Converter slag–coal cinder columns for the removal of phosphorous and other pollutants

A mixture of converter slag and coal cinder as adsorbent for the removal of phosphorous and other pollutants was studied in the paper. The maximum P adsorption capacity, pH of solution, contact time and initial phosphate concentration were evaluated in batch experiments for the two materials firstly. The data of P sorption were best fitted to Langumir equation, and the maximum adsorption capacities of converter slag and coal cinder were 2.417 and 0.398 mg P/g, respectively. The pH of solutions with converter slag and coal cinder changed dramatically with time and closed to 8 in 8 h, and the influence of initial pH on phosphate removal by coal cinder was more significant than by converter slag. Phosphate removal rate by converter slag decreased with increase of initial phosphate concentrations. Subsequently, two flow-through columns (Column 1#, V_{converter slag}:V_{coal cinder} = 1:5; Column 2#, V_{converter slag}:V_{coal cinder} = 1:3) were operated for the removal of phosphorous and other pollutants from the effluents of a vermifilter for nearly eleven months. Results indicated the average removal efficiency of total phosphorus, dissolved phosphorus, COD and NH₄⁺–N by Column 1# were 44%, 56%, 31% and 67%, and by Column 2# were 42%, 54%, 24% and 57%, respectively. Column 1# had higher removal efficiency for P and other pollutants.     

Layer-by-layer assembly of poly (N-acryloyl-N'-propylpiperazine) and poly (acrylic acid): Effect of pH and temperature

Layer-by-layer assembly technique was applied to fabricate multilayer films of poly(N-acryloyl-N'-propylpiperazine) (PAcrNPP) and poly(acrylic acid). The film buildup was followed by Quartz Crystal Microbalance, and the effect of temperature and pH on the layer-by-layer assembly was investigated. Below the lower critical solution temperature of PAcrNPP, the adsorption amount increased with increase of temperature. As the pH of dipping solutions was systematically varied from 2.0 to 7.5, adsorption amount of polymers initially increased and then decreased. The relationship between adsorption amount and degree of ionization of polymers was discussed. When an eight-bilayer film was alternately exposed to HCl aqueous solution (pH = 3.5) and neutral water (pH = 6.5), the film showed pH-response, which could be the result of polymer rearrangement.     

Adsorption of Ni(II) on oxidized multi-walled carbon nanotubes: Effect of contact time,pH, foreign ions and PAA

The adsorption of Ni(II) on oxidized multi-walled carbon nanotubes (MWCNTs) as a function of contact time, pH and foreign ions in the absence and presence of polyacrylic acid (PAA) was studied using batch technique. The results indicated that adsorption of Ni(II) on oxidized MWCNTs increased from zero to ∼99% at pH 2–9, and then maintained the high level with increasing pH. Kinetic data showed that the adsorption process achieved equilibrium within 2 h and experimental data were fitted well by the pseudo-second-order equation. A positive effect of PAA on Ni(II) adsorption was found at pH < 8, whereas a negative effect was observed at pH > 8. The effect of addition sequences of PAA/Ni(II) on the adsorption of Ni(II) to PAA–MWCNT hybrids were also studied. The results indicated that the adsorption of Ni(II) was influenced by addition sequences obviously. The adsorption of Ni(II) on oxidized MWCNTs may be mainly attributed to surface complexation and ion exchange. Oxidized MWCNTs are suitable material in the solidification and pre-concentration of Ni(II) from aqueous solutions.     

Adsorption of Supranol Yellow 4 GL from aqueous solution by surfactant-treated aluminum/chromium-intercalated bentonite

The aim of this paper is to study the adsorption of the acid dye Supranol Yellow 4 GL (S.Y. 4 GL) from aqueous solution on an inorgano–organo clay. Bentonite is naturally occurring clay with good exchanging ability. By exchanging its interlamellar cations with cetyltrimethylammonium bromide (CTAB) and hydroxyaluminic or chromium polycations, the properties of natural bentonite can be greatly improved. Batch adsorption tests of Supranol Yellow 4 GL were carried out at 20 °C and constant pH 6.5. To investigate the adsorption mechanisms, the simplified kinetic models, such as pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion are tested. The results show that adsorption follows second-order rate kinetic. The correlation coefficients obtained for second-order kinetics model are greater than 0.998 indicating a better fitting of this equation. The experimental data are analysed by Langmuir, Freundlich and Elovich isotherms. The equilibrium adsorption capacity of anionic dye is determined from the Langmuir equation and found to be 142, 85 and 128, 20 mg/g (standard deviation; Δq (%) = 3.52 and 18.51) for CTAB-Cr-B and CTAB-Al-B, respectively.     

