Coagulation Behavior of Antimony Oxyanions in Water: Influence of pH, Inorganic and Organic Matter on the Physicochemical Characteristics of Iron Precipitates.

The presence of inorganic and organic substances may alter the physicochemical properties of iron (Fe) salt precipitates, thereby stabilizing the antimony (Sb) oxyanions in potable water during the chemical treatment process. Therefore, the present study aimed to examine the surface characteristics, size of Fe flocs and coagulation performance of Sb oxyanions under different aqueous matrices. The results showed that surface properties of Fe flocs significantly varies with pH in both Sb(III, V) suspensions, thereby increasing the mobility of Sb(V) ions in alkaline conditions. The negligible change in surface characteristics of Fe flocs was observed in pure water and Sb(III, V) suspension at pH 7. The key role of Van der Waals forces of attraction as well as hydration force in the aggregation of early formed flocs were found, with greater agglomeration capability at higher more ferric chloride dosage. The higher Sb(V) loading decreased the size of Fe flocs and reversed the surface charge of precipitates, resulting in a significant reduction in Sb(V) removal efficiency. The competitive inhibition effect on Sb(III, V) removal was noticed in the presence of phosphate anions, owing to lowering of ζ-potential values towards more negative trajectory. The presence of hydrophobic organic matter (humic acid) significantly altered the surface characteristics of Fe flocs, thereby affecting the coagulation behavior of Sb in water as compared to the hydrophilic (salicylic acid). Overall, the findings of this research may provide a new insight into the variation in physicochemical characteristics of Fe flocs and Sb removal behavior in the presence of inorganic and organic compounds during the drinking water treatment process.

Enhanced removal of phosphate using pomegranate peel-modified nickel­lanthanum hydroxide.

In this work, a bimetallic Ni/La nanoparticle-laded biosorbent was fabricated from pomegranate fibers by solvothermal synthesis method. The material exhibited a high-efficient phosphate removal capability. The results of the characterization analysis showed that the surface of pomegranate fibers was rough and evenly coated with Ni and La after modification, and the specific surface area of Ni-La@Peel increased to 50.20 m2/g, providing a large number of adsorption sites for phosphate removal. The maximum phosphate removal rate of adsorbent was higher than 97% in a wide pH range (3.7-10.8). The maximum adsorption capacities of Ni-La@Peel were 226.55 mg-P/g and 220.31 mg-P/g under alkaline and acidic conditions, respectively, as calculated using the Langmuir model. Meanwhile, all the results were consistent with the Langmuir isothermal (R2 = 0.99) and kinetic pseudo-second order models (R2 = 0.99), indicating that the phosphate removal mechanism of Ni-La@Peel was mainly related to homogeneous chemisorption. Experimental results showed that in the presence of other anions, such as chloride, sulfate, nitrate, bromide and fluoride, the adsorption capacity of phosphate was only reduced by about 10% compared to the blank sample individually. In addition, the phosphate removal efficiency of Ni-La@Peel remained 82.05% at 7th adsorption-desorption cycle. These findings show that Ni-La@Peel is a promising material for purification of phosphate-containing wastewater.

Use of ballasted flocculation (BF) sludge for the manufacturing of lightweight aggregates.

Ballasted flocculation (BF) is an efficient way to remove the turbidity from surface water. The objective of the present study is to optimize the ballast (magnetite), coagulant (poly aluminum chloride) concentration and pH for efficient turbidity removal from surface water. To do this, the sludge produced from an optimized dose of a BF treatment was utilized for the production of lightweight (LW) aggregates by combining it with hard clay and sewage sludge. The LW aggregates were formed by means of rapid sintering in the temperature range of 1000-1200 °C with an exposure time of 10 min. The physical properties of the LW aggregates, in this case the leaching of heavy metals, the bulk density and the microstructure, were investigated. The results indicated that corresponding ballast and coagulant concentrations of 0.75 g/L and 30 mg/L (poly aluminum chloride (PAC)) resulted in the maximum removal efficiency of ≈95%. Using a mixture of BF sludge (30 wt%), dry sewage sludge (20 wt%), and hard clay (50 wt%), aggregates with a density of around 1.0 g/cm3 could be produced. In addition, it was confirmed that the manufactured aggregate was environmentally stable as the elution of heavy metals was suppressed.

Adsorption Capacities of Iron Hydroxide for Arsenate and Arsenite Removal from Water by Chemical Coagulation: Kinetics, Thermodynamics and Equilibrium Studies.

