Analysis of herbicides sorption behavior in soil is critical in predicting their fate and possible harmful side effects in the environment. Application of polar imidazolinone herbicides is growing in tropical agricultural fields. Imidazolinones have high leaching potential and are persistent. In this study, adsorption-desorption of imazapic and imazapyr herbicides were evaluated in different types of Malaysian agricultural soils. Effects of soil parameters were also investigated on the soils' sorption capacities. The adsorption data fitted best to Freundlich isotherm (R2 > 0.991). The herbicides adsorptions were physical and spontaneous processes as ΔG values were negative and below 40 kJ/mol. The adsorption correlated positively with clay content, total organic carbon (TOC) content, and cation exchange capacity (CEC). There were strong negative correlations between hysteresis index and these factors indicating their importance in imidazolinones immobilization and, thus, their pollution reduction in the environment.
Among abiotic stresses, salinity is the main abiotic stress limiting crop growth and yield worldwide. Improving agri-food production in salt-prone areas is the key to meet the increasing food demands in near future. A greenhouse experiment was conducted to investigate the effect of different soil conditioners, gypsum (GYP), citric acid (CA), ethylene diamine tetraacetic acid (EDTA) and polyvinyl alcohol (PVA), on growth and yield of wheat (Triticum aestivum L.) grown in salinesodic soil. Gypsum was applied at a rate of 100% soil gypsum requirement while other amendments were applied each at a rate of 5 g kg-1 of soil. The results showed that EDTA treatment increased pH and electrical conductivity (ECe) of soil while pH significantly decreased when treated with citric acid. Soil sodium adsorption ratio (SAR) and exchangeable sodium percentage (ESP) decreased in all treatments following the order: CT > PVA > EDTA > CA > GYP. Addition of CA positively affected growth parameters as compared to other soil conditioners including plant height, number of tillers per plant, number of spikes per plant, plant dry weight and grain yield while EDTA negatively affected these parameters. Addition of CA also significantly increased photosynthetic rate, stomatal conductance, transpiration rate and chlorophyll contents while EDTA decreased these parameters. We conclude that increase in plant growth and yield with CA might be due to the effect of CA on soil properties which positively affected plant physiological parameters.
The water chemistry of selected rivers in Kota Marudu, Sabah was studied based on the major ion chemistry and its suitability for drinking and irrigation purposes. Ten sampling stations were selected and water samples were collected from each station to assess its chemical properties. The physico-chemical variables including temperature, electrical conductivity (EC), total dissolved solids (TDS), salinity, dissolved oxygen (DO), pH, turbidity, ammoniacal-nitrogen (NH3-N), biological oxygen demand (BOD), chemical oxygen demand (COD) and total suspended solid (TSS) were measured. The cations (K, Mg, Ca, Na) were analyzed by ICP-MS. Most of the variables were within the drinking water quality standards stipulated by the World Health Organization (WHO) and the Ministry of Health (MOH), Malaysia except for turbidity. Sodium adsorption ratio (SAR) and salinity hazard were calculated to identify the suitability of the water as irrigation water. The Wilcox diagram classifies that only 10% of samples are not suitable for the purpose of irrigation. The overall results showed that most of the rivers in Kota Marudu are still in a clean condition and suitable for drinking and irrigation purposes except for Sumbilingan River, which is considered as slightly polluted. The results are supported by the hierarchical cluster analysis as the stations were grouped into two groups; low and high pollution intensities. This preliminary result can update the baseline data of selected water quality parameters in the Kota Marudu and could serve as tool for assisting relevant government bodies in regulating the water resources policies in the future.
The adsorption of rhodamine B (RhB) using acid modified banana peels has been examined. Chemical characteristics of the adsorbents were observed in order to determine active functional groups. The major functional groups on the surface were OH, C = O, C = C and C-O-C. Interactions between operational parameters were studied using the central composite design (CCD) of response surface methodology (RSM). The predictions of the model output indicated that operational factors influenced responses at a confidence level of 95% (P<0.05). The optimum conditions for adsorption were pH 2 at a 0.2 g/L dose within 60 minutes of contact time. Isotherm studies were carried out using the optimized process variables. The data revealed that RhB adsorption fitted the Langmuir isotherm equation while the reduction of COD followed the Freundlich isotherm. Kinetic experiments fitted the pseudo second order model for RhB removal and COD reduction. The adsorption mechanism was not the only rate controlling step. Diffusion through the boundary layer described the pattern of adsorption.
