted Date:

24 December 2019

Please cite this article as: Teshale F, Karthikeyan R, Sahu O, Synthesized Bioadsorbent from Fish Scale for Chromium (III) Removal, Micron (2019), doi: https://doi.org/10.1016/j.micron.2019.102817

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Synthesized Bioadsorbent from Fish Scale for Chromium (III) Removal

Firomsa Teshale, R. Karthikeyan and Omprakash Sahu

Department of Chemical Engineering, KiOT, Wollo University Ethiopia Department of Chemical and BioEngineering, AAiT, Addis Ababa, Ethiopia

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Corresponding author Email:[email protected]; Tel:+919752610957

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Graphical-Abstract

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Department of Chemical and Petroleum Engineering, UIE, Chandigarh University, Mohali, India

Highlights Achieving the permissible norm and avoiding the unpleasant odour

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Bioadsorption preparation form waste fish scales

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Characterisation of chemical synethised bioadsorbents before and after experiments

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Deduction of hazardous metal ions from industrial effluent

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Significant role of operating parameters on pollutant removal

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Abstract:

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Presence of heavy metal in industrial wastewater is hazardous to the surrounding environment. Biosorption of heavy metal is an effective technology for the treatment of industrial wastewater.

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This research work has been carried out on removal of chromium (III) metal ions by employing waste fish scales as bioadsorbent. A batch adsorption process was carried out with different

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adsorbent dosage, solution pH and contact time. The results show the highest 99.7518 % chromium (III) metal ions at bioadsorbent dosage 0.8g, pH of the solution 5 and contact time 90 min, initial concentration 150mg/l chromium ion. The adsorption isotherms data fitted well with the Langmuir isotherm model with R2= 0.9998, qmax= 18.3486 mg/g, and RL= 0.00007325. As

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well as pseudo-first and second kinetics model was also analyzed for the description of adsorption and found to be well fitted (R2=1) for adsorption kinetics. The surface properties activated fish scales and chromium loaded fish scale were investigated by scanning electron microscopy, X-ray spectroscopy, Fourier-transform infrared spectroscopy, and thermal analysis and agree with outcomes.

Keywords: Bioadsorbent; Effluent; Harmful; Metal ions; Toxic waste Introduction: Leather processing has emerged as an important economic activity in a developing country (Ethiopia) (Wakeford, et al., 2016). The leather goods market value forecast worldwide from 2018 to 2021 was nearly 239.78 to 271.21 billion USD (TSP-Report, 2018). It means increasing 10.47% per annum, which required a large amount of leather to fulfill the world demand.

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Tannery industries are among those industries, which required a large quantity of water for

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processing and discharge 90% of water as effluent. Nearly 40-45 liters of fresh water were required to process one kilogram of raw leather from hide or skin (Sathish et al., 2016). The

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wastewater from tannery industries loaded with a high percentage of a color compound, various

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organic and inorganic substances, toxic metallic compounds and different types of tanning materials (Chowdhury et al.,2015). Among all these pollutants, chromium that available in

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tannery effluent has significant health concerns due to high-ranking oxidizing properties (Magoling et al., 2017). Chromium is present in a trivalent and hexavalent form in an aqueous

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phase and allowable limit is 0.1mg/L for surface water and 0.05mg/L for potable water, according to world health organization (WHO, 2011). Including to lathering industry other industries like electroplating, textile and dye manufacturing, metal plating, and battery production were also contributes chromium ion in the range of 0.5mg/L to 270 mg/L

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(Kamsonlian and Shukla, 2013). Hence, it’s necessary to remove the chromium from tannery industries wastewater to make the environment safe and clean (Ghaedi and Mosallanejad, 2018). Various treatment methods have been suggested to reduce the level of chromium from

wastewater in literature like chemical precipitation (Gheju and Balcu, 2011), coagulation (Golbaz et al., 2014), electrocoagulation (Verma et al., 2013); solvent extraction (Vander

Hoogerstraete et al., 2013); electrolysis (Sadyrbaeva, 2016), membrane separation (Mohammed, K. and Sahu, 2015); ion–exchange (Kumar et al., 2017) and biological (Gutiérrez-Corona et al., 2016) etc. These methods are found to be less effective on chromium metal ion elimination, due to technical terms. As compared to all; the adsorption process has been suggested as effective in terms of economic and operation (Kobielska et al., 2018). Adsorption process has been used to different types of different industrial effluent like dye industries (Vikrant et al., 2018), fertilizer

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(Melia et al., 2017); distillery (Ioannou et al., 2015); food (Qasim and Mane, 2013);

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pharmaceutical (Deegan et al., 2011) as well as heavy metal (Visa, 2016). The commercial activated carbons used in adsorption process make expensive treatment, for this reason, an

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alternative like bioadsorbent are focusing nowadays (Enniya et al., 2018). However different

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types of bioadsorbent like Spirulina sp. (Rezaei,2016); Sugarcane bagasse (Ullah et al., 2013); Macrocystis pyrifera and Undaria pinnatifida (Cazón et al., 2012); Ulva sp. (Vijayaraghavan and

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Joshi, 2014); Orange peel (Lugo-Lugo et al., 2012); olive stone (Blazquez, et al., 2011); microalgae (Kim et al., 2011); vineyard pruning (Karaoğlu et al., 2010) has been reported for

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chromium (III) ions removal. Bioadsorbents are biomass matter, which consists a range of functional groups like amino, carboxyl, hydroxyl and phosphate on the cell wall are magnetize the heavy metals on the process (Carolin et al., 2017; Adio et al., 2019). The biomass material can be effortlessly reprocessed and dispose of after regeneration. Nearly 143.8 million tonnes of

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fish consumed per annum, which produced 50% as waste (Hollander et al., 2019). So afford has been made to develop low-cost bioadsorbent from waste fish scale for chromium (III) removal in order to meet permissible limits standards as well as to avoid unsafe disposal of waste fish scale.

