The adsorption behavior of chitosan (CS) beads modified with 3-aminopropyl triethoxysilane (APTES) for the removal of reactive blue 4 (RB4) in batch studies has been investigated. The effects of modification conditions, such as the APTES concentration, temperature and reaction time on RB4 removal, were studied. The adsorbent prepared at a concentration of 2 wt% APTES for 8h at 50 °C was the most effective one for RB4 adsorption. The adsorption capacity of modified CS beads (433.77 mg/g) was 1.37 times higher than that of unmodified CS beads (317.23 mg/g). The isotherm data are adequately described by a Freundlich model, and the kinetic study revealed that the pseudo-second-order rate model was in better agreement with the experimental data. The negative values of the thermodynamic parameters, including ΔG° (-2.28 and -4.70 kJ/mol at 30 ± 2 °C), ΔH° (-172.18 and -43.82 kJ/mol) and ΔS° (-560.71 and -129.08 J/mol K) for CS beads and APTES modified beads, respectively, suggest that RB4 adsorption is a spontaneous and exothermic process.
There is a paucity of information about the occurrence of microplastics (MPs) in edible fish tissues. Here, we investigated the potential presence of MPs in the excised organs (viscera and gills) and eviscerated flesh (whole fish excluding the viscera and gills) of four commonly consumed dried fish species (n = 30 per species). The MP chemical composition was then determined using micro-Raman spectroscopy and elemental analysis with energy-dispersive X-ray spectroscopy (EDX). Out of 61 isolated particles, 59.0% were plastic polymers, 21.3% were pigment particles, 6.55% were non-plastic items (i.e. cellulose or actinolite), while 13.1% remained unidentified. The level of heavy metals on MPs or pigment particles were below the detection limit. Surprisingly, in two species, the eviscerated flesh contained higher MP loads than the excised organs, which highlights that evisceration does not necessarily eliminate the risk of MP intake by consumers. Future studies are encouraged to quantify anthropogenic particle loads in edible fish tissues.
Adsorption performance of chitosan (CS) hydrogel beads was investigated after impregnation of CS with hexadecylamine (HDA) as a cationic surfactant, for the elimination of reactive blue 4 (RB4) from wastewater. The CS/HDA beads formed with 3.8% HDA were the most effective adsorbent. The adsorption capacity was increased by 1.43 times from 317 mg/g (CS) to 454 mg/g (CS/HDA). The RB4 removal increased with decrease in the pH of dye solution from 4 to 9. The isotherm data obtained from RB4 adsorption on CS and CS/HDA are adequately described by Freundlich model (R(2)=0.946 and 0.934, χ(2)=22.414 and 64.761). The kinetic study revealed that the pseudo-second-order rate model (R(2)=0.996 and 0.997) was in better agreement with the experimental data. The negative values of ΔG° (-2.28 and -6.30 kJ/mol) and ΔH° (-172.18 and -101.62 kJ/mol) for CS beads and HDA modified CS beads, respectively; suggested a spontaneous and exothermic process for RB4 adsorption.
Chitosan based adsorbents have received a lot of attention for adsorption of dyes. Various modifications of this polysaccharide have been investigated to improve the adsorption properties as well as mechanical and physical characteristics of chitosan. This review paper discusses major research topics related to chitosan and its derivatives for application in the removal of dyes from water. Modification of chitosan changes the original properties of this material so that it can be more suitable for adsorption of different types of dye. Many chitosan derivatives have been obtained through chemical and physical modifications of raw chitosan that include cross-linking, grafting and impregnation of the chitosan backbone. Better understanding of these varieties and their affinity toward different types of dye can help future research to be properly oriented to address knowledge gaps in this area. This review provides better opportunity for researchers to better explore the potential of chitosan-derived adsorbents for removal of a great variety of dyes.
Many industries discharge untreated wastewater into the environment. Heavy metals from many industrial processes end up as hazardous pollutants of wastewaters.Heavy metal pollution has increased in recent decades and there is a growing concern for the public health risk they may pose. To remove heavy metal ions from polluted waste streams, adsorption processes are among the most common and effective treatment methods. The adsorbents that are used to remove heavy metal ions from aqueous media have both advantages and disadvantages. Cost and effectiveness are two of the most prominent criteria for choosing adsorbents. Because cost is so important, great effort has been extended to study and find effective lower cost adsorbents.One class of adsorbents that is gaining considerable attention is agricultural wastes. Among many alternatives, palm oil biomasses have shown promise as effective adsorbents for removing heavy metals from wastewater. The palm oil industry has rapidly expanded in recent years, and a large amount of palm oil biomass is available. This biomass is a low-cost agricultural waste that exhibits, either in its raw form or after being processed, the potential for eliminating heavy metal ions from wastewater. In this article, we provide background information on oil palm biomass and describe studies that indicate its potential as an alternative adsorbent for removing heavy metal ions from wastewater. From having reviewed the cogent literature on this topic we are encouraged that low-cost oil-palm-related adsorbents have already demonstrated outstanding removal capabilities for various pollutants.Because cost is so important to those who choose to clean waste streams by using adsorbents, the use of cheap sources of unconventional adsorbents is increasingly being investigated. An adsorbent is considered to be inexpensive when it is readily available, is environmentally friendly, is cost-effective and be effectively used in economical processes. The advantages that oil palm biomass has includes the following:available and exists in abundance, appears to be effective technically, and can be integrated into existing processes. Despite these advantages, oil palm biomasses have disadvantages such as low adsorption capacity, increased COD, BOD and TOC. These disadvantages can be overcome by modifying the biomass either chemically or thermally. Such modification creates a charged surface and increases the heavy metal ion binding capacity of the adsorbent.
