Removal of ammonium and phosphates from aqueous solutions by biochar produced from agricultural waste

The concern about protecting water quantity and quality is one of the most severe challenges of the twenty-first century since the demand for water resources grows as the population and its needs grow. Additionally, and as expected, most human activities produce wastewater containing undesirable contaminants. On the other hand, the generation of agricultural waste and its inappropriate disposal causes further problems. Current wastewater treatment methods involve a combination of physical and chemical processes, technologies, and operations to remove pollutants from effluents; adsorption is an excellent example of an effective method for wastewater treatment, and biochar is currently one of the most valuable adsorbents. This review focuses on new research about applying biochar produced from agricultural waste as a low-cost and environmentally friendly method for removing ammonium and phosphates from aqueous solutions.

     

Graft Copolymerization of Methyl Acrylate onto Cellulosic Biofibers: Synthesis,Characterization and Applications

Graft copolymerization of cellulosic biopolymers with synthetic polymers is of enormous interest because of its application in biofiltration, biosorption, biomedical, biocomposites and various other eco-friendly materials. Synthesis of graft copolymers of methyl acrylate onto mercerized Grewia optiva biofibers using ferrous ammonium sulfate–potassium per sulfate as redox initiator in air was carried out. Different reaction parameters such as amount of solvent, monomer concentration, initiator molar ratio, reaction time and reaction temperature were optimized to get the maximum percentage of grafting. The graft copolymers thus formed were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and differential thermogravimetric techniques. A plausible mechanism for explanation of the graft copolymerization reactions pattern shown is offered. The effect of grafting percentage on the physico–chemical properties of raw as well as grafted Grewia optiva biofibers has also been investigated. The graft copolymers have been found to be more moisture resistant and also showed better chemical and thermal resistance. Green polymer composites were also successfully prepared through compression molding technique by using grafted Grewia optiva biofibers as reinforcement.     

Wastewater Fines Influence the Adsorption Behavior of Pollutants onto Microplastics

Millions of tons of microplastics (MPs) enter the wastewater collection systems every day and interact with raw sewage. In addition to MPs, varieties of organic and inorganic fines from urban effluents release into the sewer system and provide suitable surfaces for adsorption. To better understand the quantitative assessment of MPs sorption in wastewater and the role of fines, batch reactor experiments were performed using synthetic wastewater solutions containing organic, inorganic, and mixed organic–inorganic fines, and the results compared to a solution without fines. The MPs were two types of clean polypropylene (PP) particles, isotactic (iPP) and atactic (aPP). The results showed in all applied solutions the adsorption of pollutants was higher for the aPP averaging 1.3 mg/g compared with 0.5 mg/g for iPP, indicating that the adsorption varies with the type of polymer and surface properties. Further experiments also revealed a decrease in the sorption values of MPs for solutions containing inorganic fines, measured as the partition coefficient (K_d) and adsorbed concentration at equilibrium (q_e). The result of the measured reference conductivity (к₂₅) of the solutions for the same tests showed similar trends indicating that the magnitude of pollution adsorption onto MPs surfaces is controlled by the surface charge potential of the fine particles. The relationship between the qualitative assessments of ion removal, measured in terms of к₂₅, and their quantitative assessment of adsorption values in terms of K_d in several identical tests, verifying that the conductivity of the solution was modified after adsorption of wastewater constituents onto the MPs.

     

The development of low cost adsorbents from clay and waste materials: a review

Increased energy consumption due to industrial growth has increased the levels of carbon dioxide (CO₂) emission being released into the atmosphere. CO₂ emission is a type of greenhouse gas which is a major cause of global warming. Since the issue of CO₂ emissions has drawn much attention in recent years, the development of CO₂ capture technology has become a necessity. Although CO₂ adsorbents are still at the early development stage, it has been suggested that CO₂ adsorbents are the most effective technology in controlling CO₂ emissions. Solid adsorbents have great potential as an alternative method to conventional adsorbents in adsorbing CO₂. In this paper, low cost adsorbents including activated carbon, zeolites, mesoporous silica and clays are discussed in terms of adsorbent preparation methods and CO₂ adsorption capacity. The low cost adsorbents are mainly derived from waste materials such as fly ash, steel slag, red mud, bagasses wastes and wood wastes. Besides that, natural resources such as clays have also been applied as low cost CO₂ adsorbents. Surface modifications have also been applied to the low cost adsorbents, including metal ion exchange and amine impregnation to enhance CO₂ adsorption capacity. In the last section, the current status of CO₂ adsorbents is summarized and future trends are discussed briefly to predict the potential materials which can be applied as CO₂ adsorbents.     