The main aim of this research work is to remove chromium (III) metal ions from synthetic solution by waste fish scale as bioadsorbent. The experiment conducts in batch mode and process parameters were optimized by using surface response methodology. Bioadsorbent was characterized by scanning electron microscopy (SEM), X-ray spectroscopy (XRD), Fouriertransform infrared spectroscopy (FTIR) and thermal analysis (DTA-DTG-TG). Adsorption isotherms and kinetics models pseudo-first and second order were also studied.

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Material and methods:

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Material:

Synethic solution: A stock synthetic solution was prepared with 3.77gram of chromium sulfate

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(Cr2 (SO4)3) in one liter of deionized water.

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Bioadsorbent: The waste scale (fish) was arranged from Arbaminch Lake Ethiopia. Chemicals: A laboratory grade sulphuric acid, sodium hydroxide, calcium hydroxide and

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chromium sulphate purchase from chemical supplier Addis Ababa (Ethiopia). Methods:

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Preparation of adsorbent: To prepare the bioadsorbent, arranged fish scale was washed and soaked for 24 hrs with normal water, and subsequently cleaned with ionized water to remove the impurities. Washed fish scales were kept in sundry for 48 hrs and open-air oven at 65oC for 24 hrs to make moisture free and crispy (Kongsri et al., 2013). The dried scales were converted into

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a fine powder with help of mechanical grinder (Chen et al., 2010). The powder was sieved through octagon sieve and maintained the fraction size range of 125 to 200µm. The chemical activation was carried out with 10 gram of fish scale powder mixed with 150 ml 0.1M sulphuric acid solution (acid activation) for 2.5 hrs at 100 rpm rotary shaker in room temperature, similar procedures were followed with sodium hydroxide (base activation). The chemically treated

suspension was transferred to a vacuum filter to separate the liquid part (Iqba et al., 2011). Collected semi slurry was washed repeatedly using distilled water until a neutral pH solution was attained. Afterward, the sample was dried at room temperature for 2 hrs and on the oven at 80oC. The dried sample was kept in poly bags until used (Iqbal et al., 2011). The steps fallow to prepared bioadsorbent from waste fish scales is shown in Fig. 1. Experimental design:

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A response surface methodology (RSM) was applied for experiment design on chromium

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removal in the batch process. In this research, adsorbent dosage, a range of 0.4g; 0.8g and 1g pH range of pH 3; 5 and 8 and contact time range 30; 90 and 120 mins, considered as a factor for

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three levels, which mentioned in Table 1. The response (Y) indicates the chromium removal in

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percentage and factor coded in X1(bioadsorbent dosage); X2 (pH) and X3 (Contact time). The mathematical relationship between response and variables can be presented in an Eq. (1) and in

Y  f ( x1 , x2 , x3 .........xn )

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the form of a second order polynomial (Witek-Krowiak et al., 2014): (1)

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Where Y is the response of the system, and xi is the variables of action called factors. The independent variables are continuous and controllable by experiments with negligible errors has been assumed for an equation. The results of the Y (response) in an experiment by adsorption

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were measured by design matrix listed in Table 2. The percentage of chromium reduction efficiency was calculated using the Eq. (2).

(2) Experiment-setup:

The adsorption process was carried out in batch mode to examine removal efficiency of activated fish scales (AFS) at room temperature. The experimental setup is presented in Fig.2. The initial pH of the solution between pH 3, 5 and 8 was adjusted by adding 0.1M hydrochloric acid (HCl) and sodium hydroxide (NaOH) solution. A known volume 100ml of synthetic chromium solution was taken in 250 ml beaker and measure amount of activated bioadsorbent 0.4g, 0.8g, and 1 g was added. The conical flask (sample and bioadsorbent) was kept in magnetic stirrer plate and

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mixed at speed of 200 rpm for 30min; 90min and 150 min interval of time. After the adsorption

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process, separation of the sorbent and solutions was carried out by 90 mm diameter filter paper via vacuum filtration unit (Ding et al., 2012). The filtrate was analyzed for residual Cr (III) using

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atomic absorption spectrophotometer.

