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ABSTRACT Applications of statistical optimization techniques like artificial neural networks were rarely applied for biosorption systems. Statistically based experimental designs like response surface methodology (Artificial neural networks) are more efficient, as variables are tested simultaneously. Moreover, the interactions between different variables can be estimated. The present study aims to evaluate the efficiency of zinc sorption on gallus domesticus using Artificial intelligence techniques. Four process parameters (initial concentrations, pH, Biosorbent dosage and biosorbents particle size) served as inputs to the neural network models, and percentage biosorption of zinc served as a single output of each model. Genetic algorithms were used to optimize the input space of the neural network models to monitor the zinc sorption on Gallus domesticus. About 0.1g of gallus domesticus was found to be enough to remove 80.51% of zinc of 20mg/l from 30 ml aqueous solution in 30 min. RSM (ANN) were carried out to obtain response surface model describing zinc biosorption at various process conditions: initial concentration (20100), pH (2-6), Biosorbent dosage (0.1-0.5) and biosorbent particle size (75-212). INTRODUCTION Heavy metals are released into aquatic ecosystems as by-products from various industrial processes and acid-mine drainage residues. They are highly toxic in ionic form as well as compound form. They are soluble in water and may be rapidly absorbed by the living organisms. Zinc is one of the heavy metal enters the environment as the result of mining,

purifying of zinc, lead, and cadmium ores, steel production, coal burning, and burning of wastes. Most of the zinc in lakes or rivers settles at the bottom. However, a small amount may remain either dissolved in water or as fine suspended particles, dissolved zinc in water may increase as the acidity of water. The high levels of zinc affect human reproduction or cause birth defect, skin irritation. A wide range of work had been reviewed for removal of toxic metals, by various methods such as chemical precipitation, ion exchange, Reverse osmosis, Electro dialysis and adsorption.Biosorption is potentially an attractive technology for treatment of wastewater for retaining heavy metals from dilute solutions. Literature shows that the many biosorbents present in the nature have great capacity for removal of heavy metals. Biosrptions greatly varies with temperature, pH, adsorbent dosage, temperature, size of biosorbent and substrate dosage. Response surface methodology combines statistical experimental designs and empirical model building by regression for the purpose of process or product optimization. An artificial neural network (ANN) is a mathematical representation of the neurological functioning of a brain. A typical artificial neural network has an input layer, one or more hidden layer, and an output layer. The neurons in the hidden layer, which are linked to the neurons in the input and output layers by adjustable weights, enable the network to compute complex associations between the input and output variables. The inputs of each neuron in the hidden and output layers are summed and the resulting summation is processed by an activation function (Nagata et al. 2003). Artificial intelligence techniques can be effectively integrated to create a powerful tool for process modeling and optimization. The present study aims to monitor the zinc sorption on gallus domesticus by generating response surface plots using ANN technique at various pH, initial concentrations, biosorbent dosage and biosorbent particle size. MATERIAL AND METHODS Preparation of biosorbent

Hen egg shells were collected from MS Ramaiah Engineering hostels, MSRIT, Bangalore, Karnataka, India. Shells were washed with deionized water several times to remove dirt particles. The dried egg shells powders of 75-212 μm particle size were used as biosorbent without any pretreatment for zinc adsorption. Chemical Analytical grades of ZnSO4 7H2O, HCl and NaOH were purchased from Merck, India. Zinc ions were prepared by dissolving its corresponding sulphate salt in distilled water. The pH of solutions was adjusted with 0.1 N HCl and NaOH. Biosorption experiments Biosorption experiments were performed in a rotary shaker at 180 rpm using 250 ml Erlenmeyer flasks containing 30 ml of different zinc concentrations. After one hour of contact (according to the preliminary sorption dynamics tests), with 0.1 g egg shell powder biomass, equilibrium was reached and the reaction mixture was centrifuged for 5 min. The metal content in the supernatant was determined using Atomic Absorption Spectrophotometer (GBC Avanta Ver 1.32, Australia) after filtering the adsorbent with whatman filter paper. The pH of the solution was adjusted by using 0.1 N HCl and 0.1 N NaOH. (Kalyani et al. 2009). ARTIFICIAL NEURAL NETWORK The first step in implementing a neural network modeling approach is to design the topology of the network. The choice of design parameters for a neural network is thus often the result of empirical rules combined with trial and error. The configuration of the neural networks developed in this work (a 4-10-1 structure: four input neurons-ten neurons in one hidden layer-one output neuron) was determined after brief experimentation. The data set comprising 19 experimental runs reported was split into two categories: a training set comprising 15 experimental runs was used to optimize the

