Kinetics and Thermodynamics Study on Removal of Cr(VI) from Aqueous Solutions Using Acid-Modified Banana Peel (ABP) Adsorbents.

Banana peel waste is abundant and can be utilized as a low-cost adsorbent for removing toxic Cr (VI) from wastewater. The acid modification of banana peels significantly enhances their adsorption capacity for Cr (VI). An adsorbent was prepared by treating banana peel powder with 50% H2SO4 at 50 °C for 24 h. The acid treatment increased the surface area of the adsorbent from 0.0363 to 0.0507 m2/g. The optimum adsorbent dose was found to be 1 g/L for the complete removal of Cr (VI) from 100 ppm solutions. The adsorption capacity was 161 mg/g based on the Langmuir isotherm model. The adsorption kinetics followed a pseudo-second order model. Increasing the temperature from 20 to 50 °C increased the initial adsorption rate but had a minor effect on the equilibrium adsorption capacity. Thermodynamics studies showed that the process was spontaneous and endothermic. The activation energy was estimated as 24.5 kJ/mol, indicating physisorption. FTIR analyses before and after adsorption showed the involvement of hydroxyl, carbonyl and carboxyl groups in binding the Cr (VI). The Cr (VI) was reduced to Cr (III), which then bound to functional groups on the adsorbent. Desorption under acidic conditions could recover 36% of the adsorbed Cr as Cr (III). No desorption occurred at a neutral pH, indicating irreversible adsorption. Overall, acid-modified banana peel is an efficient, low-cost and eco-friendly adsorbent for removing toxic Cr (VI) from wastewater.

Orange peel magnetic activated carbon for removal of acid orange 7 dye from water.

Magnetic activated carbon resources with a remarkably high specific surface area have been successfully synthesized using orange peels as the precursor and ZnCl2 as the activating agent. The impregnation ratio was set at 0.5, while the pyrolysis temperature spanned from 700 to 900 °C. This comprehensive study delved into the influence of activation temperatures on the resultant pore morphology and specific surface area. Optimal conditions were discerned, leading to a magnetic activated carbon material exhibiting an impressive specific surface area at 700 °C. The Brunauer-Emmett-Teller surface area reached 155.09 m2/g, accompanied by a total pore volume of 0.1768 cm3/g, and a mean pore diameter of 4.5604 nm. The material displayed noteworthy properties, with saturation magnetization (Ms) reaching 17.28 emu/g, remanence (Mr) at 0.29 emu/g, and coercivity (Hc) of 13.71 G. Additionally, the composite demonstrated super-paramagnetic behaviour at room temperature, facilitating its rapid collection within 5 s through an external magnetic field. Factors such as absorbent dose, initial concentration of the adsorbate, contact time, and pH were systematically examined. The adsorption behaviour for acid orange 7 (AO7) was found to adhere to the Temkin isotherm models (R2 = 0.997). The Langmuir isotherm model suggested a monolayer adsorption, and the calculated maximum monolayer capacity (Qm) was 357.14 mg/g, derived from the linear solvation of the Langmuir model using 0.75 g/L as an adsorbent dose and 150-500 mg/L as AO7 dye concentrations. The pseudo-second order model proved to be the best fit for the experimental data of AO7 dye adsorption, with a high coefficient of determination (R2) ranging from 0.999 to 1.000, outperforming other kinetic models.

Enhancement of the Solubility of BS Class II Drugs with MOF and MOF/GO Composite Materials: Case Studies of Felodipine, Ketoprofen and Ibuprofen.

In this research, a novel composite material composed of Metal-Organic Framework material (MOF) and graphite oxide was synthesized and evaluated as a possible drug-loading vehicle. HKUST-1, a MOF material originally designed by the Hong Kong University of Science and Technology, was used as a model porous material. The aim was to synthesize a drug delivery vehicle for modifying the release kinetics and solubility of poorly soluble drugs (BSC Class II drugs); these are drugs that are known to have poor bioavailability due to their low solubility. We used ketoprofen, ibuprofen, and felodipine as models for BSC Class II drugs. The drugs were loaded onto composite materials through adsorption. The adsorption of these three drugs into the matrix of HKUST-1/GO (graphite oxide), HKUST-1, and graphite oxide was compared. The loading efficiency of the drugs onto the carrier was dependent on the drug molecule and the composition of the drug carrier. The inclusion of graphite oxide in the drug carrier matrix improved the drug loading capacity and modified the drug release rate. The loading of the three drugs felodipine, ketoprofen, and ibuprofen onto HKUST-1 were 33.7, 58, and 79 mg/g respectively. The incorporation of GO into the HKUST-1 matrix resulted in an increase in the loading by 16 and 4 mg/g for the ketoprofen and ibuprofen drugs. When compared to the pure drugs, the solubility of all three drugs in the HKUST-1/GO matrix increased by at least 6 folds.