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Analytical analysis:

The concentrations of chromium metal ions were determined using atomic absorption

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spectrophotometer. FT-IR spectroscopy was used to identify the functional groups in the fish scales biosorbent. FTIR spectra of the biosorbent before, after chemically modification and after

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biosorption of Cr (III) loaded were recorded in the range 4000-400 cm-1 using spectrum 65FTIR (Perkin Elmer) KBr pellets. X-ray diffraction spectra were recorded, using a step size of 10o, step time of 1s and 2θ range of 10o to 70o. The samples powder, particles retained in the sieve with 150µm was used for characterization and analysis. Scanning Electron Microscope coupled

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with Energy-dispersive X-ray spectrometer (SEM - EDX) (JSM – 7100F), was employed to determine the surface morphology of the fish scales and to determine its elemental composition (Nielsen et al., 2015). The TGA/DTA was performed on differential thermal analyzer of type (SII 6300 EXSTAR) to estimate the complete decomposition temperature of fish scales sample

by heating it from 25oC to 1100oC with 10oC/min of constant heating rate and under nitrogen flow as an inert gas. Result and discussion: Characterization of Fish Scales Fourier Transform Infrared spectrum Analysis The FTIR spectroscopy is an important analytical technique which identifies the vibration

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characteristics of chemical functional groups in a fragment. The FTIR curves of raw fish

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scales, modified fish scale and chromium (III) loaded fish scales are shown in Fig. 3 (a), (b) and (c). The raw fish scales, the stretching broadband at 3365cm-1 corresponds to O-H groups.

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The region between 3000 and 2800cm-1 exhibited medium peak, indicates the C-H stretching

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vibrations –CH3 and -CH2 functional groups (Ribeiro et al., 2015). Distinct strong peaks observed between 1715 and 1630 cm-1 characterize carbonyl groups strong stretching. From

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1300-1470 cm-1 there was the deformation stretching of CH, CH3, and CH2 functional groups as a well medium peak at 1030 cm-1, due to C–O group. Some other peaks of P-O were also

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recorded at 750 cm-1 and 550 cm-1 due to PO43- groups, those are characteristic of the inorganic phase (Nadeem et al., 2008). Changes in intensity and shift in the position of the peaks could be observed in FT-IR spectrum after Cr (III) adsorption on modified fish scales (Fig. 3 (c)). The shifting of the peak at 1660 to 1655 cm-1indicates that the involvement of

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C=O/C=C in the adsorption process. The strong peak of raw biosorbent at 1030cm-1 (Fig. 3(a) ranging from 1100 to 1020 cm-1 shifted to 1025cm1. This suggested the participation of C-O group in the binding of Cr (III). The deformation stretching peak between 1300 -1407 cm-1 (Fig. 3 (a)) was changed and PO43- medium peaks are changed to small peak (Fig. 3(c)). The result indicates that the hydroxyl and carbonyl groups are the main functional groups on the

surface of raw fish scales involved in chromium (III) uptake to the modified fish scale. The main functional groups present on the surface of synthesized fish scales were hydroxyl, carbonyl, and phosphate. These observations have good agreement with the FTIR data for Tilapia fish scales used to remove hazardous azo dye reported in the literature (Zhu et al., 2013). The FT-IR analysis, the possible mechanism of adsorption of chromium (III) ion on the fish scale may be due to physical adsorption, ion exchange, chemical reaction with surface

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sites, and complexation with functional groups. This result also agree with the removal of

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chromium (III) by other bioadsorbent like rice husk and saw dust of Eucalyptus camaldulensis

et al., 2014) and pine bark (Arim et al., 2018) etc.

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X-ray Diffraction (XRD) Analysis

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(Kanwal et al., 2012); olive-mill waste (Bautista-Toledo et al., 2014); graphene oxide (Yang

Generally X-ray diffraction phase/composition identification will distinguish the major, minor,

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and trace compounds present in a sample. X-ray diffraction was conducted for the surfaces of raw fish scales; synthesized scale and chromium loaded scale which shown in Fig. 4 (a); (b) and

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(c). The XRD patterns with a 2θ scan from 20◦ to 70◦. The peaks at 2θ of 25.96o, 28.66o 31.66o, 32.05o, 39.71o, 44.22o, and 49.66o correspond to protein and calcium. The Bragg equation d（Å） = λ/2sinθ (λ = 1.54 Å), minimum values (d) of spacing were 0.3432, 0.3115, 0.2827, 0.2792, 0.2270, and 0.1836nm calculated. The broad peaks of the XRD pattern indicate that the

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scale has low crystallinity which corresponds to an amorphous property for chromium loaded fish scale. It may be due to the significant interaction between chromium ions and calcium. This peaks are agreed with result peaked at 2θ of 25.9o, 31.9o, 39.8o, 47.2o, 49.3o, and 53.2o correspond to d spacing of 0.343, 0.281, 0.226, 0.193, 0.185, and 0.172 nm, reported by (Chakraborty et al., 2011) and peaked at 25.8o, 31.8o, 39.6o, 47.2o, 49.3o, and 53.1o corresponding

to d spacing of 0.345, 0.281, 0.227, 0.192, 0.184, and 0.172 nm (Torres et al., 2008). The chemical composition of raw fish scale is mention in Table 3. Scanning electron Micrograph: The surface structure of the activated fish scale and after adsorption scale was analyzed under a scanning electron microscope. The scanning electron micrographs of the activated fish scale (AFS) before and after the Cr (III) adsorption at 1000× magnification is shown in Fig. 5 (a) and

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(b), respectively. It can be seen honeycomb-like structures or open pores are available on the

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surface of the activated fish scale. The open pores are actively participated during the process to entrap the metal ion on their surface. These honeycomb cages formed due to inorganic material

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calcium and oxygen and organic material protein present in fish scale (Stevens and Batlokwa,

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2017). After adsorption fish scale layers have different from the native bioadsorbent. The surfaces are damaged, rough and irregular structure due to metal ion trapped on the pores. Hence

Thermal analysis:

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it confirms that physical adsorption occurred on the surface of AFS (Onwordi et al., 2019).