Arsenic (As)-laden wastewater may pose a threat to biodiversity when released into soil and water bodies without treatment. The current study investigated the sorption properties of both As(III, V) oxyanions onto iron hydroxide (FHO) by chemical coagulation. The potential mechanisms were identified using the adsorption models, ζ-potential, X-ray diffraction (XRD) and Fourier Transform Infrared Spectrometry (FT-IR) analysis. The results indicate that the sorption kinetics of pentavalent and trivalent As species closely followed the pseudo-second-order model, and the adsorption rates of both toxicants were remarkably governed by pH as well as the quantity of FHO in suspension. Notably, the FHO formation was directly related to the amount of ferric chloride (FC) coagulant added in the solution. The sorption isotherm results show a better maximum sorption capacity for pentavalent As ions than trivalent species, with the same amount of FHO in the suspensions. The thermodynamic study suggests that the sorption process was spontaneously exothermic with increased randomness. The ζ-potential, FT-IR and XRD analyses confirm that a strong Fe-O bond with As(V) and the closeness of the surface potential of the bonded complex to the point of zero charge (pHzpc) resulted in the higher adsorption affinity of pentavalent As species than trivalent ions in most aquatic conditions. Moreover, the presence of sulfates, phosphates, and humic and salicylic acid significantly affected the As(III, V) sorption performance by altering the surface properties of Fe precipitates. The combined effect of charge neutralization, complexation, oxidation and multilayer chemisorption was identified as a major removal mechanism. These findings may provide some understanding regarding the fate, transport and adsorption properties onto FHO of As oxyanions in a complex water environment.

Synergetic Effect of Organic Flocculant and Montmorillonite Clay on the Removal of Nano-CuO by Coagulation-Flocculation-Sedimentation Process.

The widespread usage of nano-copper oxide particles (nano-CuO) in several industrial products and applications raises concerns about their release into water bodies. Thus, their elimination from drinking water is essential to reduce the risk to human health. This work investigated the removal of nano-CuO from pure water and montmorillonite clay (MC) suspensions using poly aluminum ferric chloride (PAFC) as well as cationic polyacrylamide (PAM) by the coagulation-flocculation-sedimentation (C/F/S) process. Moreover, the PAFC and PAFC/PAM flocculation performance for various nano-CuO particles concentrations, dosages, pH, settling times and stirring speeds were also investigated. The findings showed that the removal of nano-CuO and turbidity in MC suspension were higher as compared to pure water. Moreover, the combined effect of PAFC/PAM on the elimination of nano-CuO and turbidity was also substantially better than the individual use of PAFC or PAM. The efficient removal of CuO was observed in the solution containing higher mass concentration in the order (10 mg/L > 2.5 mg/L > 1 mg/L) with an increased coagulant dose. The improved removal performance of nano-CuO was observed in a pH range of 7-11 under various water matrices. The C/F/S conditions of nano-CuO were further optimized by the Box-Behnken statistical experiment design and response surface methodology. The PAFC/PAM dose resulted in the maximum removal of nano-CuO (10 mg/L) in both pure water (>97%) and MC suspension (>99%). The results of particle monitoring and Fourier transform infrared of composite flocs revealed that the main removal mechanism of nano-CuO may be the combined effect of neutralization, complexation as well as adsorption.

Removal of Tannic Acid Stabilizes CuO Nanoparticles from Aqueous Media by PAFC: Effect of Process Conditions and Water Chemistry.

The increased utilization of CuO nanoparticles (CuO NPs) in various fields has raised concerns about their discharge into water containing a wide range of organic ligands. Moreover, the adsorption of these ligands can stabilize the CuO NPs in drinking water treatment plants. Thus, their removal from potable water is important to mitigate the risk to humans. The present study explored the efficacy of the coagulation-sedimentation (C/S) process for the removal of tannic acid (TA)-stabilized CuO NPs using polyaluminum ferric chloride (PAFC) as a coagulant. Moreover, the influence of process conditions (stirring speed) and water chemistry (i.e., pH and ionic strength (IS)) were also investigated to determine their impact on removal. The results showed that stirring speed in the reaction phase significantly affected the removal due to increased flocculation compared with stirring speed in the mixing phase. In addition, pH and IS affect the colloidal stability and removal efficiency of CuO NPs. A relatively better removal performance (<99%) of CuO NPs was found at lower coagulant dosage in the pH range 6-8. The addition of organic ligands reversed the surface charge potential and enhanced the colloidal stability of CuO NPs, resulting in the destabilization of TA-CuO NPs, thereby reducing the optimum PAFC dosage for removal. By contrast, the IS above the critical coagulation concentration decreased the removal efficiency due to inhibition of the ionic activity of PAFC hydrolysate in the aqueous environment. Fourier transform infrared findings of TA-CuO NPs composite flocs suggest that the primary removal mechanism might be mediated via the combined effect of neutralization, complexation as well as adsorption.

