Melanoidin removal in multi-oxidant supplemented microwave system: optimization of operating conditions using response

surface methodology and cost estimation

Binay Kumar Tripathy1, Inigo Johnson1, Mathava Kumar1*

1
Department of Civil Engineering, Indian Institute of Technology Madras, Chennai, Tamil Nadu, India - 600036

*Corresponding author: Email: mathav@iitm.ac.in; Phone: +91- 44-22574267

Supplementary material

Table S1: Experimental variables and their designed range used in CCD

Factor -α -1 0 +1 +α

PS (mg/L) 0 1250 2500 3750 5000

H2O2 (mg/L) 0 1500 3000 4500 6000

pH 2 4.5 7 9.5 12

Melanoidin Conc. 500 2875 5250 7625 10000

(mg/L as COD)

Table S2. Annova for Melanoidin removal

Melanoidin removal (mg/L/min)

Source Co. Eff df MS F-value p-value

Model 4 44.79 66.59 < 0.0001

Intercept 11.37 1

A-PS 0.8764 1 18.43 27.70 < 0.0001

B-H2O2 1.13 1 30.69 45.64 < 0.0001

C-Mel 2.28 1 124.66 185.34 < 0.0001

D-pH 0.4735 1 5.38 8 < 0.0089

Residual 26 0.6726

Lack of Fit 20 0.8608 19.07 0.001

Pure Error 6 0.0451

Table S3. Comparison of predicted and observed values for the dependent variables

Response Slope Intercept R2

Colour reduction (cubic) 1.0752 2.7985 0.8693

Colour reduction (quadratic) 0.7325 21.983 0.9146

Melanoidin removal rate 1.0964 3.8689 0.9872

Melanoidin Preparation

The prepared melanoidin solution was extracted against 95% acetone, concentrated and was dried at 60°C for 24 hours. The obtained
solid was weighed and then was used to prepare standard melanoidin solution. Concentrations upto 250mg/L were used to prepare the
calibration standard for melanoidin with measuring absorbance at a wavelength of 200-800 nm as shown in Fig S1. Absorbance at 320
nm was used for further assays since higher concentrations of hydrogen peroxide is known to interfere at wavelengths below 300 nm.

Melanoidin Spectra
1.2
(a)

0.8
Absorbance

0.6

0.4

0.2

0
200 300 400 500 600 700 800
Wavelength (nm)
 1
(b)
0.9
f(x) = 0.01 x
0.8 R² = 1 f(x) = 0.56 ln(x) − 1.95
R² = 0.98

0.7
0.6
Absorbance

0.5
0.4
0.3
0.2
0.1
0
0 20 40 60 80 100 120 140 160
Concentration (mg/L)

Fig S1. (a) Melanoidin absorbance spectrum and (b) Calibration curve for melanoidin concentration at an absorbance of 320 nm

100 ppm Linear (100 ppm) 500 ppm Linear (500 ppm)
(a) 1000 ppm Linear (1000 ppm) 2500 ppm Linear (2500 ppm)
6 5000 ppm Linear (5000 ppm)

5 f(x)
f(x) == −− 0.01
0.08
0.06
0.04
0.17 xx ++ 5.34
5.25
R²
R² == 0.98
0.95
0.97
1
0.94

4
ln (C)

0
0 5 10 15 20 25
Time (min)
(b) 100 ppm Linear (100 ppm) 500 ppm Linear (500 ppm)
1000 ppm Linear (1000 ppm) 2500 ppm Linear (2500 ppm)
5000 ppm Linear (5000 ppm)
0.1

0.09 f(x) = 0 x + 0.01

R² = 0.98
0.08

0.07

0.06
1/C (mg-1)

0.05

0.04

0.03

0.02 f(x) = 0 x + 0
R²
f(x)==0.98
0x+0
0.01
R²
f(x)==0.98
0x+0
0 f(x)
R² ==10 x + 0
0 R² = 0.99 5 10 15 20 25

