Methods to prepare biosorbents and magnetic sorbents for water treatment: a review

Access to drinkable water is becoming more and more challenging due to worldwide pollution and the cost of water treatments. Water and wastewater treatment by adsorption on solid materials is usually cheap and effective in removing contaminants, yet classical adsorbents are not sustainable because they are derived from fossil fuels, and they can induce secondary pollution. Therefore, biological sorbents made of modern biomass are increasingly studied as promising alternatives. Indeed, such biosorbents utilize biological waste that would otherwise pollute water systems, and they promote the circular economy. Here we review biosorbents, magnetic sorbents, and other cost-effective sorbents with emphasis on preparation methods, adsorbents types, adsorption mechanisms, and regeneration of spent adsorbents. Biosorbents are prepared from a wide range of materials, including wood, bacteria, algae, herbaceous materials, agricultural waste, and animal waste. Commonly removed contaminants comprise dyes, heavy metals, radionuclides, pharmaceuticals, and personal care products. Preparation methods include coprecipitation, thermal decomposition, microwave irradiation, chemical reduction, micro-emulsion, and arc discharge. Adsorbents can be classified into activated carbon, biochar, lignocellulosic waste, clays, zeolites, peat, and humic soils. We detail adsorption isotherms and kinetics. Regeneration methods comprise thermal and chemical regeneration and supercritical fluid desorption. We also discuss exhausted adsorbent management and disposal. We found that agro-waste biosorbents can remove up to 68–100% of dyes, while wooden, herbaceous, bacterial, and marine-based biosorbents can remove up to 55–99% of heavy metals. Animal waste-based biosorbents can remove 1–99% of heavy metals. The average removal efficiency of modified biosorbents is around 90–95%, but some treatments, such as cross-linked beads, may negatively affect their efficiency.

     

Efficient adsorption of carbon dioxide and methane on activated carbon prepared from glycerol with potassium acetate

In the context of global warming and the energy crisis, emissions to the atmosphere of greenhouse gases such as carbon dioxide (CO₂) and methane (CH₄) should be reduced, and biomethane from landfill biogas should be recycled. For this, there is a need for affordable technologies to capture carbon dioxide, such as adsorption of biogas on activated carbon produced from industrial wastes. Here we converted glycerol, a largely available by-product from biodiesel production, into activated carbon with the first use of potassium acetate as an activating agent. We studied adsorption of CO₂ and CH₄ on activated carbon. The results show that activated carbon adsorb CO₂ up to 20% activated carbon weight at 250 kPa, and 9% at atmospheric pressure. This is explained by high specific surface areas up to 1115 m²g⁻¹. Moreover, selectivity values up to 10.6 are observed for the separation of CO₂/CH₄. We also found that the equivalent CO₂ emissions from activated carbon synthesis are easily neutralized by their use, even in a small biogas production unit.

     

Removal of As(V) and Sb(V) in aqueous solution by Mg/Al-layered double hydroxide-incorporated polyethersulfone polymer beads (PES-LDH)

To develop a novel granular adsorbent to remove arsenic and antimony from water, calcined Mg/Al-layered double-hydroxide (CLDH)-incorporated polyethersulfone (PES) granular adsorbents (PES-LDH) were prepared using a core-shell method having 25% PES in an N,N-dimethylformamide solution. The PES-LDH displayed a spherical hollow shape having a rough surface and the average particle size of 1–2 mm. On the PES-LDH surface, nanosized CLDH (100–150 nm) was successfully immobilized by consolidation between PES and CLDH. The adsorption of Sb(V) by PES-LDH was found to be more favorable than for As(V), with the maximum adsorption capacity of As(V) and Sb(V) being 7.44 and 22.8 mg/g, respectively. The regeneration results indicated that a 0.5 M NaOH and 5 M NaCl mixed solution achieved an 80% regeneration efficiency in As(V) adsorption and desorption. However, the regeneration efficiency of Sb(V) gradually decreased due to its strong binding affinity, even though the PES-LDH showed much higher Sb(V) adsorption efficiency than As(V). This study suggested that PES-LDH could be a promising granular adsorbent for the remediation of As(V) and Sb(V) contained in wastewater.