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The thermal gravimetric analysis (TGA), differential thermal analysis (DTA) and differential thermal gravimetry (DTG) curves of activated fish scales (AFS) and chromium loaded fish scale (CLFS) absorbent in an oxidizing atmosphere is shown in Fig. 6 (a) and (b), respectively. The DTA trace shows dehydration and volatilization (removal of volatiles) of the sample up to 300oC

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losing weight of 1.4% for activated fish scales and 0.04% for chromium loaded fish scale bioadsorbent. These losses occurred due to the moisture and less unstable material present on both bioadsorbent samples (Pati et al., 2010). The peak rate of weight loss 0.7mg/min was seen at temperature Tmax 780oC for activated fish scale and 105.2 µg at Tmax 716oC for chromium loaded fish scales. Oxidizing of solids was found exothermic, 2000J/g heat evolution for

activated fish scale at 780oC. The weight loss between 300oC to 796oC was 44.6% for AFS and 39.65% weight loss up-to 765oC temperature for chromium loaded fish scale, may be due to total loss of CO2 contained in bioadsorbent (Zhao et al., 2018). Oxidation seems to be completed at a temperature of 1108oC for AFS and 1110oC for CLFS due to decomposition and burning of organic components in both bioadsorbent almost bring to an end. At 1108oC the 54.51% weight of activated fish scales ash and 59.91% weight at 1110oC of chromium loaded fish scale as ash

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found to remain. Thus chromium loaded fish scales contains more inorganic material as

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compared to the activated fish scales (Mondal et al., 2012). Statistical Analysis

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The process was analyzed for process parameters adsorbent dosage (X1), pH (X2), and contact

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time (X3) on adsorption of chromium (III) (Y) by using design expert 7. The laboratory experiment was done at a constant initial concentration (150mg/L) of pollutant at 200rpm

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shaking speed and room temperature. The experiment results analysis was carried out by using analysis of variance of the quadratic regression model for analysis significant model

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term (Srivastava et al., 2015). To determine whether or not the quadratic model is significant, it was required to perform an analysis of variance (ANOVA), mention Table 4. According to analysis model terms, probability factor (Prob. > F) values less than 0.05 are considered significant. In this work, the model terms X2, X3, X22, X32, and X1X2 are a significant model,

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while X1 is least significant terms. The values greater than 0.1000 indicates the model terms X1X3 and X2X3 are not significant. The quality of the model developed was evaluated based on the correlation coefficient (R2) and standard deviation. The "Pred R2" of 0.4716 is reasonable agreement with “Adj R2" of 0.6665, which is less than 0.2, this might be due to signal to disturbance ratio. A ratio greater than 4 is desirable; here the ratio of 8.411 indicates

an adequate signal. Therefore, this model can be used to navigate or direct the design space. The regression coefficient and the corresponding 95% confidence interval (CI) high and low were mention in Table 5. From designed experimental data, the quadratic polynomial model equation for chromium (III)

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adsorption using a modified fish scale is mention in of finial coded factor on Eq. (3):

(3)

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The generated data were also investigated for normality of the residuals and relationship

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between the actual and predicted values of response (Y), shown in Fig.7. The normal probability plot indicates that the residuals observed value is more close to normal

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distribution. These demonstrate that the experiment points in plots are fit to the straight line and the quadratic polynomial model satisfies the assumptions of analysis of variance (Mohan

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et al., 2015).

Effect of functioning parameters:

The results of different functioning parameters are presented in Fig. 8 (a), (b) and (c). An initial pH of the solution is the most important parameter affecting metal ion adsorption. The

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effect of pH on chromium absorption process was carried out at constant dosage 0.70g; time 90 min; initial Cr (III) concentration 150 mg/L and different range of pH 3 to pH 8. It was found that maximum chromium removal occurred at pH 5.8, which shown in Fig. 8 (a). The result also shows that with an increase or decrease or near to neutral pH of a solution, adsorption capacities were found to be low due to weak electrostatic force of attraction between the oppositely charged adsorbate and adsorbent (Subramaniam and Ponnusamy,

2015; Liang et al., 2018). At pH 5.8 to 6.3 rates of adsorption chromium was constant beyond this pH the efficiency of biosorbent was decreased due to increase in pH that causes a formation of soluble hydroxyl complexes and decreases adhering capacity of metal ions (Nazir et al., 2019). Almost 99.92% chromium (IV) removal was observed with Artocarpus heterophyllus peel as bioadsorbent at pH 2; 50 mg/L initial concentration, 0.3 g of biosorbent at 100 rpm, and 35 °C experiment temperature (Saranya et al., 2018).