Characteristics of diethylenetriamine-crosslinked cotton stalk/wheat stalk and their biosorption capacities for phosphate

Two polymeric biosorbents were prepared from cotton stalk (CS) and wheat straw (WS) by the epichlorohydrin-diethylenetriamine-trimethylamine method. Amine-crosslinked cotton stalk (AC-CS) and wheat stalk (AC-WS) were used for the adsorption of phosphate, and their physicochemical properties as well as biosorption properties for phosphate were discussed intensively. Results indicated that the contents of holocellulose in CS and WS corresponded to the distinct phosphate adsorption capacities between AC-CS and AC-WS. Zeta potential and Raman spectra analysis illustrated the electrostatic attraction between phosphate ions and biosorbents. The adsorption of phosphate was not strongly pH dependent when the pH was about 4.0-9.0. The Langmuir isotherm provided the better fit and the maximum adsorption capacity (Q_max) was 51.54 mg/g for AC-CS and 60.61 mg/g for AC-WS. The saturated adsorption capacities of AC-CS and AC-WS in column were 49.05 and 41.9 mg/g, which accounted for about 80.3% and 81.4% of these biosorbents’ Q_max. NaCl and HCl solutions demonstrated the excellent regeneration capacities for the biosorbents, and after three times of adsorption-desorption cycles, the column adsorption capacities of these biosorbents were still higher than 92%.     

Structural and dielectric properties of A(Fe1/2Ta1/2)O3 [A = Ba, Sr, Ca]

The complex perovskite oxide barium iron tantalate (BFT), BaFe_1/2Ta_1/2O₃, strontium iron tantalate (SFT), SrFe_1/2Ta_1/2O₃ and calcium iron tantalate (CFT), CaFe_1/2Ta_1/2O₃ are synthesized by a solid-state reaction technique. Rietveld refinement of the X-ray diffraction data of the samples shows that BFT and SFT crystallize in cubic structure, with lattice parameter a = 4.06 Å for BFT and 3.959 Å for SFT, whereas CFT crystallizes in orthorhombic structure having lattice parameters a = 5.443 Å, b = 5.542 Å and c = 7.757 Å. Fourier transform infrared spectra show two primary phonon modes of the samples at around 450 cm⁻¹ and 620 cm⁻¹. The compounds show significant frequency dispersion in its dielectric properties. The complex impedance plane plots of the samples show that the relaxation (conduction) mechanism in these materials is purely a bulk effect arising from the semiconductive grains. The relaxation mechanism of the samples is modelled by Cole-Cole equation. The frequency dependent conductivity spectra are found to follow the power law.     

Selective adsorption of tannin from flavonoids by organically modified attapulgite clay

In this study, selective adsorption of tannin on organically modified attapulgite clay was investigated. Tannin was selectively removed from model tannin/flavonoids mixtures in the solution. In adsorption isotherm experiments of tannin, obtained data fitted well to the Freundlich model. The surface sites of the octodecyl trimethyl ammonium chloride (OTMAC)-attapulgite were heterogeneous. The effect of pH on tannin adsorption was also investigated and the results showed that the adsorbed amount of tannin was highest at pH 6.0. The enthalpy values of adsorption of tannin on OTMAC-attapulgite at pH 4.0, 6.0 and 8.0 were −49.80, −74.31 and −38.62 kJ/mol, respectively. At 2–5.3 and 7.4–10, the driving forces for the adsorption may be the hydrophobic force and hydrogen bonding. And at pH 5.3–7.4 the electrostatic force may be the most important one. These facts implied that the selective adsorption of tannin on OTMAC-attapulgite was driven by the collaboration of hydrogen bonding, electrostatic force and hydrophobic interactions of tannin molecular with adsorbent. The low adsorption of isoflavones of soybean and the puerarin was ascribed to less phenolic hydroxyls of them than those of tannin, which made the low electrostatic interactions and hydrogen bonding interactions between the tannin and OTMAC-attapulgite adsorbent.     

Thorough removal of inorganic and organic mercury from aqueous solutions by adsorption on Lemna minor powder

The adsorption ability of duckweed (Lemna minor) powders for removing inorganic and organic mercury (methyl and ethyl mercury) has been studied using cold vapour atomic absorption spectrometry. The optimal adsorption conditions were: (a) the pH value of the solution 7.0 for inorganic and ethyl mercury, 9.0 for methyl mercury, and (b) equilibrium adsorption time 10, 20, and 40 min for inorganic mercury, methyl mercury, and ethyl mercury, respectively. After adsorption by L. minor powder for 40 min, when the initial concentrations of inorganic and organic mercury were under 12.0 μg L⁻¹ and 50.0 μg L⁻¹, respectively, the residual concentrations of mercury could meet the criterion of drinking water (1.0 μg L⁻¹) and the permitted discharge limit of wastewater (10.0 μg L⁻¹) set by China and USEPA, respectively. Thorough removal of both inorganic and organic mercury from aqueous solutions was reported for the first time. The significant adsorption sites were C–O–P and phosphate groups by the surface electrostatic interactions with aqueous inorganic and organic mercury cations, and then the selective adsorption was resulted from the strong chelating interaction between amine groups and mercury on the surface of L. minor cells.     