     

High removal of phosphate from wastewater using silica sulfate

This report shows that silica sulfate is removing phosphate from wastewater very efficiently. Phosphorus removal and recovery from wastewater is a worldwide issue due to pollution of natural waters by phosphate and depletion of phosphate ores. Adsorption is a process that can remove phosphate at low concentrations. Adsorption also allows the recovery of phosphate for possible re-use. Here, we studied the adsorption of phosphate from wastewater using commercial Zr ferrite, Zr-MCM 41 and silica sulfate. We calculated equilibrium isotherms, kinetic models and thermodynamic effects under conditions similar to real wastewaters. We found that the equilibrium data for the adsorption of phosphate were best fitted to the Freundlich model. The results show that the maximum uptake of phosphate was 3.36 mg g⁻¹ for Zr-MCM, 27.73 mg g⁻¹ for Zr ferrite and 46.32 mg g⁻¹ for silica sulfate. The kinetic results of the three adsorbents were satisfactorily predicted using a pseudo-second-order model. We found that silica sulfate provided excellent characteristics in terms of the maximum adsorption and rate constant for the adsorption of phosphate. The thermodynamic data showed that increasing the temperature enhanced the adsorption of phosphate onto silica sulfate. Our findings will help to define efficient methods to remove phosphate from wastewater.     

As(III) adsorption onto Fe-impregnated food waste biochar: experimental investigation,modeling, and optimization using response surface methodology

Biochar derived from food waste was modified with Fe to enhance its adsorption capacity for As(III), which is the most toxic form of As. The synthesis of Fe-impregnated food waste biochar (Fe-FWB) was optimized using response surface methodology (RSM), and the pyrolysis time (1.0, 2.5, and 4.0 h), temperature (300, 450, and 600 °C), and Fe concentration (0.1, 0.3, and 0.5 M) were set as independent variables. The pyrolysis temperature and Fe concentration significantly influenced the As(III) removal, but the effect of pyrolysis time was insignificant. The optimum conditions for the synthesis of Fe-FWB were 1 h and 300 °C with a 0.42-M Fe concentration. Both physical and chemical properties of the optimized Fe-FWB were studied. They were also used for kinetic, equilibrium, thermodynamic, pH, and competing anion studies. Kinetic adsorption experiments demonstrated that the pseudo-second-order model had a superior fit for As(III) adsorption than the pseudo-first-order model. The maximum adsorption capacity derived from the Langmuir model was 119.5 mg/g, which surpassed that of other adsorbents published in the literature. Maximum As(III) adsorption occurred at an elevated pH in the range from 3 to 11 owing to the presence of As(III) as H₂AsO₃^? above a pH of 9.2. A slight reduction in As(III) adsorption was observed in the existence of bicarbonate, hydrogen phosphate, nitrate, and sulfate even at a high concentration of 10 mM. This study demonstrates that aqueous solutions can be treated using Fe-FWB, which is an affordable and readily available resource for As(III) removal.

     

Higher Cd adsorption on biogenic elemental selenium nanoparticles

Cadmium (Cd) is a carcinogenic metal contaminating the environment and ending up in wastewaters. There is therefore a need for improved methods to remove Cd by adsorption. Biogenic elemental selenium nanoparticles have been shown to adsorb Zn, Cu and Hg, but these nanoparticles have not been tested for Cd removal. Here we studied the time-dependency and adsorption isotherm of Cd onto biogenic elemental selenium nanoparticles using batch adsorption experiments. We measured ζ-potential values to assess the stability of nanoparticles loaded with Cd. Results show that the maximum Cd adsorption capacity amounts to 176.8 mg of Cd adsorbed per g of biogenic elemental selenium nanoparticles. The ζ-potential of Cd-loaded nanoparticles became less negative from ?32.7 to ?11.7 mV when exposing nanoparticles to an initial Cd concentration of 92.7 mg L^?1. This is the first study that demonstrates the high Cd uptake capacity of biogenic elemental selenium nanoparticles, of 176.8 mg g^?1, when compared to that of traditional adsorbents such as carboxyl-functionalized activated carbon, of 13.5 mg g^?1. An additional benefit is the easy solid–liquid separation by gravity settling due to coagulation of Cd-loaded biogenic elemental selenium nanoparticles.     

