Crustacean derived calcium phosphate systems: Application in defluoridation of drinking water in East African rift valley

This research published by Elsevier B.V., 2018Calcium phosphate adsorbents, derived from prawns and crabs shell biomass wastes have been developed using wet chemistry and low temperature treatment. The adsorbents were characterized by X-ray diffractometry and Fourier transform infrared spectroscopy. Batch adsorption test were carried out to investigate their effectiveness in adsorption of fluoride from ground and surface waters. Adsorption capacities were compared with bone char and synthetic hydroxyapatite (CCHA). Results indicate that prawns derived adsorbent (PHA) formed hexagonal structure with phases identifiable with hydroxyapatite while crabs based adsorbent (CHA) formed predominantly monoclinic structure with crystalline phase characteristic of brushite. Vibrational analysis and kinetic studies predicted defluoridation occurred mainly by ion exchange and ion adsorption mechanisms. Defluoridation capacity of the adsorbents was found to be superior compared to bone char and CCHA. CHA was the most effective with efficiencies above 92% and highest capacity of 13.6 mg/g in field water with fluoride concentration of 5–70 mg/L. PHA had highest capacity of 8.5 mg/g which was still better than 2.6 mg/g recorded by CCHA and bone char. Adsorption was best described by pseudo 2nd order kinetics. The findings indicate that crustacean derived calcium phosphate systems have better potential for defluoridation than traditional bone char and synthetic systems

Study of crustacean biomass wastes for water defluoridation

A Dissertation Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Materials and Energy Science and Engineering of the Nelson Mandela African Institution of Science and TechnologyHigh levels of fluoride (F-) in community drinking water supply is recognized as one of the major public health problems. Until now no efficient and affordable F- removal technology exists in many regions. This research explored crustacean biomass waste for development of adsorbent for F- removal. Chitin and calcium carbonate components in crabs and prawns shells were selected for development of three adsorbents: chitosan, calcium phosphate systems (CAPs) and composite of chitosan and CAPs. All the adsorbents were characterized using XRD and FT-IR. Chitosan was obtained by deacetylation of chitin and then modified by cross-linking with glutaraldehyde and protonated using hydrochloric acid. Interaction of F- with the modified chitosan was studied using batch adsorption test and theoretical Density Function Theory (DFT) calculations. Results indicated that computed parameters matched well with experimental results and confirmed that electropositivity of hydrogen atoms influenced F- adsorption by electrostatic attraction. Best performance was achieved in low F- polluted water (≤ 5 mg/l) with adsorption capacity 1.6 mg/g. Calcium recovered from demineralization of shells was precipitated into CAPs using ammonium dihyhrogen phosphate. Crab shell produced dicalcium phosphate dehydrate or brushite (CaHPO4.2H2O) while prawns shell gave hydroxyapatite (Ca5(PO4)6.(OH)2) form of CAPs. Brushite was more effective in F- adsorption with efficiencies above 92% and highest capacity of 13.6 mg/g in field water with fluoride concentration of 5-70 mg/l compared to prawns shell hydroxyapatite with capacity of 8.5 mg/g. FT-IR analysis and kinetic studies predicted defluoridation occurred by ion exchange and ion adsorption mechanisms, described by pseudo 2nd order kinetics. Failure to remove microbes was identified as limitations of the CAPs. Composite of chitosan and brushite was thus developed to address the problem. Analysis with XRD and FT-IR confirmed transformation of brushite phases into hydroxyapatite and formation hybrid composite. Highest F- adsorption efficiency (88%) was achieved for water with F- ≤ 10 mg/l. Microbial count significantly reduced in treated water and final pH was within the acceptable range of 6-9. Adsorbate–absorbent interaction was best described by pseudo 2nd order kinetics

Study of interaction of chitosan with Fluoride

This research article published by Biointerface Research in Applied Chemistry, Volume 8, Issue 3, 2018Interaction of chitosan with fluoride (F- ) has been studied using experimental and computational methods. Chitosan was extracted from prawns shells and modified by cross-linking with glutaraldehyde and protonation using concentrated hydrochloric acid. Modified and pristine chitosan were characterized using XRD, FT-IR and UV–Vis. Adsorption of Ffrom solution was determined using ion selective electrode meter. β-D-glucosamine (β-GlcN) monomer was used to model chitosan. Optimization of molecular geometry, harmonic vibrations analysis and interaction energies with fluoride were computed using DFT with B3LYP/ 6-311**G (d,p) level of theory. Electronic absorption spectra of β-GlcN was calculated by Time Dependent–DFT using the same level of theory and compared with UVVIS spectra of pristine chitosan. Firefly 8.1.1 program package was used for all computations. Computed IR frequencies were assigned using Chemcraft visualization software and compared with experimental FT-IR spectra of chitosan and literature values. Equilibrium geometry calculated was compared with X-ray diffraction. Results indicated that computed parameters matched well with experimental results and confirmed that electropositivity hydrogen atoms of amine and its adjacent hydroxyl groups in chitosan influenced the adsorption of fluoride from solution by electrostatic attraction also, that protonation of the amine group increased adsorption capacity significantly