An adsorption-desorption process was applied on fermented landfill leachate to adsorb and recover acetic and butyric acid, using activated carbon. In this study, the first, volatile fatty acids adsorption process from fermented leachate was optimized, by investigating various affecting factors such as pH, time, agitation speed, activated carbon dosage, and temperature. The optimum condition for maximum adsorption of 88.94% acetic acid and 98.53% butyric acid, was 19.79 %wt activated carbon dosage, 40.00 rpm of agitation speed, in 9.45 °C and contact time of 179.89 h, while the pH of the substrate was kept fixed at pH:3.0. Results of X-ray fluorescence (XRF) spectrometry, X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and zeta potential revealed that carbon is the dominant component in the adsorbent with a significant effect to remove organic impurities, and it was observed that the activated carbon after the adsorption process showed an amorphous structure peak with a large internal surface area and pore volume. The results exposed that the adsorption on the surface of activated carbon was due to the chemisorption, and the chemisorption mechanism was supported by covalent bonding. The kinetic study displayed excellent fit to Pseudo-second order kinetics model. The second phase of this study was to recover the adsorbed VFAs using multistage desorption unit, in which application of deionized water and ethanol (as desorption agents) resulted in 89.1% of acetic acid and 67.8% of the butyric acid recovery.
In this study, chitosan/polyvinyl alcohol/TiO2 nanofiber was fabricated via electrospinning at a pump rate of 1.5 mL/h and voltage 6 kV. Field-emission scanning electron microscopic images showed bead free finer nanofiber. Fourier transform infrared spectra proved the formation of strong bond among chitosan, polyvinyl alcohol and TiO2. X-ray powder diffraction showed that TiO2 became amorphous in the composite nanofiber. Toughness and thermal stability of the chitosan/PVA nanofibrous membrane was increased with addition TiO2. The chitosan/PVA/TiO2 nanofibrous membrane was stable at basic medium. But degraded in acidic and water medium after 93 and 162 h, respectively. The adsorption mechanism of congo red obeyed the Langmuir isotherm model. On the other hand, adsorption characteristic of methyl orange fitted well with both Langmuir and Freundlich isotherm models. The maximum adsorption capacity of the resulting membrane for congo red and methyl orange is 131 and 314 mg/g, respectively. However, a high dose of adsorbent was required for congo red.
In the recent decade, deep eutectic solvents (DESs) have occupied a strategic place in green chemistry research. This paper discusses the application of DESs as functionalization agents for multi-walled carbon nanotubes (CNTs) to produce novel adsorbents for the removal of 2,4-dichlorophenol (2,4-DCP) from aqueous solution. Also, it focuses on the application of the feedforward backpropagation neural network (FBPNN) technique to predict the adsorption capacity of DES-functionalized CNTs. The optimum adsorption conditions that are required for the maximum removal of 2,4-DCP were determined by studying the impact of the operational parameters (i.e., the solution pH, adsorbent dosage, and contact time) on the adsorption capacity of the produced adsorbents. Two kinetic models were applied to describe the adsorption rate and mechanism. Based on the correlation coefficient (R2) value, the adsorption kinetic data were well defined by the pseudo second-order model. The precision and efficiency of the FBPNN model was approved by calculating four statistical indicators, with the smallest value of the mean square error being 5.01 × 10-5. Moreover, further accuracy checking was implemented through the sensitivity study of the experimental parameters. The competence of the model for prediction of 2,4-DCP removal was confirmed with an R2 of 0.99.
Heavy metal contamination in aqueous system has attracted global attention due to the toxicity and carcinogenicity effects towards living bodies. Among available removal techniques, adsorptive removal by nanosized materials such as metal oxide, metal organic frameworks, zeolite and carbon-based materials has attracted much attention due to the large active surface area, large number of functional groups, high chemical and thermal stability which led to outstanding adsorption performance. However, the usage of nanosized materials is restricted by the difficulty in separating the spent adsorbent from aqueous solution. The shift towards the use of adsorptive composite membrane for heavy metal ions removal has attracted much attention due to the synergistic properties of adsorption and filtration approaches in a same chamber. Thus, this review critically discusses the development of nanoadsorbents and adsorptive nanocomposite membranes for heavy metal removal over the last decade. The adsorption mechanism of heavy metal ions by the advanced nanoadsorbents is also discussed using kinetic and isotherm models. The challenges and future prospect of adsorptive membrane technology for heavy metal removal is presented at the end of this review.