A review for chromium removal by carbon nanotubes

Water pollution is still a serious problem for the entire world. Adsorption technology is a promising process which is based on the fabrication of novel, cheap, non-dangerous and highly sorptive materials for application in wastewater purification processes. Nanomaterials are functional groups which find use in many important fields such as medicine, food processing and agriculture. This review collects information from published works about the use of carbon nanotubes as efficient and promising adsorbents in chromium removal from (real or synthesised) wastewater. For this purpose, isotherm (Langmuir, Freundlich, etc.), kinetic (pseudo-first-, second-order, etc.), thermodynamic (free-energy Gibbs, enthalpy, entropy) and desorption–regeneration studies were discussed in detail. Moreover, significant factors such as pH, agitation time, temperature, adsorbent dosage and initial dye concentration are also reported extensively. The maximum monolayer adsorption capacities of Cr(III) and Cr(VI) ions were 0.39–238.09 and 1.26–370.3?mg/g, respectively. The absolute values of ΔG⁰ and ΔH⁰ ranged 0.237–48.62 and 0.16–58.43?kJ/mol, respectively.     

High boron removal by functionalized magnesium ferrite nanopowders

Hydroxyl-enriched materials are promising boron adsorbents. However, the use of these materials is hampered by issues of separation, recovery, and selectivity, notably due to the presence of interfering ions. Therefore, we synthesized here a cheap magnetic nanopowder, which was further functionalized with polyvinyl alcohol and glycidol to produce boron-selective adsorbents. We studied their selectivity and removal efficiency using batch and fixed-bed systems. Sorption was studied at both concentrated and trace amounts of boron. Results show that nanopowders have 5.3–6.5 nm pore sizes and 145–203 m²/g surface areas, using Brunauer–Emmett–Teller analysis. Polyvinyl alcohol-functionalized particles removed 93 % of boron at 5 mg/L at pH 7 in 30 min, whereas only 68 % of boron was removed by glycidol-functionalized particles. However, at higher boron concentration, of 50 mg/L, glycidol-functionalized particles showed higher adsorption affinity of 68.9 mg/g. We conclude that internal hydroxyl groups of polyvinyl alcohol-functionalized particles are less accessible at higher boron concentration. This is the first report on magnesium ferrites for boron recovery. The spent adsorbents were separated easily from the aqueous media by an external magnet and repeatedly used. Overall, our findings demonstrated that the hydroxyl-enriched magnetic nanopowders are a better alternative to the existing boron adsorbents regarding magnetic separation, reusability, and selectivity.     

Sulfonated graphene nanomaterials for membrane antifouling,pollutant removal,and production of chemicals from biomass: a review

Water pollution and the unsustainable use of fossil fuel derivatives require advanced catalytic methods to clean waters and to produce fine chemicals from modern biomass. Classical homogeneous catalysts such as sulfuric, phosphoric, and hydrochloric acid are highly corrosive and non-recyclable, whereas heterogeneous catalysts appear promising for lignocellulosic waste depolymerization, pollutant degradation, and membrane antifouling. Here, we review the use of sulfonated graphene and sulfonated graphene oxide nanomaterials for improving membranes, pollutant adsorption and degradation, depolymerization of lignocellulosic waste, liquefaction of biomass, and production of fine chemicals. We also discuss the economy of oil production from biomass. Sulfonated graphene and sulfonated graphene oxide display an unusual large theoretical specific surface area of 2630 m²/g, allowing the reactants to easily enter the internal surface of graphene nanosheets and to reach active acid sites. Sulfonated graphene oxide is hydrophobic and has hydrophilic groups, such as hydroxyl, carboxyl, and epoxy, thus creating cavities on the graphene nanosheet’s surface. The adsorption capacity approached 2.3–2.4 mmol per gram for naphthalene and 1-naphthol. Concerning membranes, we observe an improvement of hydrophilicity, salt rejection, water flux, antifouling properties, and pollutant removal. The nanomaterials can be reused several times without losing catalytic activity due to the high stability originating from the stable carbon–sulfur bond between graphene and the sulfonic group.

