Heavy metals from mining sites can contribute to adverse health and environmental issues. Conventional liming practice depletes natural limestone deposits. Blood cockle shell (BCS) and palm kernel shell (PKS) calcination produced alkaline ash to immobilize heavy metals in soil. This study investigates the acid neutralizing capacity (ANC) of calcined BCS and PKS composites. BCS and PKS composites were prepared at various weight ratios (i.e. 1:0, 1:1, 1:5, 1:10, and 0:1) and were combusted for 1 hour at 400°C and 900°C, respectively. BCS and PKS composites were determined by its yield, pH, and ANC. The combustion characteristics for composites was conducted using thermogravimetric analysis (TGA). Elemental analysis was conducted using X-ray fluorescence (XRF) spectroscopy. Fourier transform infra-red (FTIR) was conducted for functional groups analysis. Ash content of composites increased when the portion of PKS feedstock is decreased. Increasing combustion temperature from 400°C to 900°C reduced the ash contents. The pH of raw and combusted composite (at 400°C) decreased as the portion of PKS feedstock is increased. Calcined composites at 900°C have slightly different pH value except for 0:1 sample. ANC value increased as PKS portion in composites reduced. Higher content of calcium oxide (CaO) in the composites increased the ANC value.
The potential of Pleurotus ostreatus spent mushroom compost (PSMC) as a green biosorbent for nickel (II) biosorption was investigated in this study. A novel approach of using the half-saturation concentration of biosorbent to rapidly determine the uptake, kinetics and mechanism of biosorption was employed together with cost per unit uptake analysis to determine the potential of this biosorbent. Fifty per cent nickel (II) biosorption was obtained at a half-saturation constant of 0.7 g biosorbent concentration, initial pH in the range of 4-8, 10 min contact time, 50 mL 50 mg/L nickel (II) initial concentration. The experimental data were well fitted with the Langmuir isotherm model and the maximum nickel (II) biosorption was 3.04 mg/g. The results corresponded well to a second pseudo order kinetic model with the coefficient of determination value of 0.9999. Based on FTIR analysis, the general alkyl, hydroxyl or amino, aliphatic alcohol and carbonyl functional groups of biosorbent were involved in the biosorption process. Therefore, biosorption of nickel (II) must involve several mechanisms simultaneously such as physical adsorption, chemisorption and ion exchange. Cost comparison for PSMC with Amberlite IRC-86 ion exchange resin indicates that the biosorbent has the potential to be developed into a cost effective and environmentally friendly treatment system.
Cat manure (CM) possesses high level of nutrients for growing food crop. However, animal manure may contain toxic elements that may contaminate food crop. Spent coffee ground (SCG) may be used to reduce mobility of heavy metals and reduce crop uptake. In this study, SCG was composted with CM for 31 days to produce a co-compost (SCG-CM) for growing spinach (Spinacia oleracea). The growth rate of spinach was assessed until its maturity, and the metal uptake of spinach shoot was determined thereafter using inductively coupled plasma-optical emission spectroscopy (ICP-OES). The effect of soil treatment with SCG-CM on the height and elemental composition of spinach were compared with that of chicken manure compost (CMC). The prepared composts were primarily organic matter (72.9-81.4 % w/w) with the rest are ash (13.3-23.4 % w/w) and moisture (1.2-2.6 % w/w). Zinc content in SCG-CM (1261 ± 0.1 mg/kg) is significantly higher than that of soil and CMC (p < 0.05) and has exceeded the maximum permissible limit set by European Union Standard (2002) and the Malaysian Compost Quality Standard and Guidelines (2000). Matured spinach reached maximum plant height after 33 days. The amendment of SCG-CM significantly increased the height of spinach (32 ± 6 cm) compared to that of CMC (13 ± 1 cm) (p < 0.05). However, contents of Zn, Cu, Pb and Cd were not increased for spinach grown in the SCG-CM-amended soil, and the level of those elements are below permissible limit set by the Malaysian Food Act 1983 and Food Regulations 1985. This study shows that SCG-CM is effective in improving yield without causing accumulation of toxic trace elements in spinach.