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The effects of adsorbent dosage on the chromium (III) removal at room temperature

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was investigated by varying the amount of sorbent from 0.4g to 1g in a stock solution having Cr (III) ion concentration 150mg/l at pH 5.5 and time 90 mins. The result presented in Fig.8

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(b). It can be observed that chromium percentage removal increases with increase in

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bioadsorbent dosage from 0.4g to 0.8g. This might be due to the availability of more adsorbent sites and enhanced the free surface area (Aman et al., 2018). Addition of activated

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fish scale beyond 0.8g the percentage removal of chromium was more or less near to constant. This may be due to particulate interaction such as agglomeration or equilibrium between

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chromium ions and the solid phase was reached (Huang et al., 2016; Anastopoulos et al., 2019). Hence the positive correlation between adsorbent dose and chromium removal can be related to increasing the adsorbent surface area and the availability of more adsorption sites (Wu et al., 2017). Similarly 5mg/L of fish scale bioadsorbent dose was found to be suitable to

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remove 94.2% of chromium at initial concentration 50mg/L chromium; pH 5 and experiment time 5 hours (Prabu et al., 2012). The effect of contact time on chromium reduction was carried at different time interval

30 min to 150 min. An experiment conducted at constant dosage 0.70g and pH 5.50; initial concentration of 150 mg/L at room temperature (21oC), which shown in Fig.8(c). It observed that

removal efficiency sharply increase with an increase in time from 30 min to 80 min and then attains equilibrium at 110 min. This is probably due to the availability of larger surface area on activated fish scale surface, which prolonged contact between the adsorbent surface and adsorbate (metal ions) in solution (Ooi et al., 2017). The active sites of adsorbent were exhausted when equilibrium achieved the rate of uptake is controlled by the rate at which the adsorbate is transported from the exterior to the interior sites of the sorbent particles (Gogoi et al., 2018).

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Lower adsorption efficiency rate afterward 110min may be due to challenges for Cr3+ ions to

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occupying the leftover vacant surface sites of adsorbents in bulk solution (Zare-Dorabei et al., 2016). Author reported 99% Cr (III) removal was noted at 14 hrs with eggshell and 30 min with

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marble powder as bioadsorbent respectively (Elabbas et al., 2016).

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Interaction of process variables on chromium (III) Uptake

The interaction among the process variables was analyzed with surface response methodology

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and plotted three-dimensional graphs to optimize the chromium uptake. The 3D plotted and contour plot is presented in Fig.9 (a); (b) and (c).

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Interaction of adsorbent dosage and solution pH The response (Y) of chromium (III) ions removal efficiency as a function of adsorbent dosage and solution pH, are represented as three dimensional and contour plot in Fig.9(a). The graph ascribes that with an increase in pH 3 of solution and adsorbent dosage 0.4mg/l, the

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percentage of chromium removal efficiency increases to 96.43 % at invariable time 90.0 min. This efficiency increases up to 99.95 % chromium ions when sorbent dosage 0.8 mg/l and pH 5 increased at contact time. The increases in percentage removal of Cr3+ ion attributes to increase in an adsorbent dose that offered more surface area and completely consume the active site by an adsorbent at low pH (Daoud et al., 2015). Usually, as pH increases at the

lower level of adsorbent dosage and as adsorbent increases at the low level of pH gives a positive effect on the chromium removal efficiency (Liu et al., 2018). Interaction of adsorbent dosage and contact time The interaction of adsorbent dosage and contact time on chromium elimination efficiency were shown as three dimension and contour plots in Fig. 9(b). The results reveal that at a definite contact time 90 to 120 min, a performance of chromium removal increased and reached to peak

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beyond 120 min of contact time performance decreases. However, increasing the dose beyond

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0.8g, there is gradual decreases removal efficiency of chromium ions by activated fish scale. The reason may be due sorbent particulate agglomeration, which rejects active site for adsorption

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surface area (Hu et al., 2016). Hence, maximum percentage removal of chromium (III) ion using

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activated fish scale was achieved at a medium value of dosage and higher contact time 110120min. The plots indicate maximum adsorption 99.985% Cr3+ ion take place between 0.7 to 0.8

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g dosage and 110 to 120 min of contact time. Hence it’s confirmed that as contact time increase lower adsorbent dosage gives positive effects on the efficiency of chromium removal and

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decreases in efficiency at a higher dose to lower contact time (Hashem et al., 2019). Interaction of solution pH and contact time The interaction of solution pH and contact time on chromium ions reduction is plotted on Fig. 9(c). The graph illustrated that contact time increases at the lower level of pH and pH value

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increases at the low level of contact time have a significant impact on chromium (III) ions removal efficiency. It can be observed that as contact time increases up to 110 min, removal efficiency increased, additional of contact time beyond 110 min attains the stability and then decrease the performance of chromium removal. In the same way, when pH value increase from pH 3 to pH 5.8 chromium (III) removal efficiency increases, beyond the pH 5.8 value of

removal efficiency decreased. This might be due to dissociation of the biomass surface and solution chemistry of the heavy metals, which strongly affect with pH (Samuel et al., 2015). For this reason, when contact time increase at lower of pH and pH of the solution increases at lower contact time has beneficial effects on the removal efficiency of chromium (III) ions with activated fish scale (AFS) (Batool et al., 2019). Adsorption Isotherm

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To examine the distribution of a solute between liquid and solid phase different mathematical

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relation such as standard Langmuir and Freundlich models has been suggested in the literature (Guyo et al., 2015). In this work, the isotherm studies were performed at initial concentration

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150mg/l, pH 5; adsorbent dosage 0.8g; contact time 2.5 hrs; shaking speed 200 rpm and

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temperature ± 25oC. The biosorption equilibrium uptake capacity for each sample was

(4)

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calculated according to mass balance on the ions expressed in the Eq. (4).

Where V is the sample volume (L), C0 is the initial ion concentration (mg/L), Ce is the equilibrium or final ion concentration (mg/L), M is the biomass dry weight (g), and q e is the biomass biosorption equilibrium ions uptake capacity (mg/g).