     

Adsorption of vanadate(V) on Fe(III)/Cr(III) hydroxide waste

Adsorption of vanadate(V) from aqueous solution onto industrial solid ‘waste’ Fe(III)/Cr(III) hydroxide was investigated. HCl treated Fe(III)/Cr(III) hydroxide was found to be more efficient for the removal of vanadate(V) compared to untreated adsorbent. The adsorption follows second-order kinetics. Langmuir and Freundlich isotherms have been studied. The Langmuir adsorption capacity (Q ₀) of the treated and untreated adsorbents was found to be 11.43 and 4.67 mg g⁻¹, respectively. Thermodynamic parameters showed that the adsorption process was spontaneous and endothermic in the temperature range 32–60°C. Maximum adsorption was found at system pH 4.0. The adsorption mechanism was predominantly ion exchange. Effect of other anions such as phosphate, selenite, molybdate, nitrate, chloride, and sulfate on adsorption of vanadium has been examined.     

The origin of high hydrocarbon groundwater in shallow Triassic aquifer in Northwest Guizhou,China

Original high hydrocarbon groundwater represents a kind of groundwater in which hydrocarbon concentration exceeds 0.05 mg/L. The original high hydrocarbon will significantly reduce the environment capacity of hydrocarbon and lead environmental problems. For the past 5 years, we have carried out for a long-term monitoring of groundwater in shallow Triassic aquifer in Northwest Guizhou, China. We found the concentration of petroleum hydrocarbon was always above 0.05 mg/L. The low-level anthropogenic contamination cannot produce high hydrocarbon groundwater in the area. By using hydrocarbon potential, geochemistry and biomarker characteristic in rocks and shallow groundwater, we carried out a comprehensive study in Dalongjing (DLJ) groundwater system to determine the hydrocarbon source. We found a simplex hydrogeology setting, high-level water–rock–hydrocarbon interaction and obviously original hydrocarbon groundwater in DLJ system. The concentration of petroleum hydrocarbon in shallow aquifer was found to increase with the strong water–rock interaction. Higher hydrocarbon potential was found in the upper of Guanling formation (T₂g³) and upper of Yongningzhen formation (T₁yn⁴). Heavily saturated carbon was observed from shallow groundwater, which presented similar distribution to those from rocks, especially from the deeper groundwater. These results indicated that the high concentrations of original hydrocarbon in groundwater could be due to the hydrocarbon release from corrosion and extraction out of strata over time.

     

Adsorptive removal of mercury from acid mine drainage: a comparison of silica and maghemite nanoparticles

Mercury adsorption by silica and maghemite nanoparticles (NPs) was studied with the aim of comparing their performance in the remediation of acid mine drainage (AMD) contaminated water. Calculated distribution coefficients (K_d) showed that both NPs are exceptional adsorbents. However, adsorbate coverage per unit area was 30 times higher for maghemite than for silica NPs, despite the latter having a surface area ～15 times greater. Maghemite adsorbed 75% of available Hg compared to 56% by silica, making it a more efficient sorbent than silica under AMD conditions. Kinetics and isotherm data for both adsorbents were fitted by the pseudo-second-order (R² = 1) and the Freundlich (R² ≥ 0.98) models, implying that adsorption to both NP types was by chemisorption. Adsorption increased with NP concentrations and pH and was enhanced in the presence of manganese and sulfate ions although adsorption to silica was inhibited in 1:2 Hg-to-Mn systems. Importantly, trends in simulated wastewater were replicated in actual AMD-contaminated water samples. This study highlights the fact that properties besides surface area and charge of adsorbents determine adsorbent performance, and superior attributes may not always lead to higher adsorption efficiencies.     

Enhanced desorption of fluoxetine from polyethylene terephthalate microplastics in gastric fluid and sea water

There are concerns that microplastics act as a vector of pharmaceuticals in the aquatic environment. Most studies have focussed on pharmaceutical adsorption and have not investigated desorption in the various matrices that microplastics enter. Therefore we studied the desorption of the antidepressant drug fluoxetine from polyethylene terephthalate (PET) microplastics in river water, sea water, and simulated gastric and intestinal fluids. We found that most desorption occurred rapidly, within a few hours of exposure. Fluoxetine desorption fitted well to the Freundlich isotherm with r² values ranging from 0.97 to 0.99. Desorption decreased in the following order: gastric fluid at 20 °C and 37 °C; sea water at 20 °C; intestinal fluid at 20 °C and 37 °C; then river water at 20 °C. The little difference in desorption in gastrointestinal fluids at 20 °C and 37 °C suggests a similar exposure risk to cold- and warm-blooded organisms following PET microplastic ingestion. Total desorption following sequential incubation 2 h in gastric fluid then 4 h in intestinal fluid to mimic gastrointestinal digestion was 37% at 20 °C and 41% at 37 °C. Interestingly, higher desorption of 18–23% occurred in sea water compared to river water, of 4–11%. Under a worst-case scenario, more than 44 mg kg⁻¹ body weight d⁻¹ or more than 52 mg kg⁻¹ body weight d⁻¹ of PET microplastics from river water or sea water, respectively, need to be consumed to exceed the mammalian acceptable daily intake for fluoxetine. Further studies are needed on microplastic ingestion and the bioavailability of adsorbed pharmaceuticals to a range of exposed aquatic organisms.