Mercury contamination in the riparian ecosystem during the reservoir discharging regulated by a mega dam.

Mercury (Hg) is extremely poisonous and can be absorbed through touch, inhalation, or consumption. In the living environment, Hg in contaminated sediment can be transferred into grass by the direct absorption through the roots or shoots. The intake of Hg due to Hg emissions may pose a threat to living bodies especially to human beings. The present study aims to provide a novel insight about total mercury (THg) and methyl mercury (MeHg) in a riparian grass (Cynodon dactylon (L).Pers) and sediments during the discharging phase (summertime at 145 m water level) in Three Gorges Reservoir (TGR-China); where C. dactylon is a dominant perennial herb in the riparian zone. Yet, the potential risk of Hg contamination in the riparian ecosystem is not thoroughly assessed in the dam regulated reservoir. This study was conducted in the riparian zones of the reservoir formed by a mega dam (Three Gorge Dam) which regulates the water levels during the summer and winter period in the TGR. Our results showed that riparian sediments were acting as a sink for THg and MeHg. Insignificant correlation of THg and MeHg was found between the amphiphyte C. dactylon and its surrounding sediments in the TGR. Bioconcentration factors values for MeHg were found higher than 1 in all study locations in the riparian zones in TGR, which could be due to action of certain bacteria/purely chemical-based methylation on inorganic form of Hg. Additionally, translocation factor indices also highlighted that the amphiphyte C. dactylon was MeHg accumulator in riparian zones. These results suggested that since riparian sediment was found acting as the sink for THg and MeHg during discharging phase, MeHg contamination in the amphiphyte C. dactylon in riparian zones was not caused by the riparian sediments but by other factors, for instance, the anthropogenic activities in the TGR. Finally, this study leads to conclude that amphiphyte C. dactylon can be used as biomonitoring agent for Hg pollution in the TGR.

Mercury and its form in a dammed reservoir ecosystem during the charging phase.

Throughout continents, reservoirs tend to have elevated methylmercury (MeHg) concentration transformed from mercury (Hg/total Hg). This impact may be pronounced in the reservoir with less velocity of water during the charging period resulted in the deposition of sediments. In sediments on favorable conditions, methylation may be enhanced by the decomposition of flood organic material, which can release Hg and enhance microbial activity. However, much less is known about the transfer ratio of Hg and its form MeHg from sediment to biota in the hydrological reservoir during the dam charging phase. The objective of our study was to understand the interrelationship between total Hg and MeHg in two key components sediment and fish in the reservoir ecosystem. This study was performed at the Three Gorges Reservoir (TGR) located on upstream of the Yangtze River in China. At the TGR charging phase, during winter time, the water level was high due to blockade of water by Three Gorges Dam (TGD). Sediment and fish samples were collected in winter season for total Hg, MeHg, and several ancillary parameters. The results showed that total Hg in sediment samples of the winter season were ranged from 6.2 ± 0.001 to 193.3 ± 0.001 × 10-3 mg/kg, with an average value of 53.76 ± 51.80 × 10-3 mg/kg, and for MeHg was ranged from 12.1 ± 0.04 to 348.7 ± 0.16 × 10-2 ng/g, with an average value of 98.96 ± 93.07 × 10-2 ng/g. Total Hg and MeHg in fish samples of the winter season were from 42.48 ± 6.71 to 166 ± 52.56 ng/g, with an average value of 76.22 ± 31.23 ng/g, and from 21.09 ± 2.31 to 61.60 ± 13.30 ng/g, with an average value of 37.89 ± 11.96 ng/g. The relationship of total Hg and MeHg concentrations in fish to those of sediments from corresponding sites showed a negative relationship. This might include a strong association of total Hg with an inorganic component of sediment (e.g., bound to sulfides or coprecipitated with other metal oxides such as manganese and iron). The average concentration of fish MeHg found in this study, at rates greater than 1.72 g/day, was estimated hazardous to human health. This study concludes sediment was acting as sequestrate for total Hg and MeHg in TGR. The bioaccumulation of total Hg and MeHg in fish was not controlled by sediment further investigation about pathological routes and dietary habits of fish needed to be identified for total Hg and MeHg study in TGR.