Evaluation of synthetic adsorbents for cleanup of herbicide-laden wastewater

Small-and large-scale farm operators and applicators urgently need user-friendly and cost-effective on-site methods to treat dilute-formulated herbicide-laden wastewater (i.e., rinsate). In this study, we investigated solvent-regenerable synthetic adsorbents, Ambersorb® 563 adsorbent, Ambersorb 572 adsorbent, and Ambersorb 575 adsorbent, as alternatives to activated carbon (Filtrasorb ® 400) for cleanup of water containing Dual 8E (a.i., metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide]) or Banvel 4L (a.i., dicamba [3,6-dichloro-2-methoxybenzoic acid]). Batch-type adsorption experiments were conducted to compare adsorptive capacities of the various adsorbents. Adsorption maxima, obtained from adsorption isotherms, indicated that of the Ambersorb adsorbents tested, Ambersorb 572 adsorbent generally exhibited the highest adsorptive capacities for the herbicides tested and was comparable to Filtrasorb 400. Solvent (methanol) regenerability studies demonstrated that herbicide was readily recovered from Ambersorb 572 adsorbent and Filtrasorb 400. In general, metolachlor was more readily recoverable than dicamba. In fixed-bed column studies, Ambersorb 572 adsorbent exhibited twice the adsorptive capacity of Filtrasorb 400. Fixed-bed columns were more effective in removing metolachlor from herbicide containing water regardless of the adsorbent used. Multicycling of Ambersorb 572 adsorbent resulted in 30% loss of adsorptive capacity for dicamba as Banvel 4L and no loss of adsorptive capacity for metolachlor as Dual 8E. Working capacity was reached after three adsorption-regeneration cycles. Fixed-bed columns packed with solvent-regenerable adsorbents may prove useful as part of an on-site wastewater disposal system.     

Synthesis and Characterization of Chitosan-Grafted-Poly(2-Hydroxyaniline) Microstructures for Water Decontamination

Chitosan as a biopolymer, biodegradable, safe, non-toxic and widely abundant in nature was grafted with poly(2-hydroxyaniline) (P2-HA) through aqueous chemical oxidative copolymerization using ammonium persulphate in acetic acid medium. The grafting conditions were studied by varying grafting parameters. The effect of oxidant, 2-hydroxyaniline (2-HA) and acetic acid concentrations on the rate of copolymerization was studied. The synthesized graft characterized using UV–Vis, FTIR, TGA, XRD, and scanning electron microscope and compared with chitosan and P2-HA. The grafting enhances the thermal properties of chitosan. The effect of temperature on the rate of grafting copolymerization reaction was studied. The apparent activation energy (Ea) of the copolymerization reaction found to be 21.1116 kJ/mol. Also, ΔH^* and ΔS^*, were calculated and found to 22.8630 kJ/mol and ?109.4290 J/mol K respectively. The mechanism of the grafting copolymerization reaction discussed. Chitosan, P2-HA and chitosan-graft-P2-HA used for the removal of Cr, Fe, Mn, Cu and Zn divalent ions from a contaminated water samples. The adsorption isotherm parameters are given.     