In this work, chitosan (Chi) was cross-linked with glyoxal (Gly) and deposited onto glass plate to be a superior adsorbent film for two structurally different reactive orange 16 (RO-16) and methyl orange (MO) dyes by using non-conventional adsorption system without filtration process. The characterizations indicate that the cross-linked chitosan-glyoxal (Chi-Gly) film has a low swelling index, high adherence strength on glass plate, amine group (NH2) content was 32.52%, and pHpzc of ∼6.0 indicating a negative surface charge occurs above pHpzc. The adsorption isotherm data of RO-16 and MO by Chi-Gly film were in agreement with Langmuir isotherm, with maximum adsorption capacities of 1554.3 mg/g and 1451.9 mg/g, respectively. The pseudo-first-order kinetic model best described the kinetic data. The adsorption process was spontaneous and exothermic in nature at Chi-Gly film thickness of 8.55 μm, and pH ~3. The mechanism of adsorption included mainly electrostatic attractions, dipole-dipole hydrogen bonding interactions, n-π stacking attractions, and Yoshida H-bonding. This study reveals that immobilized Chi-Gly film as a good candidate for adsorption of reactive and acid dyes as it does not require any filtration process and adsorbent recovery during and post-adsorption process.
Polyacrylonitrile nanofiber membrane functionalized with tris(hydroxymethyl)aminomethane (P-Tris) was used in affinity membrane chromatography for lysozyme adsorption. The effects of pH and protein concentration on lysozyme adsorption were investigated. Based on Langmuir model, the adsorption capacity of P-Tris nanofiber membrane was estimated to be 345.83 mg/g. For the operation of dynamic membrane chromatography with three-layer P-Tris nanofiber membranes, the optimal operating conditions were at pH 9, 1.0 mL/min of feed flow rate, and 2 mg/mL of feed concentration. Chicken egg white (CEW) was applied as the crude feedstock of lysozyme in the optimized dynamic membrane chromatography. The percent recovery and purification factor of lysozyme obtained from the chromatography were 93.28% and 103.98 folds, respectively. Our findings demonstrated the effectiveness of P-Tris affinity nanofiber membrane for the recovery of lysozyme from complex CEW solution.
In this study, poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) dual-layer membranes filled with 0-3 wt% cellulose nanowhisker (CNWs) were fabricated with aim to remove metal ions from wastewater. An integrated method was employed in the membrane fabrication process by combining water vapor-induced and crystallization-induced phase inversions. The membrane thickness was measured in between 11 and 13 μm, which did not pose significant flux deviation during filtration process. The 3% CNW filled membrane showed prominent and well-laminated two layers structure. Meanwhile, the increase in CNWs from 0 to 3% loadings could improve the membrane porosity (43-74%) but reducing pore size (2.45-0.54 μm). The heat resistance of neat membrane enhanced by 1% CNW but decreased with loadings of 2-3% CNWs due to flaming behavior of sulphated nanocellulose. Membrane with 3% CNW displayed the tensile strength (23.5 MPa), elongation at break (7.1%), and Young's modulus (0.75 GPa) as compared to other samples. For wastewater filtration performance, the continuous operation test showed that 3% CNW filled membrane exhibited the highest removal efficiency for both cobalt and nickel metal ions reaching to 83% and 84%, respectively. We concluded that CNWs filled dual-layer membranes have potential for future development in the removal of heavy metal ions from wastewater streams.
The presence of dyes in the aquatic environment as a result of anthropogenic activities, especially textile industries, is a critical environmental challenge that hinders the availability of potable water. Different wastewater treatment approaches have been used to remediate dyes in aquatic environments; however, most of these approaches are limited by factors ranging from high cost to the incomplete removal of the dyes and contaminants. Thus, the use of adsorption as a water treatment technology to remove dyes and other contaminants has been widely investigated using different adsorbents. This study evaluated the significance of chitosan as a viable adsorbent for removing dyes from water treatment. We summarised the literature and research results obtained between 2009 and 2020 regarding the adsorption of dyes onto chitosan and modified chitosan-based adsorbents prepared through physical and chemical processing, including crosslinking impregnation, grafting, and membrane preparation. Furthermore, we demonstrated the effects of various chitosan-based materials and modifications; they all improve the properties of chitosan by promoting the adsorption of dyes. Hence, the application of chitosan-based materials with various modifications should be considered a cutting-edge approach for the remediation of dyes and other contaminants in aquatic environments toward the global aim of making potable water globally available.