Single, simultaneous and consecutive biosorption of Cr(VI) and Orange II onto chemically modified masau stones.

Novel and low cost chemically modified masau stone (CMMS) was investigated for its biosorption of an anionic azo dye, Orange II (OII), and toxic hexavalent chromium (Cr(VI)) from aqueous systems: individually, simultaneously and consecutively. XPS and FTIR analyses indicated the introduction of quaternary-Nitrogen to the CMMS surface after activation with epichlorohydrin (etherifying agent) and diethylenetriamine (crosslinking agent). The effects of pH, contact time and initial concentration (Co), and loading order on mechanisms of biosorption/reduction of OII and Cr(VI) onto CMMS were examined in detail. Several analytical techniques were employed to characterise the physio-chemical properties of the CMMS and determine the biosorption mechanisms. The pseudo second order and redox models were able to adequately predict the kinetics of biosorption. The Langmuir maximum OII biosorption capacity (qmax) was calculated as 136.8 mg/g for the dye onto the Cr(VI)-loaded CMMS consecutive system at Co = 100 mg/dm3. The qmax for the Cr(VI) system was found to be 87.32 mg/g at the same Co max. This reveals that the biosorption of OII and Cr(VI) mainly takes place via two different mechanisms i.e. hydrogen bonding and electrostatic attraction for the dye, and biosorption-coupled reduction for Cr(VI).

Manufacturing of novel low-cost adsorbent: Co-granulation of limestone and coffee waste.

Limestone and coffee waste were used during the wet co-granulation process for the production of efficient adsorbents to be used in the removal of anionic and cationic dyes. The adsorbents were characterized using different analytical techniques such as XRD, SEM, FTIR, organic elemental analysis, the nitrogen adsorption method, with wettability, strength and adsorption tests. The adsorption capacity of granules was determined by removal of methylene blue (MB) and orange II (OR) from single and mixed solutions. In the mixed solution, co-granules removed 100% of MB and 85% of OR. The equilibria were established after 6 and 480 h for MB and OR, respectively.

Effect of poly ethylene glycol on the mechanical and thermal properties of bioactive poly(ε-caprolactone) melt extrudates for pharmaceutical applications.

This paper investigates the effects of polyethylene glycol (PEG), on the mechanical and thermal properties of nalidixic acid/poly ε-caprolactone (NA)/PCL blends prepared by hot melt extrusion. The blends were characterized by tensile and flexural analysis, dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis and X-ray diffraction. Results show that loading PEG in the PCL had a detrimental effect on the tensile strength and toughness of the blends, reducing them by 20-40%. The partial miscibility of the PCL-PEG system, causes an increase in Tg. While increases in the crystallinity is attributed to the plasticisation effect of PEG and the nucleation effect of NA. The average crystal size increased by 8% upon PEG addition. Experimental data indicated that the addition of NA caused loss of the tensile strength and toughness of PCL. Thermal analysis of the PCL showed that on addition of the thermally unstable NA, thermal degradation occurred early and was autocatalytic. However, the NA did benefit from the heat shielding provided by the PCL matrix resulting in more thermally stable NA particles.

Mechanisms of Alizarin Red S and Methylene blue biosorption onto olive stone by-product: Isotherm study in single and binary systems.

The biosorption process of anionic dye Alizarin Red S (ARS) and cationic dye methylene blue (MB) as a function of contact time, initial concentration and solution pH onto olive stone (OS) biomass has been investigated. Equilibrium biosorption isotherms in single and binary systems and kinetics in batch mode were also examined. The kinetic data of the two dyes were better described by the pseudo second-order model. At low concentration, ARS dye appeared to follow a two-step diffusion process, while MB dye followed a three-step diffusion process. The biosorption experimental data for ARS and MB dyes were well suited to the Redlich-Peterson isotherm. The maximum biosorption of ARS dye, qmax = 16.10 mg/g, was obtained at pH 3.28 and the maximum biosorption of MB dye, qmax = 13.20 mg/g, was observed at basic pH values. In the binary system, it was indicated that the MB dye diffuses firstly inside the biosorbent particle and occupies the biosorption sites forming a monodentate complex and then the ARS dye enters and can only bind to untaken sites; forms a tridentate complex with OS active sites.