Time (min)

Fig S2. Rate constant for MW-PS system in (a) Pseudo-first order and (b) second-order kinetic model

100 ppm Linear (100 ppm) 500 ppm

(a) Linear (500 ppm) 1000 ppm Linear (1000 ppm)
3000 ppm Linear (3000 ppm) 6000 ppm
Linear (6000 ppm)
5.4

f(x) = − 0
0.02
0.01
x + x5.36
+ 5.36
5.3 R² = 0.93
0.99
0.97

5.2
ln (C)

5.1

4.9

4.8
0 5 10 15 20 25

Time (min)
 100 ppm Linear (100 ppm) 500 ppm
(b) Linear (500 ppm) 1000 ppm Linear (1000 ppm)
3000 ppm Linear (3000 ppm) 6000 ppm
Linear (6000 ppm)

0.01

f(x) = 0 x + 0
R² = 0.99
0.01
f(x) = 0 x + 0
R² = 0.99
0.01
f(x) = 0 x + 0
R² = 0.98
1/Co (mg-1)

0.01 f(x) = 0 x + 0
R² = 0.93

f(x) = 0 x + 0
0.01 R² = 0.93

0
0 5 10 15 20 25

Time (min)

Fig S3. Rate constant for MW- H2O2 system in (a) Pseudo first-order and (b) second-order kinetic model

(a) 0.12
H2O2 PS
0.1

0.08
K (min-1)

0.06

0.04

0.02

0
0 500 1000 1500 2000 2500 3000
Oxidant dosage (mg/L)
 (b) 1.6

1.4 H2O2 PS

1.2

K (Lmg-1min-1)
1

0.8

0.6

0.4

0.2

0
0 500 1000 1500 2000 2500 3000
Oxidant dosage (mg/L)

Fig S4. Change in rate constant in MW-PS and MW-H2O2 system with oxidant dosage in (a) pseudo first- order and (b) second-order
kinetics

(a) 6
6000 ppm PS+100 ppm H2O2 Linear (6000 ppm PS+100 ppm H2O2)
3000 ppm PS,500 ppm H2O2 Linear (3000 ppm PS,500 ppm H2O2)
1000 ppm PS,1000 ppm H2O2 Linear (1000 ppm PS,1000 ppm H2O2)
0.12
0.19
f(x) = − 0.02 5.51
0.25 x + 5.49
0.05 5.48
5.45
R²
R² == 1
0.95
0.97
0.89
5

4
ln C (min-1)

0
0 5 10 15 20 25

Time (min)
 6000 ppm PS,100 ppm H2O2 Linear (6000 ppm PS,100 ppm H2O2)
(b) 3000 ppm PS, 500 ppm H2O2 Linear (3000 ppm PS, 500 ppm H2O2)
1000 ppm PS,1000 ppm H2O2 Linear (1000 ppm PS,1000 ppm H2O2)
0.3

0.25 f(x) = 0.01 x + 0

R² = 1

0.2
1/Co (Lmg-1min-1 )

0.15

0.1
f(x) = 0 x + 0
R² = 0.98

0.05

f(x) = 0 x + 0
R² = 0.93
0 f(x) == 0
0 xx ++ 0
0 f(x)
R²
0 5 10 15 20 25
R² == 0.98
0.98
Time (min)

Fig S5. Rate constant for MW-PS/H2O2 system in (a) Pseudo first-order (b) Second-order kinetic model

Fig. S6. Calibration curve for OH• concentration

Fig. S7. Error analysis of cubic model of CCD (a) Actual vs Predicted values, (b) Relative error percentage or each run
20
120
18
100
16
14 f(x) = x
(%)

80 R² = 1
Value

12
Error

10
60
Predicted

8
Relative

6
40
4
20
2
0
0 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31
10 20 30 40 50 60 70 80 90 100
Actual
Run No.
Value