In this study optimization of drying oil palm trunk core lumber (OPTCL) biomass using microwave radiation was reported. Optimizing of the drying conditions using microwave, avoid burning, shrinkage and increasing the permeability of OPT was aimed to develop a new value added material. A set of experiments was designed by central composite design using response surface methodology (RSM) to statistically evaluate the findings. Three independent process variables including time (2-10 min), sample weight (300-1000 g) and input power (660-3300 W) were studied under the given conditions designed by Design Expert software. The results showed the effectiveness of microwave drying in reducing the time and better removal of moisture as compared to that of oven drying with no significant changes. Employing optimum conditions at 6.89 min of time with a microwave power set at 4 for a sample of 1000 g, predicting 14.62% of moisture content.
Development of new materials for different applications especially as bio-composites has received great attention. This study concentrates on development of a biopolymer based on chitosan (CT) and halloysite nanotubes (HNT) and evaluates the copper removal intake as a potential application of this bio-composite. In this study, CT/HNT beads were prepared by ultrasonic-assisted extrusion-dripping method for the first time. Two sources of HNTs (i.e. Dragonite and Matauri Bay) were added into a chitosan solution (2wt.%) at various loading fractions (25, 50, 75wt.%). The effect of ultrasound as a mixing device was also studied by varying the amplitude at constant frequency of 25%, 50% and 75%. Characteristics and physical properties of the prepared CT/HNT beads were also analyzed by SEM, FTIR, TGA and BET the results show that introducing HNT to chitosan increases the adsorption capacity toward copper ions; however HNT loading fraction above 50wt.% resulted in a decrease in adsorption capacity attributed to limited accessibility of the amino groups. The adsorption capacity of the CT/HNT beads prepared from Dragonite source had a larger adsorption capacity of 14.2mg/g as compared to that of Matauri Bay, 10.55mg/g. It was observed that the adsorption capacity of the beads toward copper ions decreased when the loading fraction of HNT is increased at constant ultrasound amplitude. The result of this study helps to understand the links between the characteristics and adsorption abilities of CT/HNT beads.
The occurrence of microplastics (MPs) in saltwater bodies is relatively well studied, but nothing is known about their presence in most of the commercial salts that are widely consumed by humans across the globe. Here, we extracted MP-like particles larger than 149 μm from 17 salt brands originating from 8 different countries followed by the identification of their polymer composition using micro-Raman spectroscopy. Microplastics were absent in one brand while others contained between 1 to 10 MPs/Kg of salt. Out of the 72 extracted particles, 41.6% were plastic polymers, 23.6% were pigments, 5.50% were amorphous carbon, and 29.1% remained unidentified. The particle size (mean ± SD) was 515 ± 171 μm. The most common plastic polymers were polypropylene (40.0%) and polyethylene (33.3%). Fragments were the primary form of MPs (63.8%) followed by filaments (25.6%) and films (10.6%). According to our results, the low level of anthropogenic particles intake from the salts (maximum 37 particles per individual per annum) warrants negligible health impacts. However, to better understand the health risks associated with salt consumption, further development in extraction protocols are needed to isolate anthropogenic particles smaller than 149 μm.
This study is focused on nanocrystalline cellulose (NCC) flakes for methylene blue (MB) removal via adsorption. NCC flakes exhibit a high adsorption capacity (188.7 mg/g fixed at 0.7 g/L adsorbent dosage, 25 °C and pH 6) compared to other nanomaterials, such as carbon nanotube and other cellulosic materials, such as coffee husks. Unlike NCC powder, it was observed that NCC flakes can be easily separated from wastewater containing MB. Further adsorption studies were conducted on NCC flakes, and it was found that 0.7 g/L was the optimum adsorbent dosage, which fitted well with the Langmuir Isotherm. The mean free energy value from Dubinin-Radushkevich isotherm was less than 8 kJ/mol. ΔGo values at different temperatures were within the -20 kJ/mol to 0 kJ/mol range. In conclusion, NCC flakes is a promising and practical 'green' nanomaterial that can be further developed for industrial applications.
