Nitrate removal from aqueous solutions by magnetic cationic hydrogel: Effect of electrostatic adsorption and mechanism

Excessive nitrate(NO_3~-) is among the most problematic surface water and groundwater pollutants.In this study,a type of magnetic cationic hydrogel(MCH) is employed for NO_3~-adsorption and well characterized herein.Its adsorption capacity is considerably pHdependent and achieves the optimal adsorption(maximum NO_3~--adsorption capacity is95.88±1.24 mg/g) when the pH level is 5.2-8.8.The fitting result using the homogeneous surface diffusion model indicates that the surface/film diffusion controls the adsorption rate,and NO_3~-approaches the center of MCH particles within 30 min.The diffusion coefficient(D_s) and external mass transfer coefficient(k_F) in the liquid phase are1.15 × 10~(-6) cm~2/min and 4.5 × 10~(-6) cm/min,respectively.The MCH is employed to treat surface water that contains 10 mg/L of NO_3~-,and it is found that the optimal magnetic separation time is 1.6 min.The high-efficiency mass transfer and magnetic separation of MCH during the adsorption-regeneration process favors its application in surface water treatment.Furthermore,the study of the mechanism involved reveals that both-N~+(CH_3)_3 groups and NO_3~-are convoluted in adsorption via electrostatic interactions.It is further found that ion exchange between NO_3~-and chlorine occurs.     

Optimized photocatalytic regeneration of adsorption-photocatalysis bifunctional composite saturated with Methyl Orange

Photo-responsive adsorption-photocatalysis nanocomposites are generally used in water and wastewater decontamination; however, the prolonged adsorption capacity of composites and the role of adsorption in concomitant photocatalysis are typically neglected. These composites can be regenerated under light irradiation as their adsorption capacity decreases. Herein, a novel adsorption-photocatalysis bifunctional nanocomposite, Bi-doped TiO₂ supported on powdered activated carbon (Bi₂O₃/TiO₂/PAC), was prepared using the sol-impregnation-hydrothermal procedure. Bi₂O₃/TiO₂/PAC with a secondary calcination temperature of 700°C under a nitrogen atmosphere was selected for maximum adsorption capacity on Methyl Orange (MO). The composite displayed an excellent adsorption capacity and was easily separated and recycled. The results demonstrate that 71.2% photocatalytic regeneration efficiency could be attained under visible light irradiation for 1 hr at an intensity of 750?W/m² and pH 7. Characterization of the as-prepared Bi₂O₃/TiO₂/PAC nanocomposite (700°C) indicates that it possesses a highly specific surface area and great optical properties, showing bifunctional adsorption-photocatalysis characteristics. The p-n heterojunction of the composite played a dominant role in the photocatalytic regeneration process, and effective degradation of MO could be achieved along with composite regeneration.     

Adsorption mechanisms of PFOA onto activated carbon anchored with quaternary ammonium/epoxide-forming compounds: A combination of experiment and model studies

When wood-based activated carbon was tailored with quaternary ammonium/epoxide (QAE) forming compounds (QAE-AC), this tailoring dramatically improved the carbon's effectiveness for removing perfluorooctanoic acid (PFOA) from groundwater. With favorable tailoring, QAE-AC removed PFOA from groundwater for 118,000 bed volumes before half-breakthrough in rapid small scale column tests, while the influent PFOA concentration was 200 ng/L. The tailoring involved pre-dosing QAE at an array of proportions onto this carbon, and then monitoring bed life for PFOA removal. When pre-dosing with 1 mL QAE, this PFOA bed life reached an interim peak, whereas bed life was less following 3 mL QAE pre-dosing, then PFOA bed life exhibited a steady rise for yet subsequently higher QAE pre-dosing levels. Large-scale atomistic modelling was used herein to provide new insight into the mechanism of PFOA removal by QAE-AC. Based on experimental results and modelling, the authors perceived that the QAE's epoxide functionalities cross-linked with phenolics that were present along the activated carbon's graphene edge sites, in a manner that created mesopores within macroporous regions or created micropores within mesopores regions. Also, the QAE could react with hydroxyls outside of these pore, including the hydroxyls of both graphene edge sites and other QAE molecules. This latter reaction formed new pore-like structures that were external to the activated carbon grains. Adsorption of PFOA could occur via either charge balance between negatively charged PFOA with positively charged QAE, or by van der Waals forces between PFOA's fluoro-carbon tail and the graphene or QAE carbon surfaces.     