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Langmuir and Freundlich isotherms models were employed to describe the equilibrium between adsorbed ions on the sorbent (qe, q) and ions in the solution (Ce, q) in this research work.

Langmuir Isotherm Model: The Langmuir isotherm is valid for monolayer adsorption onto a surface containing a finite number of identical sites. This describes quantitatively the formation of a monolayer adsorbate on the outer surface of the adsorbent, and after that no further adsorption takes place. Based upon these assumptions, Langmuir derived in linear from represented, mention

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in Eq.(5):

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(5)

Where, Ce, qe, qmax and KL representing the equilibrium concentration of chromium (III),

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adsorption capacity of activated fish scales at equilibrium, the maximum capacity of

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bioadsorbent and Langmuir constant respectively. The qmax and RL in the Langmuir isotherm can be determined by plotting (Ce/qe) versus (Ce), which shown in Fig.10 (a). The essential

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characteristics of Langmuir isotherm can be expressed by the dimensionless constant called

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equilibrium parameter RL, that mention in Eq. (6):

(6)

Where Co is the initial concentration of metal ion (mg/l), RL is a dimensionless equilibrium parameter. The characteristics of the RL value indicate the nature of biosorption: - unfavorable

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(RL> 1), linear (RL = 1), favorable (0 < RL< 1) and irreversible (RL = 0) (Reddi et al., 2017). Freundlich isotherm model

The Freundlich isotherm model is describing the adsorption of solutes from an aqueous phase to a solid surface. This isotherm model assumes that the uptake of metal ions occurs on a heterogeneous surface by multilayer adsorption and that the amount of adsorbate adsorbed increases infinitely with an increase in concentration (Karimifard et al., 2016). Freundlich

adsorption isotherm is the relationship between the amounts adsorbed per unit mass of adsorbent, qe, and the concentration of Cr (III) at equilibrium, Ce. The linear form of the logarithmic equation for Freundlich isotherm is written in Eq. (7)

(7)

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Where Kf and n are the Freundlich constants, Kf and n are the indicators of the adsorption

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capacity and adsorption intensity respectively. In this case, the plot of log C e vs log qe was employed to generate the intercept value of Kf and the slope of = 1/ n. Freundlich biosorption

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models for the removal of chromium (III) on the activated surface is shown in Fig. 10 (b). The calculated qmax, KL, and correlation coefficients [R2] for the Langmuir equation and RL

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values and Kf, 1/n, and [R2] for the Freundlich equation at constant temperatures are mentions

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in Table 6. The regression coefficient (R2) for Langmuir and Freundlich isotherms was 0.9998, and 0.9599, respectively. Therefore, the result of correlation coefficient R2

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comparison of Langmuir and Freundlich isotherm models, the Langmuir adsorption isotherm is the fit model for chromium (III) ion adsorption onto the modified fish scale sorbent. The Langmuir isotherm (R2 = 0.9998) fits the experimental data very well, this describes that homogeneous distribution of active sites onto AFS surface. The adsorbent, Langmuir and

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Freundlich adsorption isotherms were plotted and obtained correlation coefficients. It can be concluded that adsorption of ions studied on prepared adsorbent gives correlation coefficient higher than 0.9998 follows by Langmuir isotherm (Xu et al., 2015).

Adsorption kinetics model The rate kinetics of Cr (III) adsorption by the modified fish scales adsorbent was analyzed using the pseudo-first-order and second-order rate kinetics model. The kinetics of chromium

(III) adsorption was studied from the time versus percentage of removal curves (mg/g), shown in Fig. 11 (a). The relationship time and amount of chromium adsorbed per adsorbent (mg/g) which is used to analyze adsorption kinetics model at initial concentration 150mg/l, pH 5, adsorbent dosage 0.8g, contact time varies from 30 min to 130min. Pseudo-first-order Kinetic Model In order to investigate the mechanism of adsorption, the pseudo-first-order equations were

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used to test experimental data of initial concentrations. The pseudo-first-order kinetic

(8)

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equation is presented in Eq (8):

Where, qe and qt are the adsorption capacities at equilibrium and time t respectively (mg/g) and

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into Eq (9):

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k1 is the rate constant of pseudo-first-order adsorption (mn-1). The equation can be rearranged

(9)

The values of log (qe - qt) were linearly correlated with t. The plot of log (qe - qt) vs. t should

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give a linear relationship. The first-order rate constant k1 (1/min) and the equilibrium capacity qe can be obtained from the slope and intercept, respectively, which shown in Fig. 11 (b). The observed rate constant for the removal of Cr (III) ions on AFS for Pseudo-first-order kinetic model was described in Table 7. Pseudo-second-order Kinetic Model The pseudo-second-order adsorption kinetic is expressed in Eq (10):

(10) For the boundary conditions t=0 to t=t and qt= 0 and qt=qt, the integrated form of the above equation will be written in Eq. (11).