Removal of Arsenic Oxyanions from Water by Ferric Chloride-Optimization of Process Conditions and Implications for Improving Coagulation Performance.

The chronic ingestion of arsenic (As) contaminated water has raised significant health concerns worldwide. Iron-based coagulants have been widely used to remove As oxyanions from drinking water sources. In addition, the system's ability to lower As within the maximum acceptable contamination level (MCL) is critical for protecting human health from its detrimental effects. Accordingly, the current study comprehensively investigates the performance of As removal under various influencing factors including pH, contact time, temperature, As (III, V) concentration, ferric chloride (FC) dose, and interfering ions. The optimum pH for As (V) removal with FC was found to be pH 6-7, and it gradually decreased as the pH increased. In contrast, As (III) removal increased with an increase in pH with an optimum pH range of 7-10. The adsorption of As on precipitated iron hydroxide (FHO) was better fitted with pseudo-second order and modified Langmuir-Freundlich models. The antagonistic effect of temperature on As removal with FC was observed, with optimum temperature of 15-25 °C. After critically evaluating the optimum operating conditions, the uptake indices of both As species were developed to select appropriate an FC dose for achieving the MCL level. The results show that the relationship between residual concentration, FC dose, and adsorption affinity of the system was well represented by uptake indices. The higher FC dose was required for suspensions containing greater concentration of As species to achieve MCL level. The As (V) species with a greater adsorption affinity towards FHO require a relatively smaller FC dose than As (III) ions. Moreover, the significant influence of interfering species on As removal was observed in simulated natural water. The author hopes that this study may help researchers and the drinking water industry to develop uptake indices of other targeted pollutants in achieving MCL level during water treatment operations in order to ensure public health safety.

Adsorptive removal of phosphate by the bimetallic hydroxide nanocomposites embedded in pomegranate peel.

This study aimed to fabricate new and effective material for the efficiency of phosphate adsorption. Two types of adsorbent materials, the zirconium hydroxides embedded in pomegranate peel (Zr/Peel) and zirconium-lanthanum hydroxides embedded in pomegranate peel (Zr-La/Peel) were developed. Scanning electronic microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD) were evaluated to give insight into the physicochemical properties of these adsorbents. Zr-La/Peel exceeded the adsorption efficiency of Zr/Peel adsorbents in batch adsorption experiments at the same pH level. The peel as a host can strive to have a strong "shielding effect" to increase the steadiness of the entrenched Zr and La elements. La and Zr are hydroxide metals that emit many hydrogen ions during the hydrolysis reaction, which contribute to protonation and electrostatic attraction. The highest adsorption capacity of La-Zr/Peel for phosphate was calculated to be 40.21 mg/g, and pseudo second-order equation is very well fitted for kinetic adsorption. Phosphate adsorption efficiency was reduced by an increase of pH. With the background of coexisting Cl-, little effect on adsorption efficiency was observed, while adsorption capacities were reduced by almost 20-30% with the coexistence of [Formula: see text] , [Formula: see text] and humic acid (HA).

Effect of Water Chemistry on Antimony Removal by Chemical Coagulation: Implications of ζ-Potential and Size of Precipitates.

The process of coagulation and precipitation affect the fate and mobility of antimony (Sb) species in drinking water. Moreover, the solubility and physico-chemical properties of the precipitates may be affected by the media chemistry. Accordingly, the present study aimed to investigate the removal of Sb(III, V) species by ferric chloride coagulation under various water chemistry influences with a particular focus on the role of the properties of the precipitates. The results indicated that the amount of Sb(III) removed increased with increasing solution pH, showing the insignificant effects of the hydrodynamic diameter (HDD) and ζ-potential of the precipitates. However, no Sb(V) removal occurred at alkaline pH values, while a highly negative ζ-potential and the complete dissolution of precipitates were observed in the aqueous solution. The solution pH was also useful in determining the dominant coagulation mechanisms, such as co-precipitation and adsorption. The Fe solubility substantially affects the Sb removal at a certain pH range, while the HDD of the precipitates plays an insignificant role in Sb removal. The presence of divalent cations brings the ζ-potential of the precipitates close to point of zero charge (pzc), thus enhancing the Sb(V) removal at alkaline pH conditions. Pronounced adverse effects of humic acid were observed on Sb removal, ζ-potential and HDD of the precipitates. In general, this study may provide critical information to a wide group of researchers dealing with environmental protection from heavy metal pollution.