Sustainable wastewater treatment is one of the biggest issues of the 21st century. Metals such as Zn2+ have been released into the environment due to rapid industrial development. In this study, dried watermelon rind (D-WMR) is used as a low-cost adsorption material to assess natural adsorbents' ability to remove Zn2+ from synthetic wastewater. D-WMR was characterized using scanning electron microscope (SEM) and X-ray fluorescence (XRF). According to the results of the analysis, the D-WMR has two colours, white and black, and a significant concentration of mesoporous silica (83.70%). Moreover, after three hours of contact time in a synthetic solution with 400 mg/L Zn2+ concentration at pH 8 and 30 to 40 °C, the highest adsorption capacity of Zn2+ onto 1.5 g D-WMR adsorbent dose with 150 μm particle size was 25 mg/g. The experimental equilibrium data of Zn2+ onto D-WMR was utilized to compare nonlinear and linear isotherm and kinetics models for parameter determination. The best models for fitting equilibrium data were nonlinear Langmuir and pseudo-second models with lower error functions. Consequently, the potential use of D-WMR as a natural adsorbent for Zn2+ removal was highlighted, and error analysis indicated that nonlinear models best explain the adsorption data.
The efficiency of the extraction and removal of pollutants from food and the environment has been an important issue in analytical science. By incorporating inorganic species into an organic matrix, a new material known as an organic-inorganic hybrid material is formed. As it possesses high selectivity, permeability, and mechanical and chemical stabilities, organic-inorganic hybrid materials constitute an emerging research field and have become popular to serve as sorbents in various separaton science methods. Here, we review recent significant advances in analytical solid-phase extraction employing organic-inorganic composite/nanocomposite sorbents for the extraction of organic and inorganic pollutants from various types of food and environmental matrices. The physicochemical characteristics, extraction properties, and analytical performances of sorbents are discussed; including morphology and surface characteristics, types of functional groups, interaction mechanism, selectivity and sensitivity, accuracy, and regeneration abilities. Organic-inorganic hybrid sorbents combined with extraction techniques are highly promising for sample preparation of various food and environmental matrixes with analytes at trace levels.
In this work, palm shell waste powder activated carbon coated by magnesium silicate (PPAC-MS) were synthesized by the impregnation of magnesium silicate (MgSiO3) using economical material (silicon dioxide powder) via mild hydrothermal approach for the first time. As an effective adsorbent, PPAC-MS simultaneously removes BPA and Pb(II) in single and binary mode. Surprisingly, PPAC-MS exhibited a homogeneous thin plate mesh-like structure, as well as meso- and macropores with a high surface area of 772.1m2g-1. Due to its specific morphological characteristics, PPAC-MS had adsorption capacities of Pb(II) as high as 419.9mgg-1 and 408.8mgg-1 in single mode and binary mode based on Freudliuch isotherm model while those for BPA by PPAC-MS were 168.4mgg-1 and 254.7mgg-1 for single mode and binary modes corresponding to Langmuir isotherm model. Experiment results also indicated that the synergistic removal of BPA occurred because the precipitation process of Pb(II) leads to the co-precipitation of BPA with Pb(OH)2 compound. PPAC-MS showed a good reusability for 5 regeneration cycles using Mg(II) solution followed by thermal treatment. Overall, PPAC-MS has a high potential in the treatment process for wastewater containing both toxic heavy metals and emerging pollutants due to its high sorption capacities and reusability.
This study focused on the residue detection of the herbicides triclopyr and glufosinate ammonium in the runoff losses from the Tasik Chini oil palm plantation area and the Tasik Chini Lake under natural rainfall conditions in the Malaysian tropical environment. Triclopyr and glufosinate ammonium are post-emergence herbicides. Both herbicides were foliar-sprayed on 0.5 ha of oil palm plantation plots, which were individualized by an uneven slope of 10-15%. Samples were collected at 1, 3, 7, 15, 30, 45, 60, 90, and 120 days after treatment. The concentrations of both herbicides quickly diminished from those in the analyzed sample by the time of collection. The highest residue levels found in the field surface leachate were 0.031 (single dosage, triclopyr), 0.041 (single dosage, glufosinate ammonium), 0.017 (double dosage, triclopyr), and 0.037 μg/kg (double dosage, glufosinate ammonium). The chromatographic peaks were observed at "0" day treatment (2 h after herbicide application). From the applied active ingredients, the triclopyr and glufosinate losses were 0.025 and 0.055%, respectively. The experimental results showed that both herbicides are less potent than other herbicides in polluting water systems because of their short persistence and strong adsorption onto soil clay particles.