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The Eq.(11) has been rearranged to obtain a linear form of Eq (12):

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(11)

(12)

-p

Where qe and qt are the sorption capacity at equilibrium and time t (mg/g), respectively, k 2 is the rate constant of the pseudo-second-order sorption (g/mg min). The k2 and qe are found

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from the intercept and slope of t/qt versus t linear plot such that qe = 1/slope and k2 =

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slope2/intercept. The second order kinetic plot is shown in Fig. 11 (c). The comparison of experimental sorption capacities (qexp) and the predicted values (qcal, K1, K2,

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and R2) from the pseudo first order and second order are given in Table 7. According to results pseudo-second-order kinetic equations having high R2 (R2= 1) values and sorption capacity qe (mg/g) as well as calculated and experimental value is near to same value (Asfaram et al., 2015). Hence second-order kinetics models were considered as the fit equations for bioadsorption of

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chromium (III) ion using activated fish scales. Comparatively, study: Present research work for chromium (III) ions removal was compared with other research findings, which is mention in Table 8. Form the all the result it has been concluding that activated fish scale was found to be superior to eliminate the chromium (III) ion from tannery wastewater. In this research work pH is near to natural (pH=5); other research removed at the highly acidic solution (pH 2 to pH 4). The treatment time is 90 mins,

but others experimental time is almost more than 120 min. The efficiency 99.75% was also highest among all the finding till time. Conclusion Removal of chromium (III) form of tannery wastewater solutions was possible with waste fish scale as bioadsorbent. The result indicates that activated fish scales have great potential to removal Cr(III) from tannery wastewater. An experimental output confirms that using

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activated fish scales 99.7518% chromium metal ion can be achieved at adsorbent dosage 0.8g,

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pH 5, and contact time 90 min and initial concentration 150mg/l. The adsorption process of Cr(III) depends on pH and contact time and justified the removal efficiency increases till

-p

equilibrium. The FTIR analysis describes that the adsorbent fish scales contain carboxyl,

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amine, and hydroxyl functional groups. Based on the FTIR spectra, these functional groups are participating on adsorption of chromium on activated fish scales surface. The X-ray

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diffraction analysis indicates that fish scales have properties of an amorphous, these results agree with scanning electron micrograph and thermal analysis. The adsorption kinetics studies

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indicated at equilibrium attained at 130min of contact between the activated fish scale and chromium solution and followed by pseudo-second-order. The Langmuir and Freundlich isotherm were studied and Langmuir isotherms showed a better fit to the process R2= 0.9998. In future, it can study real tannery wastewater and regeneration of bioadsorbent. With the

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above result it can be concluding that employing waste fish scale for chromium removal is best alternative to minimise the pollution from surrounding. Acknowledgment: Authors acknowledge to Environment chair, School of Chemical and Bio Engineering, Addis Ababa Institute of Technology, Addis Ababa Ethiopia for providing lab facilities.

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Preparation

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from

waste

fish

scales

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Fig.2: Experimental arrangement of adsorption process for chromium removal

of ro -p re lP ur na Jo Fig.3: Fourier Transform Infrared spectrum Analysis of (a) raw fish scales; (b) chemical modified scales and (c) chromium loaded scales

of ro -p re lP ur na Jo Fig.4: X-ray diffraction of (a) raw fish scales; (b) activated scales and (c) chromium loaded scale

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Fig.5: Scanning electron micrograph analysis of fish scales (a) before adsorption process and (b) after adsorption process

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Fig.6: DTA-DTG-TG curve of (a) activated fish scale and (b) chromium loaded fish scale

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lP

re

Fig.7: actual and predicted values of chromium removal

of ro -p re lP ur na Jo Fig.8: Effect of different functioning parameters on (a) initial pH; (b) dosage of bioadsorbent and (c) contact time

of ro -p re lP ur na

Jo

Fig. 9(a): Interaction three dimension plot and contour plot of adsorbent dosage and solution pH

of ro -p re lP ur na

Jo

Fig. 9(b): Interaction three dimension plot and contour plot of adsorbent dosage and contact time

of ro -p re lP ur na

Jo

Fig. 9(c): Interaction three dimension plot and contour plot of solution pH and contact time

of ro -p re lP ur na Jo

Fig. 10: Adsorption isotherms of chromium (a) Langmuir and (b) Freundlich models

of ro -p re lP ur na Jo Fig.11: Adsorption kinetics model (a) relationship time and amount of chromium adsorbed per adsorbent (mg/g) (b) Pseudo-first-order kinetic model and (c) Pseudo-second-order kinetic model

of

ro

-p

re

lP

ur na

Jo

Table 1: Variables designed for the adsorption process.

Range and level variables

Adsorbent dosage(g) (A)

0.4

0.8

pH(B)

3

5

Contact time(min)(C)

30

90

₊α

of

α

1 8

Jo

ur na

lP

re

-p

−α

ro

Independent variables

150

Table 2: Full factorial design used for the chromium removal by adsorption process S.No

X1: Dosage(g) X2: pH

X3: Contact Y:Response time (min) Efficiency (%)