Complexation of Antimony with Natural Organic Matter: Performance Evaluation during Coagulation-Flocculation Process.

The presence of natural organic matter (NOM) in drinking water sources can stabilize toxic antimony (Sb) species, thus enhancing their mobility and causing adverse effects on human health. Therefore, the present study aims to quantitatively explore the complexation of hydrophobic/hydrophilic NOM, i.e., humic acid (HA), salicylic acid (SA), and L-cysteine (L-cys), with Sb in water. In addition, the removal of Sb(III, V) species and total organic carbon (TOC) was evaluated with ferric chloride (FC) as a coagulant. The results showed a stronger binding affinity of hydrophobic HA as compared to hydrophilic NOM. The optimum FC dose required for Sb(V) removal was found to be higher than that for Sb(III), due to the higher complexation ability of hydrophobic NOM with antimonate than antimonite. TOC removal was found to be higher in hydrophobic ligands than hydrophilic ligands. The high concentration of hydrophobic molecules significantly suppresses the Sb adsorption onto Fe precipitates. An isotherm study suggested a stronger adsorption capacity for the hydrophobic ligand than the hydrophilic ligand. The binding of Sb to NOM in the presence of active Fe sites was significantly reduced, likely due to the adsorption of contaminants onto precipitated Fe. The results of flocs characteristics revealed that mechanisms such as oxidation, complexation, charge neutralization, and adsorption may be involved in the removal of Sb species from water. This study may provide new insights into the complexation behavior of Sb in NOM-laden water as well as the optimization of the coagulant dose during the water treatment process.

Interaction of Arsenic Species with Organic Ligands: Competitive Removal from Water by Coagulation-Flocculation-Sedimentation (C/F/S).

The co-occurrence of arsenic (As) and organic ligands in water bodies has raised environmental concerns due to their toxicity and adverse effects on human health. The present study aims to elucidate the influences of hydrophobic/hydrophilic organic ligands, such as humic acid (HA) and salicylic acid (SA), on the interactive behavior of As species in water. Moreover, the competitive removal behaviors of As(III, V) species and total organic carbon (TOC) were systematically investigated by coagulation-flocculation-sedimentation (C/F/S) under various aqueous matrices. The results showed the stronger binding affinity of As(V) than As(III) species, with a higher complexation ability of hydrophobic ligands than hydrophilic. The media containing hydrophilic ligands require smaller ferric chloride (FC) doses to achieve the higher As(III, V) removal, while the optimum FC dose required for As(III) removal was found to be higher than that for As(V). Moreover, hydrophobic ligands showed higher TOC removal than hydrophilic ligands. The pronounced adverse effect of a higher concentration of hydrophobic ligands on the removal efficiencies of As(V) and TOC was observed. The adsorption of As(V) on Fe precipitates was better fitted with the Langmuir model but the Freundlich isotherm was more suitable for As(III) in the presence of hydrophilic SA. Moreover, TOC removal was substantially decreased in the As(V) system as compared to the As(III) system due to the dissolution of Fe precipitates at higher As(V) concentrations. The results of FC composite flocs demonstrated that the combined effect of oxidation, charge neutralization and adsorption played an important role in the removal of both toxicants during the C/F/S process. In summary, the findings of the present study provide insights into the fate, mobility and competitive removal behavior of As(III, V) species and organic ligands in the water treatment process.

The Influence of Ionic and Nonionic Surfactants on the Colloidal Stability and Removal of CuO Nanoparticles from Water by Chemical Coagulation.