     

Study of the interactions of dissolved organic matter with zinc ion and the impact of competitive metal ions (Ca2+ and Mg2+) by in situ absorbance

The bioavailability and toxicity of zinc to aquatic life depend on dissolved organic matter (DOM), such as Suwannee River Fulvic Acid (SRFA), which plays an important role in the speciation of zinc. This study examined reactions of SRFA with zinc at different concentrations from pH 3.0 to 9.0, and competitive binding of calcium/magnesium and zinc to SRFA at pH 6.0, using in situ absorbance. Interactions of Zn²⁺ with SRFA chromophores were evidenced by the emergence of features in Zn-differential spectra. Among all Zn²⁺–SRFA systems, dominant peaks, located at 235, 275 and 385 nm, and the highest intensity at 235 nm indicated the replacement of protons by the bound Zn²⁺. The Zn²⁺ binding with SRFA could be quantified by calculating the changes of the slopes of Zn-differential log-transformed absorbance in the wavelength range of 350–400 nm (denoted as DS_350–400) and by comparing the experimental data with predictions using the Non-Ideal Competitive Adsorption (NICA–Donnan) model. DS_350–400 was correlated well with the bound Zn²⁺ concentrations predicted by NICA–Donnan model with or without Ca²⁺ or Mg²⁺. Ca²⁺ and Mg²⁺ only affect intensity of the Zn-differential and Zn-differential log-transformed absorbance, not shape. In situ absorbance can be used to gain further information about Meⁿ⁺–DOM interactions in the presence of various metals.

     

Removal of selenite using ‘waste’ Fe(III)/Cr(III) hydroxide: Adsorption kinetics and isotherms

Removal of selenite [Se (IV)] from aqueous solution on to industrial solid ‘waste’ Fe(III)/Cr(III) hydroxide as adsorbent was investigated in the present article. Maximum adsorption was found to be at pH 4.0. Pretreated Fe(III)/Cr(III) hydroxide was found to be more efficient for the removal of selenite compared to untreated adsorbent. Langmuir and Freundlich isotherms have been studied. The Langmuir adsorption capacity (Q ₀) of the pretreated and untreated adsorbents was found to be 15.63 and 6.04?mg?g^?1, respectively. The adsorption process fit into the second-order kinetics. Thermodynamic parameters show that the adsorption process is spontaneous and endothermic in the temperature range 32 to 60°C. Coexisting anions vanadate and phosphate significantly affect the adsorption of selenite for both the pretreated and untreated adsorbents. Molybdate, thiocyanate, sulphate, nitrate and chloride do not significantly affect the removal of selenite for pretreated adsorbent.     

Synthesis and potential applications of cyclodextrin-based metal–organic frameworks: a review

Metal–organic frameworks are porous polymeric materials formed by linking metal ions with organic bridging ligands. Metal–organic frameworks are used as sensors, catalysts for organic transformations, biomass conversion, photovoltaics, electrochemical applications, gas storage and separation, and photocatalysis. Nonetheless, many actual metal–organic frameworks present limitations such as toxicity of preparation reagents and components, which make frameworks unusable for food and pharmaceutical applications. Here, we review the structure, synthesis and properties of cyclodextrin-based metal–organic frameworks that could be used in bioapplications. Synthetic methods include vapor diffusion, microwave-assisted, hydro/solvothermal, and ultrasound techniques. The vapor diffusion method can produce cyclodextrin-based metal–organic framework crystals with particle sizes ranging from 200 nm to 400 μm. Applications comprise food packaging, drug delivery, sensors, adsorbents, gas separation, and membranes. Cyclodextrin-based metal–organic frameworks showed loading efficacy of the bioactive compounds ranging from 3.29 to 97.80%.