Thermo-mechanical properties of poly ε-caprolactone/poly L-lactic acid blends: addition of nalidixic acid and polyethylene glycol additives.

The search for ideal biomaterials is still on-going for tissue regeneration. In this study, blends of poly ε-caprolactone (PCL) with poly l-lactic acid (PLLA), nalidixic acid (NA) and polyethylene glycol (PEG) were prepared. Mechanical and thermal properties of the blends were investigated by tensile and flexural analysis, DSC, TGA, WXRD, MFI, BET, SEM and hot stage optical microscopy. Results showed that the loading of PLLA caused a significant decrease in tensile strength and almost total eradication of the elongation at break of PCL matrix, especially after PEG and NA addition. Increased stiffness was also noted with additional NA, PEG and PLLA, resulting in an increase in the flexural modulus of the blends. Isothermal degradation indicated that bulk PCL, PLLA and the blends were thermally stable at 200°C for the duration of 2h making extrusion of the blends at this temperature viable. Morphological study showed that increasing the PLLA content and addition of the very low viscosity PEG and powder NA decreased the Melt Flow Indexer and increased the viscosity. At the higher temperature, the PLLA begins to soften and eventually melts allowing for increased flow and, coupling this with, the natural increase in MFI caused by temperature is enhanced further. The PEG and NA addition increased dramatically the pore volume which is important for cell growth and flow transport of nutrients and metabolic waste.

The variability in nutrient composition of Anaerobic Digestate granules produced from high shear granulation.

This study investigates the production of organic fertilizer using Anaerobic Digestate (as a nutrient source) and limestone powder as the raw materials. A two-level factorial experimental design was used to determine the influence of process variables on the nutrient homogeneity within the granules. Increasing the liquid-to-solid ratio during granulation resulted in increased granule nutrient homogeneity. Increasing the processing time and the impeller speed were also found to increase the nutrient homogeneity. In terms of nutrients release into deionized water, the granules effectively released both potassium and phosphate into solution.

Influence of solution chemistry on Cr(VI) reduction and complexation onto date-pits/tea-waste biomaterials.

Tea waste (TW) and Date pits (DP) were investigated for their potential to remove toxic Cr(VI) ions from aqueous solution. Investigations showed that the majority of the bound Cr(VI) ions were reduced to Cr(III) after biosorption at acidic conditions. The electrons for the reduction of Cr(VI) may have been donated from the TW and DP biomasses. The experimental data obtained for Cr(VI)-TW and Cr(VI)-DP at different solution temperatures indicate a multilayer type biosorption, which explains why the Sips isotherm accurately represents the experimental data obtained in this study. The Sips maximum biosorption capacities of Cr(VI) onto TW and DP were 5.768 and 3.199 mmol/g at 333 K, respectively, which is comparatively superior to most other low-cost biomaterials. Fourier transform infrared spectroscopic analysis of the metal loaded biosorbents confirmed the participation of -COOH, -NH(2) and O-CH(3) groups in the reduction and complexation of chromium. Thermodynamic parameters demonstrated that the biosorption of Cr(VI) onto TW and DP biomass was endothermic, spontaneous and feasible at 303-333 K. The results evidently indicated that tea waste and date pits would be suitable biosorbents for Cr(VI) in wastewater under specific conditions.

An investigation of the influence of process and formulation variables on mechanical properties of high shear granules using design of experiment.

Being able to predict the properties of granules from the knowledge of the process and formulation variables is what most industries are striving for. This research uses experimental design to investigate the effect of process variables and formulation variables on mechanical properties of pharmaceutical granules manufactured from a classical blend of lactose and starch using hydroxypropyl cellulose (HPC) as the binder. The process parameters investigated were granulation time and impeller speed whilst the formulation variables were starch-to-lactose ratio and HPC concentration. The granule properties investigated include granule packing coefficient and granule strength. The effect of some components of the formulation on mechanical properties would also depend on the process variables used in granulation process. This implies that by subjecting the same formulation to different process conditions results in products with different properties.