The widespread use of copper oxide nanoparticles (CuO NPs) and surfactants in various consumer products makes it likely that they coexist in aqueous environments, making it important to study the effects of surfactants on the fate and transport behavior of CuO NPs. The present study aims to investigate the influence of anionic sodium lauryl sulfate (SLS) and nonionic nonylphenol ethoxylate (NPEO, Tergitol NP-9), on CuO NPs adsorption, aggregation, and removal from water by the coagulation process. The result of the sorption study indicates that both surfactants could be adsorbed on the surface of CuO NPs, and that SLS remarkably decreases the ζ potential as well as the hydrodynamic diameter (HDD) of CuO as compared to NP-9. The kinetic aggregation study showed that both SLS and NP-9 reduced the HDD of CuO NPs and retarded the settling rates at surfactant concentrations above 0.015% (w:v) over a 24 h-period. Moreover, enhanced aggregation of CuO NPs was observed in two environmental waters as compared to pure water, which could be related to their high ionic strength. The addition of surfactants in natural waters has been shown to reduce the aggregation and sedimentation of CuO; however, the reductive effect of SLS was more pronounced than that of NP-9. Finally, the coagulation results showed that the removal efficiencies of CuO, Cu2+, and the surfactant in all tested waters at optimum ferric chloride dosage reached around 98, 95, and 85%, respectively. Furthermore, the coagulation mechanism revealed that the combination of charge neutralization and adsorptive micellar flocculation (AMF) might be involved in the removal of both pollutants. The results of the present study provide new insight into the environmental behavior of coexisting NPs and surfactants in wastewater treatment processes.

The Removal of CuO Nanoparticles from Water by Conventional Treatment C/F/S: The Effect of pH and Natural Organic Matter.

The increased use of engineered nanoparticles (ENPs), such as copper oxide nanoparticles (CuO NPs), in commercial products and applications raises concern regarding their possible release into freshwater sources. Therefore, their removal from water is important to eliminate adverse environmental and human health effects. In this study, the effects of pH and natural organic matter (NOM), i.e., humic acid (HA) and salicylic acid (SA) on the removal of CuO NPs by coagulation/flocculation/sedimentation (C/F/S) were evaluated. The results indicated that pH significantly affects the coagulation efficiency, where 10⁻60% CuO NPs removal was achieved under extreme acidic/alkaline conditions. However, at neutral pH, removal of up to 90% was observed with a lower ferric chloride (FC) dosage (0.2 mM). The coagulation efficiency and mechanism were strongly affected by the type of Fe species present in the aqueous phase, which is mainly controlled by pH. Higher concentrations of both HA and SA decrease the CuO NPs agglomeration rate, and thereby improve the colloidal stability due to the NOM molecules adsorbed onto the NPs surface. The presence of hydrophobic HA needs a higher FC dosage of 0.5⁻0.8 mM than a dosage of hydrophilic SA of 0.25⁻0.35 mM, to obtain a similar CuO coagulation efficiency. Moreover, higher removals of dissolved organic carbon (DOC) and UV254 were observed more in hydrophobic NOM than in hydrophilic. The results of the Fourier transform infrared (FT-IR) analysis of FC composite flocs confirm that the charge neutralization and enmeshment of coagulant might be a possible removal mechanism. The findings of the current study may provide critical information in the prediction of the fate, mobility, and removal of CuO NPs during C/F/S in water treatment.

Interaction between Persistent Organic Pollutants and ZnO NPs in Synthetic and Natural Waters.

The use of zinc oxide nanoparticles (ZnO NPs) and polybrominated diphenyl ethers (PBDPEs) in different products and applications leads to the likelihood of their co-occurrence in the aquatic system, making it important to study the effect of PBDPEs on the fate and transport of ZnO NPs. In this study, we determine the influence of PBDPEs (BDPE-47 and BDPE-209) on the colloidal stability and physicochemical properties of ZnO NPs in different aqueous matrices. The results indicated the shift in ζ potential of ZnO NP from positive to negative in the presence of both PBDPEs in all tested waters; however, the effect on the NPs surface potential was specific to each water considered. The lower concentration of the PBDPEs (e.g., 0.5 mg/L) significantly reduced the ζ potential and hydrodynamic diameter (HDD) of ZnO NP, even in the presence of high content of dissolved organic matter (DOM) in both freshwater and industrial wastewater. Moreover, both BDPE-47 and BDPE-209 impede the agglomeration of ZnO NP in simple and natural media, even in the presence of monovalent and polyvalent cations. However, the effect of BDPE-47 on the ζ potential, HDD, and agglomeration of ZnO NP was more pronounced than that of BDPE-209 in all tested waters. The results of Fourier transform infrared (FT-IR) and X-ray Photon Spectroscopy (XPS) further confirm the adsorption of PBDPEs onto ZnO NP surface via aromatic ether groups and Br elements. The findings of this study will facilitate a better understanding of the interaction behavior between the ZnO NPs and PBDPEs, which can reduce the exposure risk of aquatic organisms to both pollutants.