     

Prediction of Cd toxicity to Daphnia magna in the mixture of multi-walled carbon nanotubes and kaolinite

In this study, we investigated cadmium toxicity created by adsorption kinetics in several mixtures containing two types of multi-walled carbon nanotubes (COOH-MWCNT and NH₂-MWCNT) and natural kaolinite. Characteristics of two types of MWCNTs were measured by zeta potential and ATR FT-IR graphs and TEM images. The solution of CNTs and kaolinite was tested to study Cd adsorption kinetics and mechanisms of differentiation-associated toxicity using Daphnia magna in a binary system (Cd–MWCNTs and Cd–kaolinite) and a ternary system (Cd–MWCNTs–kaolinite). In the binary system, Cd removal efficiency was nearly 100% and 40% for MWCNTs and kaolinite because of surface charge, respectively, with increasing sorbent concentration. In the ternary system, the trend of adsorption rate was similar to that of binary system. In comparison with percent mortality in the binary system, the solution in the ternary system showed higher toxicity due to the interaction of MWCNTs–kaolinite coagulated particles, thereby decreasing Cd adsorption onto CNTs and kaolinites. Overall, kaolinite can affect the adsorption process of Cd on MWCNTs in negative ways, depending on adsorption state. In conclusion, our studies suggest that kaolinite differs with adsorption ability of Cd by MWCNTs, and toxicity is likely to be produced by multivariable regression in the adsorption state.

     

Physicochemical aspects of using natural scavengers in removing methylene blue (basic dye) from solution

Effluent from dyeing and finishing processes is an important source of water pollution. The effectiveness of bentonite, kaolinite and sediment from a local deposit in removing methylene blue as a cationic dye from aqueous solutions has been investigated. The adsorption equilibrium (isotherm) has been determined according to Freundlich and Langmuir equations. The optimum amount is 0.5 g for all adsorbents, and the optimum pH ranges are 2–8 for bentonite and 2–6 for kaolinite and sediment. With respect to kinetic modelling, the adsorption of methylene blue on various adsorbents was fitted to a second-order equation. Also, the thermodynamic parameters were determined. The negative free energy values indicate the feasibility of the process and spontaneous nature of adsorption. The positive ΔH° values indicate the endothermic nature of the process. Thus, Egyptian clay minerals and sediments have a great tendency to remove the dye from solutions.     

Chemistry,abundance, detection and treatment of per- and polyfluoroalkyl substances in water: a review

Per- and polyfluoroalkyl substances (PFAS) encompass a wide range of compounds containing carbon–fluorine bonds. Due the strength of this bond and the high electronegativity of fluorine atoms, PFAS display stability, wettability and other characteristics that are unique for industrial applications and products. However, PFAS induce adverse effects on the environment and human health. Here we review the chemistry, synthesis, properties, analysis, occurrence in water, filtration, removal and oxydation of PFAS.  We highlight emerging hybrid treatments to remove PFAS from water.

     

Suitability of various chemically prepared activated carbons for the removal of copper(II) ions

Studies on the suitability of various chemically prepared activated carbons (CPACs) like straw carbon (SC), sawdust carbon (SDC), dates nut carbon (DNC) and commercial activated carbon (CAC) for the removal of copper(II) ions by adsorption from simulated wastewater have been carried out under batch mode at 30?±?1°C and the results are compared. The percentage removal of Cu(II) ions increased with a decrease in initial concentration, particle size and added electrolytes (ionic strength) and increased with an increase in contact time, dose of adsorbent and initial pH of the solution. The adsorption data were fitted with the Langmuir isotherm. The applicability of the first order kinetic equation viz. Lagergren equation was tested by correlation analysis. The adsorption process is concluded to be a spontaneous, first order reaction, occurring with increased randomness at the solid–liquid interface. Studies on the desorption of Cu²⁺-loaded activated carbons (ACs) were carried out with nitric acid (0.2–1?N). The possibility of reuse of the regenerated ACs in cycle (in cue-one after another) was tested. SC was found to be a suitable adsorbent alternative to CAC among CPACs for the removal of metal ions, in general, and Cu²⁺ ions, in particular.