Pristine chitosan beads were modified with sulfur (S)-containing functional groups to produce thiolated chitosan beads (ETB), thereby increasing S donor ligands and crosslinks. The effect of temperature, heating time, carbon disulfide (CS2)/chitosan ratio, and pH on total S content of ETB was examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The total S content of ETB increased with increasing CS2/chitosan ratio and decreased with decreasing pH and increasing temperature (>60 °C) and heating time (at 60 °C). Spectroscopic analyses revealed the presence of thiol (-SH)/thione, disulfide (-S-S-), and sulfonate groups in ETB. The thiolation mechanism involves decomposition of dithiocarbamate groups, thereby forming thiourea crosslinks and trithiocarbonate, resulting in -SH oxidation to produce -S-S- crosslinks. The partially formed ETB crosslinks contribute to its acid stability and are thermodynamically feasible in adsorbing Cd and Cu. The S-containing functional groups added to chitinous wastes act as sorbents for metal remediation from acidic environments.
An effective hydrothermally prepared chitosan-benzaldehyde/SiO2 adsorbent (CTA-BZA/SiO2) employed functionalization of a CTA biopolymer with SiO2 nanoparticles and BZA. CTA-BZA/SiO2 is an adsorbent that was utilized for the adsorption of an acidic dye (acid red 88, AR88) from synthetic wastewater. The fundamental adsorption variables (A: CTA-BZA/SiO2 dosage (0.02-0.1 g); B: pH (4-10); and C: duration (10-60)) were optimized via the Box-Behnken design (BBD). The Langmuir and Freundlich isotherms (coefficients of determination R2 = 0.99) agreed well with empirical data of AR88 adsorption by CTA-BZA/SiO2. The pseudo-first-order model showed reasonable agreement with the kinetic data of AR88 adsorption by CTA-BZA/SiO2. The maximal AR88 adsorption capacity (qmax) for CTA-BZA/SiO2 was identified to be 252.4 mg/g. The electrostatic attractions between both the positively charged CTA-BZA/SiO2 adsorbent and the AR88 anions, plus the n-π, π-π, and H-bond interactions contribute to the favourable adsorption process. This study reveals that CTA-BZA/SiO2 has the capacity to be a suitable adsorbent for the removal of a wider range of organic dyes from industrial effluents.
Herein, the polymer nanomatrix of chitosan/SiO2 (CHI/n-SiO2) was enriched with a π-π electron donor-acceptor system using diaromatic rings of benzil (BEZ) assisted via a hydrothermal process to obtain an effective adsorbent of chitosan-benzil/SiO2 (CHI-BEZ/n-SiO2). The polymer nanomatrix (CHI/n-SiO2) and the resulting adsorbent (CHI-BEZ/n-SiO2) were applied to remove the anionic acid red 88 (AR88) dye from aqueous media in a comparative mode. Box-Behnken design (BBD) was adopted to optimize AR88 adsorption onto CHI/n-SiO2 and CHI-BEZ/n-SiO2 with respect to variables that influence AR88 adsorption (adsorbent dose: 0.02-0.1 g/100 mL; pH: 4-10; and time: 10-90). The adsorption studies at equilibrium were conducted with a variety of initial AR88 dye concentrations (20-200 mg/L). The adsorption isotherm results reveal that the AR88 adsorption by CHI/n-SiO2 and CHI-BEZ/n-SiO2 are described by the Langmuir model. The kinetic adsorption profiles of AR88 with CHI/n-SiO2 and CHI-BEZ/n-SiO2 reveal that the pseudo-first-order model provides the best fit results. Interestingly, CHI-BEZ/n-SiO2 has a high adsorption capacity (261.2 mg/g), which exceeds the adsorption capacity of CHI/n-SiO2 (215.1 mg/g) that relates to the surface effects of SiO2 and the functionalization of chitosan with BEZ. These findings show that CHI-BEZ/n-SiO2 represents a highly efficient adsorbent for the removal of harmful pollutants from water, which outperforming the CHI/n-SiO2 system.