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. 2023 May 22;13(1):8267.
doi: 10.1038/s41598-023-34523-y.

Flax fiber based semicarbazide biosorbent for removal of Cr(VI) and Alizarin Red S dye from wastewater

Magda A Akl  1 , Abdelrahman S El-Zeny  2 , Mohamed A Hashem  2 , El-Sayed R H El-Gharkawy  2 , Aya G Mostafa  2
Affiliations

Flax fiber based semicarbazide biosorbent for removal of Cr(VI) and Alizarin Red S dye from wastewater

Magda A Akl et al. Sci Rep. .

Abstract

In the present study, flax fiber based semicarbazide biosorbent was prepared in two successive steps. In the first step, flax fibers were oxidized using potassium periodate (KIO4) to yield diadehyde cellulose (DAC). Dialdehyde cellulose was, then, refluxed with semicarbazide.HCl to produce the semicarbazide functionalized dialdehyde cellulose (DAC@SC). The prepared DAC@SC biosorbent was characterized using Brunauer, Emmett and Teller (BET) and N2 adsorption isotherm, point of zero charge (pHPZC), elemental analysis (C:H:N), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analyses. The DAC@SC biosorbent was applied for the removal of the hexavalent chromium (Cr(VI)) ions and the alizarin red S (ARS) anionic dye (individually and in mixture). Experimental variables such as temperature, pH, and concentrations were optimized in detail. The monolayer adsorption capacities from the Langmuir isotherm model were 97.4 mg/g and 18.84 for Cr(VI) and ARS, respectively. The adsorption kinetics of DAC@SC indicated that the adsorption process fit PSO kinetic model. The obtained negative values of ΔG and ΔH indicated that the adsorption of Cr(VI) and ARS onto DAC@SC is a spontaneous and exothermic process. The DAC@SC biocomposite was successfully applied for the removal of Cr(VI) and ARS from synthetic effluents and real wastewater samples with a recovery (R, %) more than 90%. The prepared DAC@SC was regenerated using 0.1 M K2CO3 eluent. The plausible adsorption mechanism of Cr(VI) and ARS onto the surface of DAC@SC biocomposite was elucidated.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Figure 1
Figure 1
(a) Alizarin red S (ARS), (b) hexavalent chromium, Cr(VI).
Figure 2
Figure 2
(a) Filtrate of 0.25 M hydroxylamine after stirring for 2.5 h with DAC; (b) after titration with 0.1 M NaOH.
Figure 3
Figure 3
Synthesis of DAC@SC biocomposite.
Figure 4
Figure 4
Optical images of (a) Native flax fibers, (b) oxidized flax fibers (DAC), (c) Semicarbazide modified flax fibers (DAC@SC), (d) DAC@SC-ARS, (e) DAC@SC-Cr(VI), (f) regenerated DAC@SC.
Figure 5
Figure 5
SEM of (a) native flax fiber, (b) oxidized flax fiber, and (c) DAC@SC biocomposite.
Figure 6
Figure 6
Transmission electron micrograph (TEM) of a cross section of DAC@SC composite.
Figure 7
Figure 7
IR spectra of (a) native flax fiber, (b) oxidized flax fiber, (c) DAC@SC, (d.1) DAC@SC-Cr(VI), and (d.2) DAC@SC-ARS.
Figure 8
Figure 8
1H NMR of (a) DAC and (b) DAC@SC biocomposite.
Figure 9
Figure 9
XRD patterns of flax, oxidized flax and DAC@SC samples.
Figure 10
Figure 10
Thermal analysis of (a) DAC and (b) DAC@SC composite.
Figure 11
Figure 11
Effect of pH on adsorption of (a) Cr(VI) and (b) ARS (conditions: 0.1 g of DAC@SC in 50 mL of the 100 mg/L Cr(VI) solution. 0.15 g of DAC@SC in 50 mL of the 100 mg/L ARS aqueous solution at 25 °C for 2 h).
Figure 12
Figure 12
Effect of sorbent dose on adsorption of (a) Cr(VI) and (b) ARS(conditions: 50 mL aqueous solution of 200 mg/L for Cr(VI) solution and 100 mg/L for ARS solution at 25 °C for 2 h at pH 2).
Figure 13
Figure 13
Effect of sorbent dose on adsorption of (a) Cr(VI) and (b) ARS (conditions: 0.1 g of DAC@SC for Cr(VI) and 0.15 g of DAC@SC for ARS were taken at pH 2 for 2 h in range 50–350 ppm for Cr(VI) and 25–400 ppm for ARS).
Figure 14
Figure 14
Biosorption isotherms by DAC@SC: (a) Langmuir isotherm model for Cr(VI), (b) Langmuir isotherm model for ARS, (c) Freundlich isotherm model for Cr(VI), (d) Freundlich isotherm model for ARS, (e) DR isotherm model for Cr(VI), and (f) D-R isotherm model for ARS.
Figure 15
Figure 15
Effect of oscillation time on adsorption of (a) Cr(VI) (conditions: 0.1 g of DAC@SC, 50 mL of 200 mg/L Cr(VI), Temp.: 25 °C, time: 30–140 min). (b) ARS (conditions: 0.15 g DAC@SC, 50 mL of 100 mg/L of ARS, Temp.: 25 °C and time: 15–180 min).
Figure 16
Figure 16
Adsorption kinetics by DAC@SC: (a) Pseudo 1st order for Cr(VI), (b) Pseudo 1st order for ARS, (c) Pseudo 2nd order for Cr(VI), (d) Pseudo 2nd order for ARS, (e) IPD model for Cr(VI)and (f) IPD model for ARS.
Figure 17
Figure 17
Plot of ln KC vs (1/T) absolute temperature for the adsorption of (a) Cr(VI); (b) ARS.
Figure 18
Figure 18
Effect of ionic strength on adsorption of: (a) Cr(VI); (b) ARS.
Figure 19
Figure 19
Optical image of (a) Cr(VI) solution before and after adsorption, (b) ARS solution before and after adsorption, (c) mixture of ARS and Cr(VI) solution before and after adsorption.
Figure 20
Figure 20
UV spectra of (a) of Cr (VI) before adsorption, (b) ARS before adsorption (c) UV spectra of mixture of Cr (VI) and ARS before and after adsorption by DAC@SC at different time intervals.
Figure 21
Figure 21
Plausible mechanism of biosorption of (a) Cr(VI) ions and (b) ARS onto DAC@SC.
Figure 22
Figure 22
Synthesis of DAC@SC and its use for biosorption of Cr(VI) and ARS.
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