Facile one-step synthesis of functionalized biochar from sustainable prolifera-green-tide source for enhanced adsorption of copper ions

The use of biochars formed by hydrothermal carbonization for the treatment of contaminated water has been greatly limited,due to their poorly developed porosity and low content of surface functional groups.Also,the most common modification routes inevitably require post-treatment processes,which are time-consuming and energy-wasting.Hence,the objective of this research was to produce a cost-effective biochar with improved performance for the treatment of heavy metal pollution through a facile one-step hydrothermal carbonization process coupled with ammonium phosphate,thiocarbamide,ammonium chloride or urea,without any posttreatment.The effects of various operational parameters,including type of modification reagent,time and temperature of hydrothermal treatment,and ratio of modification reagent to precursor during impregnation,on the copper ion adsorption were examined.The adsorption data fit the Langmuir adsorption isotherm model quite well.The maximum adsorption capacities(mg/g) of the biochars towards copper ions followed the order of 40-8 h-1.0-APBC(95.24) 140-8 h-0-BC(12.52) 140-8 h-1.0-TUBC(12.08) 140-8 h-1.0-ACBC(7.440) 140-8 h-1.0-URBC(5.277).The results indicated that biochars modified with ammonium phosphate displayed excellent adsorption performance toward copper ions,which was 7.6-fold higher than that of the pristine biochar.EDX and FT-IR analyses before and after adsorption demonstrated that the main removal mechanism involved complexation between the phosphate groups on the surface of the modified biochars and copper ions.     

Comparison of activated carbon and iron/cerium modified activated carbon to remove methylene blue from wastewater

The methylene blue(MB)removal abilities of raw activated carbon and iron/cerium modified raw activated carbon(Fe–Ce-AC)by adsorption were researched and compared.The characteristics of Fe–Ce-AC were examined by N_2adsorption,zeta potential measurement,FTIR,Raman,XRD,XPS,SEM and EDS.After modification,the following phenomena occurred:The BET surface area,average pore diameter and total pore volume decreased;the degree of graphitization also decreased.Moreover,the presence of Fe_3O_4led to Fe–Ce-AC having magnetic properties,which makes it easy to separate from dye wastewater in an external magnetic field and subsequently recycle.In addition,the equilibrium isotherms and kinetics of MB adsorption on raw activated carbon and Fe–Ce-AC were systematically examined.The equilibrium adsorption data indicated that the adsorption behavior followed the Langmuir isotherm,and the pseudo-second-order model matched the kinetic data well.Compared with raw activated carbon,the maximum monolayer adsorption capacity of Fe–Ce-AC increased by27.31%.According to the experimental results,Fe–Ce-AC can be used as an effective adsorbent for the removal of MB from dye wastewater.     

Formation of CoAl layered double hydroxide on the boehmite surface and its role in tungstate sorption

Sorption of tungstate on boehmite(γ-Al OOH)is increased by co-sorption with Co~(2+)over the near-neutral p H range.Batch uptake experiments show up to a 3-fold increase in tungstate uptake over the range WO_4~(2-)=50–1000μmol/L compared to boehmite not treated with Co~(2+).Desorption experiments reveal a corresponding decrease in sorption reversibility for tungstate co-sorbed with Co~(2+).Reaction of boehmite with Co~(2+)results in the formation of Co Al layered double hydroxide(LDH),as confirmed by X-ray diffraction and X-ray absorption spectroscopy.Tungsten L_3-edge X-ray absorption near edge structure(XANES)reveals that W(VI)is octahedrally coordinated in all sorption samples,with polymeric tungstate species forming at higher tungstate concentrations.X-ray diffraction and X-ray absorption spectroscopy indicate that the mechanism for enhancement of tungstate uptake is the formation of surface complexes on boehmite at low tungstate concentrations,while exchange into the Co Al LDH becomes important at higher tungstate concentrations.The results provide a basis for developing strategies to enhance tungstate sorption and to limit its environmental mobility at near-neutral pH conditions.     