weights of the neural networks and a validation set comprising 3 experimental runs was used to evaluate their predictive capability. Because empirical models like neural networks do not extrapolate data well, data for network training should be selected carefully if the best results are to be achieved. In this study the data selected for network training covered the lower and upper bounds of the two output neurons (Nagata et al. 2003). MATLAB software (Version 6.5, MathWorks, Inc, USA) used for this study. Table 1: Experimental data fed to Matlab software for performing Artificial Neural Networks based on preliminary studies S. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Biosorbant Concentration (g/100ml) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.3 0.4 0.5 0.1 0.1 0.1 0.1 0.1 pH 2 3 4 5 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Metal Concentration (mg/l) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 40 60 80 100 Particle size (µm) 145 145 145 145 145 75 105 150 212 145 145 145 145 145 145 145 145 145 145 % Biosorption 29.12 52.14 77.14 81.41 87.31 86.51 85.54 80.12 77.45 86.51 87.56 89.78 92.74 95.24 86.33 84.45 83.20 82.02 73.41

Response surface plots showing % adsorption at various concentrations, biosorbant dosage, pH and initial concentration. The contour plots given in Figures 1-6 show the relative effects of any two variables when the concentration of the third variable is maintained at a constant level. These constant levels are the central levels of each variable taken in the respective ranges considered. In all cases, the contours were more or less spherical and there were no saddle points. An idea of the approximate ranges of the three factors, which could result in maximum synthesis of pectinase under these conditions, was obtained from the contour plots. The coordinates of the central point

within the highest contour level in each of these figures will correspond to the optimum concentrations of the respective components. Fig 1a shows the relative effect of biosorbent concentration and zinc concentration on percentage adsorption of zinc. The contours in this figure are plotted for a constant adsorbent particle size (145 µm) and pH (6). The highest contour level in this figure corresponds to 80% biosorption. The relative effect of Zinc concentration and adsorbant particle size is considered at a constant biosorbent concentration (0.1 g) and pH (6) (Fig. 1b). At a constant metal concentration (20 mg/ml) and particle size (145 µm), Fig. 1c describes the effect of pH and Biosorption concentration on percentage Biosorption. Fig 1d shows the effect of particle size and pH on percentage Biosorption of zinc at constant zinc concentration (20 mg/ml) and biosorbent concentration (0.1 g). Fig 1e and Fig 1f describes the effect of ‘particle size and biosorbent concentration’ & ‘biosorbent concentration and zinc concentration’ on percentage Biosorption at constant ‘pH (6) and zinc concentration (20 mg/ml)’ & ‘particle size (145 µm) and pH (6)’.







Fig 1: Response surface plots, drawn using trainlm function in Matlab software At a constant corn concentration of 18.5 kg/m3, Fig. 3 gives the synthesis of pectinase as a function of ammonium sulphate and glucose levels. In this case, the coordinates of the central point within the contour level of 1.65 U corresponds to about kg/m3 of ammonium sulphate and about 31 kg/m3 of glucose. CONCLUSION This work found that neural networks provided better fits to experimental data than Conventional biosorption equilibrium studies (Like Langumuir, Freundlich) The input space of a neural network model can be optimized using genetic algorithms which do not require the objective function to be continuous or differentiable. The hybrid neural network-genetic algorithm approach described in this work serves as a viable alternative to the standard approach for the modeling of biosorption processes.

REFERENCES 1. Nagata Yuko, Chu KH Optimization of a fermentation medium using neural networks and genetic algorithms. Biotechnology Letters 25: 1837–1842(2003). 2. Kalyani1, G. Babu Rao, B. Vijaya Saradhi ,Prasanna Kumar Y Equilibrium and kinetic studies on biosorption of zinc onto gallus domesticus shell powder, ARPN Journal of Engineering and Applied Sciences 4(1):39-49(2009) 3. S. Mahesh kumar, G M. Madhu, M. A. Lourdu Antony Raj, Adsorption isotherms and brekthrouh curves for phenol on granular activated carbon in fixed beds, Indian Chem. Engg., Section A, Vol., 4 234-239, 2004. 4. S.R. Nair, T. Panda (1997) Statistical optimization of medium components for improved synthesis of pectinase by Aspergillus niger, Bioprocess Engineering 16:169-173

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