A Study on Benzoylation and Graft Copolymerization of Lignocellulosic Cannabis indica Fiber

Present work deals with the surface modification of Cannabis indica fiber through benzoylation and graft copolymerization of acrylonitrile (AN) onto C. indica fibers under the influence of microwave radiations. The Benzoylation of C. indica fiber was carried out by treating raw fiber with varying concentrations of benzoyl chloride solution. Different reaction parameters for graft copolymerization, such as reaction time, initiator concentration, nitric acid concentration, pH and monomer concentration were optimized to get the maximum percentage of grafting (25.54%). A suitable mechanism to explain benzoylation and graft copolymerization has been also proposed. Raw C. indica fiber, graft copolymerized and benzoylated fibers were subjected to evaluation of some of their properties like swelling behavior, moisture absorbance and resistance towards chemicals. Cannabis indica fibers treated with 5% benzoyl chloride solution and AN graft copolymerized fibers have been found to show more resistant towards moisture, water and chemicals when compared with that of untreated fibers. Morphological, structural changes, thermal stability and crystallanity of raw, graft copolymerized and benzoylated fibers have also been studied by SEM, FTIR, TGA and XRD techniques. It has been observed that the crystallinity of fiber decreases but thermal stability increases on surface modification.     

Flocculants—an Ecofriendly Approach

Although water-soluble synthetic polymers find wide applications as flocculants, the potential problem associated with their use is lack of biodegradability and high cost. Polysaccharides owing to their distinctive features like ability to undergo different chemical reactions, biodegradability and sustainability inspire hope to obtain effective, economical viable and safe substitute of the synthetic flocculants. In this regard, chemical modification of Cassia tora and guar gum was carried out through different substitution and grafting reactions. The modified products were tested against kaolin under laboratory conditions vis-a-vis polyacrylamide based synthetic flocculant.     

煤矸石的改性及其对稀土生产废水中氨氮的吸附

采用热改性、盐酸改性、硫酸改性、碱改性的方法分别制备了4种改性煤矸石吸附剂,研究了吸附工艺条件对4种改性煤矸石吸附剂对稀土生产废水中氨氮去除效果的影响以及吸附机理.实验结果表明:4种改性煤矸石吸附剂吸附氨氮的最佳工艺条件为:吸附剂加入量0.02 g/mL,振荡时间2.5 h,废水pH 7～8;4种吸附剂氨氮去除率大小顺序为:碱改性煤矸石＞硫酸改性煤矸石＞盐酸改性煤矸石＞热改性煤矸石;碱改性煤矸石的氨氮去除率最高,为59.19％;碱改性煤矸石吸附剂对含氨废水中氨氮的吸附较好地符合Langmuir方程和Freundlich方程,在一定程度上符合Temkin方程.     

Synthesis and Characterization of a Thin-Film Composite Nanofiltration Membrane Based on Polyamide-Cellulose Acetate: Application for Water Purification

Membrane separation has been widely used for various applications including microfiltration (MF), ultrafiltration (UF), and nanofiltration (NF) processes in the fields of biomedicine, food, and water purification. In this work, a facile synthesis of new polyamide thin-film composite nanofiltration membranes (NF-TFC) for water purification was described. The polyamide thin film was deposed over a synthetic cellulose acetate (CA) support by interfacial polymerization method. 1,3 cyclohexane bis (methylamine) (CHMA) and trimesoyl chloride (TMC) were used as monomers. The membranes were characterized using Scanning Electron Microscopy (SEM), Fourier Transform Infrared spectroscopy (FT-IR), water uptake, porosity, contact angle, water permeability and rejection towards specific salt and dye molecules. The effect of the variation of the CHMA concentration (0.2–2 wt.%) on the morphology, porosity, water permeation and rejection properties of the prepared membranes was studied. SEM results displayed the growth of the membrane thickness when the CHMA concentration increased from 0.2 to 2 wt.%. The strong adhesion between the cellulose acetate substrate and the polyamide layer explained by the formation of the polyamide film in the substrate surface and inside the pores. The water permeability varied from 36.02 to 17.09 L h^?1 m^?2 bar^?1. The salt rejection of Na₂SO₄ and NaCl increased from 9 to 68% and from 38.41% to 89.4%, respectively, when the CHMA concentration was changed from 0.2 to 2 wt.%. The prepared membranes were further applied successfully for the removal of malachite green and congo red. The results indicated that the maximum rejection reached 89% and 85% for malachite green and congo red, respectively.