Preparation and characterization of a novel hybrid chelating material for effective adsorption of Cu(Ⅱ) and Pb(Ⅱ)

The discharge of heavy metal ions such as Cu~2+and Pb~2+poses a severe threat to public health and the environment owing to their extreme toxicity and bioaccumulation through food chains Herein, we report a novel organic–inorganic hybrid adsorbent, Al(OH)_3-poly(acrylamide dimethyldiallylammonium chloride)-graft-dithiocarbamate(APD), for rapid and effectiv removal of Cu~2+and Pb~2+. In this adsorbent, the "star-like" structure of Al(OH)3 poly(acrylamide-dimethyldiallylammonium chloride) served as the support of dithiocarbamat(DTC) functional groups for easy access of heavy metal ions and assisted development of larg and compact floccules. The synthesized adsorbent was characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR), and thermogravimetric analysis(TGA). APD was demonstrated to hav rapid adsorption kinetics with an initial rate of 267.379 and 2569.373 mg/(g·min) as well a superior adsorption capacities of 317.777 and 586.699 mg/g for Cu~2+and Pb~2+respectively. Th adsorption process was spontaneous and endothermic, involving intraparticle diffusion and chemical interaction between heavy metal ions and the functional groups of APD. To assess it versatility and wide applicability, APD was also used in turbid heavy metal wastewater, and performed well in removing suspended particles and heavy metal ions simultaneously through flocculation and chelation. The rapid, convenient and effective adsorption of Cu~2+and Pb~2+give APD great potential for heavy metal decontamination in industrial applications.     

Influence of sodium dodecyl sulfate coating on adsorption of methylene blue by biochar from aqueous solution

Biochar is regarded as a promising new class of materials due to its multifunctional character and the possibility of effectively coupling different properties. With increasing introduction into the environment, environmental chemicals such as surfactants will load onto the released biochar and change its physicochemical characteristics and adsorption behavior toward pollutants. In this study, sodium dodecyl sulfate(SDS), as one type of anionic surfactant, was coated onto biochar with different loading amounts. The influence of SDS loading onto biochar's physicochemical properties were investigated by Fourier transform infrared(FT-IR) spectroscopy, elemental analysis, zeta potential and Brunauer–Emmett–Teller(BET) surface area and pore size distribution analysis. Results showed that the pore size of the biochar decreased gradually with the increase of SDS loading because of the surface-adsorption and pore-blocking processes; the p H of the point of zero charge(pHPZC) decreased with increasing SDS loading. Although surface-coating with SDS decreased the pore size of the biochar, its adsorption capacity toward Methylene Blue(MB) significantly increased. The biochar-bound SDS introduced functional groups and negative charges to the biochar surface, which could thus enhance the adsorption of MB via hydrogen bonding and electrostatic interaction. The results can shed light on the underlying mechanism of the influence of anionic surfactants on the adsorption of MB by biochar.     

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes

Iron oxide(FeO)coated by natural organic matter(NOM)is ubiquitous.The associations of minerals with organic matter(OM)significantly changes their surface properties and reactivity,and thus affect the environmental fate of pollutants,including nutrients(e.g.,phosphorus(P)).In this study,ferrihydrite/goethite-humic acid(FH/GE–HA)complexes were prepared and their adsorption characteristics on P at various p H and ionic strength were investigated.The results indicated that the Fe O–OM complexes showed a decreased P adsorption capacity in comparison with bare Fe O.The maximum adsorption capacity(Q_(max))decreased in the order of FH(22.17 mg/g)FH-HA(5.43 mg/g)GE(4.67 mg/g)GE-HA(3.27 mg/g).After coating with HA,the amorphous FH–HA complex still showed higher P adsorption than the crystalline GE–HA complex.The decreased P adsorption observed might be attributed to changes of the Fe O surface charges caused by OM association.The dependence of P adsorption on the specific surface area of adsorbents suggests that the Fe O component in the complexes is still the main contributor for the adsorption surfaces.The P adsorptions on Fe O–HA complexes decreased with increasing initial p H or decreasing initial ionic strength.A strong dependence of P adsorption on ionic strength and p H may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the Fe O component and P.Therefore,previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils,especially in humic-rich areas.