The present work was aimed at evaluating the multi-metals column adsorption of lead(II), cadmium(II) and manganese(II) ions onto natural bentonite. The bentonite clay adsorbent was characterized for physical and chemical properties using X-ray diffraction, X-ray fluorescence, Brunauer-Emmett-Teller surface area and cation exchange capacity. The column performance was evaluated using adsorbent bed height of 5.0 cm, with varying influent concentrations (10 mg/L and 50 mg/L) and flow rates (1.4 mL/min and 2.4 mL/min). The result shows that the breakthrough time for all metal ions ranged from 50 to 480 minutes. The maximum adsorption capacity was obtained at initial concentration of 10 mg/L and flow rate of 1.4 mL/min, with 2.22 mg/g of lead(II), 1.71 mg/g of cadmium(II) and 0.37 mg/g of manganese(II). The order of metal ions removal by natural bentonite is lead(II) > cadmium(II) > manganese(II). The sorption performance and the dynamic behaviour of the column were predicted using Adams-Bohart, Thomas, and Yoon-Nelson models. The linear regression analysis demonstrated that the Thomas and Yoon-Nelson models fitted well with the column adsorption data for all metal ions. The natural bentonite was effective for the treatment of wastewater laden with multi-metals, and the process parameters obtained from this work can be used at the industrial scale.
Chitosan ionic liquid beads were prepared from chitosan and 1-butyl-3-methylimidazolium based ionic liquids to remove Malachite Green (MG) from aqueous solutions. Batch adsorption experiments were carried out as a function of initial pH, adsorbent dosage, agitation time and initial MG concentration. The optimum conditions were obtained at pH 4.0, 0.008g of adsorbent dosage and 20min of agitation time were utilized in the kinetic and isotherm studies. Three kinetic models were applied to analyze the kinetic data and pseudo-second order was found to be the best fitted model with R2>0.999. In order to determine the adsorption capacity, the sorption data were analyzed using the linear form of Langmuir, Freundlich and Temkin equations. The isotherm was best fitted by Langmuir isotherm model. The maximum adsorption capacity (qmax) obtained from Langmuir isotherm for two chitosan beads 1-butyl-3-methylimidazolium acetate A and 1-butyl-3-methylimidazolium B are 8.07mgg-1 and 0.24mgg-1 respectively.
The main challenge in the lead removal simulation is the behaviour of non-linearity relationships between the process parameters. The conventional modelling technique usually deals with this problem by a linear method. The substitute modelling technique is an artificial neural network (ANN) system, and it is selected to reflect the non-linearity in the interaction among the variables in the function. Herein, synthesized deep eutectic solvents were used as a functionalized agent with carbon nanotubes as adsorbents of Pb2+. Different parameters were used in the adsorption study including pH (2.7 to 7), adsorbent dosage (5 to 20 mg), contact time (3 to 900 min) and Pb2+ initial concentration (3 to 60 mg/l). The number of experimental trials to feed and train the system was 158 runs conveyed in laboratory scale. Two ANN types were designed in this work, the feed-forward back-propagation and layer recurrent; both methods are compared based on their predictive proficiency in terms of the mean square error (MSE), root mean square error, relative root mean square error, mean absolute percentage error and determination coefficient (R2) based on the testing dataset. The ANN model of lead removal was subjected to accuracy determination and the results showed R2 of 0.9956 with MSE of 1.66 × 10-4. The maximum relative error is 14.93% for the feed-forward back-propagation neural network model.
A chitosan/polyvinyl alcohol (PVA)/zeolite composite was fabricated in this study. The composite was analyzed through field emission scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis, and weight loss test. FTIR and XRD results revealed a strong interaction among chitosan, PVA, and zeolite. Weight loss test results indicated that the composite was stable in acidic and basic media. Congo red was removed through flocculation, and the removal rate was 94% at an initial concentration of 100mg/L for a dose of 1g/L. The removal rate of methyl orange was controlled by adsorption at an initial concentration of less than 100mg/L. Flocculation occurred at high concentrations. The removal rate was also 94% at an initial concentration of 500mg/L for a dose of 5g/L. The adsorption behavior of the composite for the removal of methyl orange and Cr(VI) was described by using a pseudo-second-order kinetic model. The adsorption capacity of the composite for Cr(VI) was 450mg/g. Therefore, the synthesized composite exhibited versatility during the removal of dyes and heavy metals.