     

膨润土吸附水中有机污染物的应用进展

论述了膨润土的吸附机理,介绍了膨润土的物理及化学改性方法及其对有机染料废水,焦化废水,烟草废水,煤泥水,含酚类、石油烃类、抗生素废水及微污染水等的处理效果。针对膨润土作为环保吸附剂存在的问题指出了今后的研究方向:1)将研究成果应用于实际废水;2)研究环境友好且效果好的改性工艺及材料;3)研究新的吸附剂制备形式;4)加大膨润土在废气处理上的研究力度;5)研制吸附效果更佳且能处理复杂成分污水的新型复合吸附剂。     

An Overview on Starch-Based Sustainable Hydrogels: Potential Applications and Aspects

Hydrogels are a kind of three dimensional polymeric network system which has a significant amount of water imbibing capacity despite being soluble in it. Because of the potential applications of hydrogels in different fields such as biomedical, pharmaceutical, personal care products, biosensors, and cosmetics, it has become a very popular area of research in recent decades. Hydrogels, prepared from synthetic polymers and petrochemicals are not ecofriendly. For preparing biodegradable hydrogels, most available plant polysaccharides like starch are utilized. In its structure, starch has a large number of hydroxyl groups that aid in hydrogel networking. For their easy availability and applications, starch-based hydrogels (SHs) have gained huge attention. Moreover, SHs are non-toxic, biocompatible, and cheap. For these reasons, SHs can be an alternative to synthetic hydrogels. The main focus of this review is to provide a comprehensive summary of the structure and characteristics of starch, preparation, and characterization of SHs. This review also addresses several potential multidimensional applications of SHs and shows some future aspects in accordance.

Graphic abstract

     

Handling leachate from glass cullet stockpiles

Mixed glass cullet (crushed recycled glass containers) is stockpiled uncovered before use as roadway construction aggregate or daily cover in landfills. Rainwater that leaches through the stockpiles dissolves and suspends contaminants such as those from food residuals and paper labels. The objective of this study was to determine leachate quantity and quality from cullet stockpiles as a basis for development of Best Management Practices (BMPs). Four 35-tonne field stockpiles were set up for leachate analysis and to determine the effects of mechanical turning treatment on the leachate. Field-collected leachate and laboratory-generated washwater of cullet (water:cullet = 3:1 by weight) were both analyzed for basic wastewater parameters, which showed pollutant levels comparable to or higher than those of untreated domestic wastewater or urban stormwater. While organic contamination decreased substantially (e.g., washwater BOD > 95% reduction), TKN and total-phosphorus levels in leachate ranged between 11.6–154 mg L^?1 and 1.6–12.0 mg L^?1, respectively, and remained comparable to levels found in untreated domestic wastewater after four months. Turning enhanced the degradation of the organic constituents inside the stockpiles, which was confirmed by elevated temperatures. Based on this study, leachate from glass cullet stockpiles should not be released to surface water. For leachate from long-term cullet stockpiles, release to groundwater should be only done after treatment to reduce nitrogen levels.     

A sustainable system for decontamination of cephalexin antibiotic using electrocoagulation technology and response surface methodology

The emergence of synthetic micropollutants in wastewater due to domestic and industrial use has presented new challenges for treatment processes. Among these pollutants, pharmaceutical and personal care products (PPCPs) are considered emerging contaminants due to their potential to enter drinking water sources. Antibiotics, in particular, are of significant concern due to their high consumption in veterinary and human applications. In this study, the electrocoagulation (EC) process is used as an efficient technique for the removal of cephalexin (CFX) from pharmaceutical wastewater. The study aims to explore the ability of the EC process to remove CFX and optimize its performance using the response surface method based on Central Composite Design (RSM-CCD). The effects of initial CFX concentration, electrolysis time, initial pH, and electrode type (non-insulated and insulated) were considered in the optimization process. This research is distinct as it examines the influence of key factors on the elimination of CFX. The results showed that electrolysis time had the most significant effect on CFX removal using the EC process. The analysis of variance (ANOVA) test was used to evaluate the importance of independent variables and their interaction. The optimal operating conditions for maximum removal efficiency (86.53%) were an initial CFX concentration, reaction time, and initial pH of 34 mg/L, 34.35 min, and 6.5, respectively, using an insulated electrode. Under these optimal conditions, predicted CFX removal was 93.54%. These findings demonstrate that RSM-CCD is a useful tool for optimizing electrochemical removal processes for micropollutants such as CFX from wastewater streams. The study highlights the importance of considering electrode type in optimizing EC processes for micropollutant removal from wastewater.     