0.4

3 30

93.45

2

0.8

3 30

92.14

3 4 5 6 7 8 9 10 11 12 13 14

1 0.4 0.8 1 0.4 0.8 1 0.4 0.8 1 0.4 0.8

3 5 5 5 8 8 8 3 3 3 5 5

30 30 30 30 30 30 30 90 90 90 90 90

94.99 96.87 97.96 98.79 97.43 94.01 92.13 97.68 99.42 98.41 98.19 99.75

15 16 17 18 19 20 21 22 23 24 25 26 27

1 0.4 0.8 1 0.4 0.8 1 0.4 0.8 1 0.4 0.8 1

5 8 8 8 3 3 3 5 5 5 8 8 8

90 90 90 90 150 150 150 150 150 150 150 150 150

ro

-p

re lP

ur na

Jo

of

1

99.10 99.52 99.53 99.67 93.60 97.06 97.65 99.27 99.37 98.90 98.23 98.39 98.60

Table 3: Chemical composition of waste fish scale Chemical composition

Symbol

Percentage

1

Oxygen

O

37.9

2

Chlorine

Cl

35.4

3

Copper

Cu

8.7

4

Lead

Pb

6.2

5

Mercury

Hg

5.1

6

Zinc

Zn

7

Moisture

H2O

of

S.No

Jo

ur na

lP

re

-p

ro

5.9 1.8

Table 4: Analysis of variance (ANOVA) for response surface quadratic model Sum of

DF Mean square

pvalue

Prob>F

Model

114.7

9

12.74

6.85

0.0004

Significant

X1-Dosage

0.46

1

0.46

0.24

0.6275

Less significant

X2- Ph

12.21

1

12.21

6.49

0.0208

Significant

X3 -Cont. 27.87 time X12 0.036

2

27.87

14.81

0.0013

1

0.036

0.019

0.8922

of

Squares

F value

X22

25.14

1

25.14

13.36

0.0020

Significant

X32

35.44

1

35.44

18.84

0.004

Significant

X1X2

10.90

1

10.90

5.79

0.0278

Significant

X1X3

3.81

1

3.81

X2X3

1.81

1

1.81

Residual

31.99

17

Cor Total

146.69

26

Jo

re

-p

ro

Significant

2.02

0.1731

Insignificant

0.96

0.3410

In significant

lP

ur na

1.88

Significant

Table 5: Regression coefficient and the corresponding 95% CI High and Low

Standard

95% Cl

Low

High

Estimate

intercept

100.59

1

0.76

98.98

102.20

X1-Dosage

0.16

1

0.32

-0.52

0.84

1.04

X2-Ph

0.83

1

0.33

0.14

1.52

1.03

X3-Contact time X12

1.26

1

0.33

0.57

1.95

1.02

-0.088

1

0.64

-1.44

1.27

1.04

X22

-2.15

1

0.59

-3.39

-0.91

1.01

X32

-2.43

1

0.56

-3.61

-1.25

1.00

X1X2

-0.93

1

0.39

-1.74

-0.11

1.02

X1X3

0.55

1

0.39

-0.27

1.37

1.02

X2X3

0.39

1

0.39

-0.44

1.22

1.01

lP ur na Jo

VIF

-p

of

Factor

re

DF Error

95% CL

ro

Coefficient

Table 6: Constant values of Langmuir and Freundlich isotherm model

Freundlich parameters kf = 14.9107

KL= 91.001L/mg

1/n=0.008

3

RL = 0.00007325

-

4

R2=0.9998

R2= 0.9599

Jo

ur na

lP

re

-p

ro

2

of

Isotherms/Constant Langmuir parameters qmax= 18.3486mg/g 1

Table 7: Adsorption kinetic model parameters for chromium adsorption Pseudo 2nd order kinetic model

Initial Cr(III) qe(mg/g) ions (cal) concentration (mg/l) 18.8323

qe(mg/g)

K2

(exp)

(g/mg.min)

18.70116 0.0627

R2

qe(cal)

1

16.5576

1st

-p re lP ur na Jo

order

K1(min-1)

0.0953

ro

150mg/l

Pseudo model

kinetic R2

of

Kinetics

0.827

Table 8: Different bioadsorbent used for chromium (III) metal ions S.No

Bioadsorbent

Optimum parameters

1

Fish scale

IC= 250mg/50mL; 96% CT=120 min; D=20 g

Magsi et al., 2019

2

Chitosan

CT= 24hrs

Eladlani 2018

3

Jatropha curcas pH=5.5; D=8g/L; CT= 22.88mg/g L. 60mins

Gonçalves et al., 2017

4

Spirulina sp

Rezaei, et al., 2016

5

Residual brewing industry

6

Garden grass

IC=50mg/L; 90% (19.4 mg/g) Sulaymon et al., CT=180min; D=2g; pH= 2014 o 4; Temp=21 C

7

Ulva sp.

pH=4.5

8

Sugarcane bagasse

NA

9

Macrocystis pH=4 pyrifera and Undaria pinnatifida

10

Olive stone

70%

43.3%

re

lP

na

Vineyard pruning

12

Sargassum alga

et

al.,

Ferraz et al., 2015

-p

from IC=390 mg/L

Author

ro of

IC= 50mg/L; CT= 120 90.91 mg/g min; D= 0.1g; pH=5; Temp= 25oC

ur

Jo 11

Efficiency

2.89 mmol/g

Vijayaraghavan. and Joshi, 2014

73%

Ullah et al, 2013

0.77mmol/g and Cazón et al., 2012 0.74mmole/g

pH =4

5.18 mmole/g

Blázquez 2011

et

al.,

pH=4.2

12.45 mg/g

Karaoğlu 2010

et

al.,

sp. IC= 4.29mg/L; pH=3.5; 2.04 mg/g Temp=30oC

57

Silva et al., 2010

Waste fish scale IC=150 mg/L; CT= 90 99.75% min; D= 0.8g; pH =5; Temp= 21oC

Present research

Jo

ur

na

lP

re

-p

ro of

13

58