A composite chitosan/nano-activated carbon (CS-NAC) aminated by (3-aminopropyl)triethoxysilane (APTES) was prepared in the form of beads and applied for the removal of acetaminophen from aqueous solutions. NAC and APTES concentrations were optimized to obtain a suitable adsorbent structure for enhanced removal of the pharmaceutical. The aminated adsorbent (CS-NAC-APTES beads) prepared with 40% w/w NAC and 2% v/v APTES showed higher adsorption capacity (407.83 mg/g) than CS-NAC beads (278.4 mg/g). Brunauer-Emmett-Teller (BET) analysis demonstrated that the surface area of the CS-NAC-APTES beads was larger than that of CS-NAC beads (1.16 times). The adsorption process was well fitted by the Freundlich model (R2 > 0.95), suggesting a multilayer adsorption. The kinetic study also substantiated that the pseudo-second-order model (R2 > 0.98) was in better agreement with the experimental data. Finally, it was proved that the prepared beads can be recycled (by washing with NaOH solution) at least 5 times before detectable performance loss.
No report was found on the occurrence of microplastics in processed seafood products that are manufactured for direct human consumption. This study investigates the potential presence of micro- and mesoplastics in 20 brands of canned sardines and sprats originating from 13 countries over 4 continents followed by their chemical composition determination using micro-Raman spectroscopy. The particles were further inspected for their inorganic composition through energy-dispersive X-ray spectroscopy (EDX). Plastic particles were absent in 16 brands while between 1 and 3 plastic particles per brand were found in the other 4 brands. The most abundant plastic polymers were polypropylene (PP) and polyethylene terephthalate (PET). The presence of micro- and mesoplastics in the canned sardines and sprats might be due to the translocation of these particles into the edible tissues, improper gutting, or the result of contamination from the canneries. The low prevalence of micro- and mesoplastics sized >149μm, and the absence of potentially hazardous inorganic elements on them, might indicate the limited health risks associated with their presence in canned sardines and sprats. Due to the possible increase in micro- and mesoplastic loads in seafood products over time, the findings of this study suggest their quantification to be included as one of the components of food safety management systems.
So far, several classes of digesting solutions have been employed to extract microplastics (MPs) from biological matrices. However, the performance of digesting solutions across different temperatures has never been systematically investigated. In the first phase of the present study, we measured the efficiency of different oxidative agents (NaClO or H2O2), bases (NaOH or KOH), and acids [HCl or HNO3; concentrated and diluted (5%)] in digesting fish tissues at room temperature (RT, 25°C), 40, 50, or 60°C. In the second phase, the treatments that were efficient in digesting the biological materials (>95%) were evaluated for their compatibility with eight major plastic polymers (assessed through recovery rate, Raman spectroscopy analysis, and morphological changes). Among the tested solutions, NaClO, NaOH, and diluted acids did not result in a satisfactory digestion efficiency at any of the temperatures. The H2O2 treatment at 50°C efficiently digested the biological materials, although it decreased the recovery rate of nylon-6 (NY6) and nylon-66 (NY66) and altered the colour of polyethylene terephthalate (PET) fragments. Similarly, concentrated HCl and HNO3 treatments at RT fully digested the fish tissues, but also fully dissolved NY6 and NY66, and reduced the recovery rate of most or all of the polymers, respectively. Potassium hydroxide solution fully eliminated the biological matrices at all temperatures. However, at 50 and 60°C, it degraded PET, reduced the recovery rate of PET and polyvinyl chloride (PVC), and changed the colour of NY66. According to our results, treating biological materials with a 10% KOH solution and incubating at 40°C was both time and cost-effective, efficient in digesting biological materials, and had no impact on the integrity of the plastic polymers. Furthermore, coupling this treatment with NaI extraction created a promising protocol to isolate MPs from whole fish samples.
Stretchable self-healing urethane-based biomaterials have always been crucial for biomedical applications; however, the strength is the main constraint of utilization of these healable materials. Here, a series of novel, healable, elastomeric, supramolecular polyester urethane nanocomposites of poly(1,8-octanediol citrate) and hexamethylene diisocyanate reinforced with cellulose nanocrystals (CNCs) are introduced. Nanocomposites with various amounts of CNCs from 10 to 50 wt% are prepared using solvent casting technique followed by the evaluation of their microstructural features, mechanical properties, healability, and biocompatibility. The synthesized nanocomposites indicate significantly higher tensile modulus (approximately 36-500-fold) in comparison to the supramolecular polymer alone. Upon exposure to heat, the materials can reheal, but nevertheless when the amount of CNC is greater than 10 wt%, the self-healing ability of nanocomposites is deteriorated. These materials are capable of rebonding ruptured parts and fully restoring their mechanical properties. In vitro cytotoxicity test of the nanocomposites using human dermal fibroblasts confirms their good cytocompatibility. The optimized structure, self-healing attributes, and noncytotoxicity make these nanocomposites highly promising for tissue engineering and other biomedical applications.