Potential of microalgae Bio-Coke as a sustainable solid fuel alternative to coal coke

Energy and environmental issues have triggered the search for new sources of green energy alternatives in recent years. Biofuel production from renewable sources is widely considered one of the most sustainable alternatives for environmental and economic sustainability. Microalgae are currently being promoted as one of the most promising liquid biofuel feedstocks due to their rapid growth, high lipid production capacity, and carbon–neutral cycle. In this study, whole microalgae cells were utilized as raw material to produce solid biofuel, i.e., Bio-Coke, and this study aimed to investigate the possibility of microalgae Bio-Coke as an alternative to coal coke. The results show that Bio-Coke can be produced from microalgae in the temperature range of 80–100 °C. The apparent density is between 1.253 and 1.261 g/cm³, comparable to the apparent density of lignocellulosic Bio-Coke. Additionally, the calorific value is higher than the calorific value of lignocellulosic Bio-Coke and within the range of the calorific value of subbituminous coal. Therefore, microalgae Bio-Coke can be utilized to replace coal coke usage in the future.

     

Priority and emerging pollutants in sewage sludge and fate during sludge treatment

This paper aims at characterizing the quality of different treated sludges from Paris conurbation in terms of micropollutants and assessing their fate during different sludge treatment processes (STP). To achieve this, a large panel of priority and emerging pollutants (n = 117) have been monitored in different STPs from Parisian wastewater treatment plants including anaerobic digestion, thermal drying, centrifugation and a sludge cake production unit. Considering the quality of treated sludges, comparable micropollutant patterns are found for the different sludges investigated (in mg/kg DM – dry matter). 35 compounds were detected in treated sludges. Some compounds (metals, organotins, alkylphenols, DEHP) are found in every kinds of sludge while pesticides or VOCs are never detected. Sludge cake is the most contaminated sludge, resulting from concentration phenomenon during different treatments. As regards treatments, both centrifugation and thermal drying have broadly no important impact on sludge contamination for metals and organic compounds, even if a slight removal seems to be possible with thermal drying for several compounds by abiotic transfers. Three different behaviors can be highlighted in anaerobic digestion: (i) no removal (metals), (ii) removal following dry matter (DM) elimination (organotins and NP) and iii) removal higher than DM (alkylphenols – except NP – BDE 209 and DEHP). Thus, this process allows a clear removal of biodegradable micropollutants which could be potentially significantly improved by increasing DM removal through operational parameters modifications (retention time, temperature, pre-treatment, etc.).     

Evaluating the strength development of mortar using clinker fine aggregate with a combination of fly ash and its inhibitory effects on alkali–silica reaction and delayed ettringite formation

The aggregate composed of cement clinker, an intermediate cement product, improves strength development and mass transfer resistance of concrete. Fly ash (FA) is a supplementary cementitious material that can be substituted by cement. This study investigated the strength development of highly FA-substituted mortar mixed with cement clinker fine aggregate (CL) and tested its inhibitory effect against the alkali–silica reaction (ASR). In addition to these, this study provides the testing results of evaluating the effects of using cement clinker fine aggregate on delayed ettringite formation (DEF), which can be problematic for precast concrete products. The study results revealed that at 91 days of age, in the case of 80% replacement ratio of fly ash to cement, using CL exhibited similar strength development as mortar with limestone fine aggregate and no FA substitution. Furthermore, mortars with 70% and 80% FA substitution did not exhibit clear ASR-induced expansion even at 182 days of age. Lastly, mortar using clinker fine aggregate could suppress DEF-induced expansion at 182 days of age, which was similar to the effect obtained using FA. These results can promote the utilization of CL resources for concrete and using clinker as fine aggregate in precast concrete products.

     

Effective bioremoval of Fe(III) ions using paprika (Capsicum annuum L.) pomace generated in the food industry

In these studies, removal of Fe(III) ions by biosorption processes from aqueous solutions was carried out using paprika (Capsicum annuum L.) pomace generated during processing in the food industry. The biosorbent material was characterized using several analytical methods, including particle size distribution, XRD, SEM–EDS, electrokinetic zeta potential, surface area analysis (BET, BJH), thermogravimetry, morphology (SEM), spectrophotometry FT-IR. Several factors, such as biosorbent dosage, initial concentration, contact time and initial pH were analyzed to show an effect on the bioremoval process, efficiency and adsorption capacity. As a result, the maximum adsorption efficiency and capacity were determined to be 99.1% and 7.92 mg/g, respectively. Based on the kinetics analysis, the bioremoval process is better described by the Langmuir isotherm model and the pseudo-second order equation model. In conclusion, the achieved research results suggest that paprika biomass can be an effective material for efficiently removing iron(III) from wastewater and improving water quality. These studies on the recovery of iron metal from the environment fit in the latest trends in the concept of the global circular economy.

     

A case study for a cost-benefit-based,stepwise optimization of thermo-chemical WAS pre-treatment for anaerobic digestion

Waste-activated sludge (WAS) may be considered a resource generated by wastewater treatment plants and used for biogas-generation but it requires pre-treatment (PT) for enhanced biogas-yields and reduced WAS disposal costs. To date, a number of studies on the optimization of such PT focused on improved biogas yields but neglected inferred energy and resource consumption. Here, we aimed to identify the most promising thermo-chemical PT-strategy in terms of net energy output and cost-efficiency by optimizing PT temperature and the amount and sort of the alkaline reagent used. We compared methane-potentials and disposal costs of untreated and treated WAS and conducted an annual cost-benefit calculation. We defined 70 °C and 0.04 M NaOH as ideal PT-conditions being both, low-energy demanding and efficient. Applying these conditions, enhanced biogas-yields and improved dewaterability led to reduced electricity and disposal costs of 22 and 27%, respectively, resulting in savings of approx. 28% of the yearly WAS-related expenditures of a wastewater treatment plant. Despite multiple benefits in running costs, the implementation of WAS-PT was not recommendable in the presented case study due to high investment costs.

     

Adsorptive Separation of Lysozyme from Aqueous Solutions Using Sulphonyl and Carboxyl Functionalized Stearyl Alcohol Grafted Epichlorohydrin

In the present work ability of the two novel adsorbents, sulphonyl and carboxyl functionalized stearyl alcohol-grafted epichlorohydrin, SA-g-E-SO₃H, SA-g-E-COOH; to remove lysozyme (LYZ) from aqueous solution was assessed. The adsorbent characterization was done using FTIR, XRD, SEM and TGA analyses. The adsorption efficiency was influenced by solution pH and the optimum operating pH was found to be 4.0 for SA-g-E-SO₃H and 5.0 for SA-g-E-COOH and their adsorption efficiency was evaluated using the various isotherm and kinetics models. The Sips isotherm model and pseudo-second-order kinetic model were found to be the best for describing the equilibrium and kinetic behaviors of the adsorption process. Batch adsorption/desorption studies in acidic medium, for over six cycles showed excellent regeneration capability of the adsorbents and could lead to the development of viable and promising technology for the adsorptive recovery of LYZ from aqueous solutions. The efficiency of the adsorbents for the LYZ adsorption was verified using egg white. The result obtained from this study revealed that adsorption ability of 25 mg of SA-g-E-COOH is 98.4 % which is more than that of SA-g-E-SO₃H (96.2 %). The efficiency of SA-g-E-SO₃H to remove LYZ from aqueous solution was found to be higher compared to SA-g-E-COOH.