Solid-state synthesis of amorphous iron(III) phosphate at room temperature and its absorption properties for Hg(II) and Ag(I) ions

Amorphous iron(III) phosphate has been synthesized by solid-state reaction at room temperature and was characterized by several methods. The non-crystalline sample displayed the particle size within the range of 100-200 nm, and it had a strong fluorescence emission peak centered at 306.6 nm. Moreover, its absorption properties for Hg(II) and Ag(I) heavy metal ions have been investigated. The experimental research results revealed that its excellent absorption capacity for Hg(II) and Ag(I) could reach to 1.831 mmol/g and 1.354 mmol/g, respectively, at pH = 5.98 and the absorption time t = 6 h. The absorption properties for Hg(II) were usually stronger that those for Ag(I).     

Application of dolochar in the removal of cadmium and hexavalent chromium ions from aqueous solutions

Dolochar, a waste material generated in sponge iron industry, is processed and put to test as an adsorbent for removal of Cd(II) and Cr(VI) ions from aqueous solutions. The dolochar samples were characterised to determine the different phases and their distribution by reflection microscopy. The analysis indicated that the sample consists of metallic iron, fused carbon, and Ca-Mg bearing phases (Ca-Mg-silicate-oxide) along with lots of voids and pores. The fixed carbon (FC) content of the material is 13.8% with a Langmuir surface area of 81.6 m²/g and micropore area of 34.1 m²/g. Batch adsorption experiments have been conducted to study the sorption behaviour of Cd(II) and Cr(VI) ions on dolochar as a function of particle size, contact time, adsorbent dosages, pH and temperature. It is observed that higher pH and temperature enhances sorption of Cd(II) ions. In contrast, the adsorption for Cr(VI) is found to be better in acidic pH in comparison to alkaline media. The equilibrium adsorption isotherm data are tested by applying both Langmuir and Freundlich isotherm models. It is observed that Langmuir isotherm model fitted better compared to the Freundlich model indicating monolayer adsorption. The thermodynamic parameters such as ΔG°, ΔH° and ΔS° indicate the effectiveness of dolochar to remove Cd(II) and Cr(VI) ions from aqueous solution. The kinetics of adsorption is found to better fit to pseudo second order reaction.     

Effect of pH value on particle morphology and electrochemical properties of LiFePO4 by hydrothermal method

Lithium iron phosphate was prepared by hydrothermal synthesis using LiOH·H₂O, FeSO₄·7H₂O and H₃PO₄ as raw materials. The effects of pH value of reaction solution on particle morphology and electrochemical property were investigated. The pH value of the reaction solution was adjusted in the range of 2.5-8.8 by dilute sulfuric acid and ammonia water. The samples were characterized by field-emission scanning electronic microscope (FE-SEM), X-ray powder diffraction (XRD), constant-current charge/discharge cycling tests and chemical analysis. The results indicated that the particles exhibited acute angle diamond flake-like morphology at pH = 2.5, and as the pH value increased, the particle became hexagon flake-like, round flake-like and irregular flake-like morphology gradually. The optimal sample synthesized at pH = 6.4 exhibited discharge capacities of 151.8 mAh g⁻¹ at 0.2 C rate and 129.3 mAh g⁻¹ at 3 C rate. It was found that pH value affected the morphologies and properties of the product by means of different crystal growth rates.     

High surface area neodymium phosphate nano particles by modified aqueous sol-gel method

Synthesis of nano rod shaped neodymium phosphate (NdPO₄) particles with specific surface area as high as 107 m²g⁻¹ and an average length of 50 nm with aspect ratio 5 was achieved using modified sol gel method. Crystallite size calculated from the X-ray diffraction data by applying Scherer equation was 5 nm for the precursor gel after calcination at 400 °C. NdPO₄ was first precipitated from neodymium nitrate solution using phosphoric acid followed by peptization using dilute nitric acid and further gelation in ammonia atmosphere. The calcined gel powders were further characterized by surface area (Brunauer-Emmet-Teller nitrogen adsorption analysis), Transmission electron microscopy, scanning electron microscopy, UV-vis and FT-IR analysis. Transmission electron microscopy confirms the formation of rod like morphology from the sol, gel and the calcined particles in nano size range. These particles could be compacted and sintered at as low as 1300 °C to a density of 98.5% (theoretical) with an average grain size of ∼1 μm.     

Effect of competitive ions on the arsenic removal by mesoporous hydrous zirconium oxide from drinking water

Adsorption properties of 302-type commercially available hydrous zirconium oxide (302-HZO) towards arsenic and some competitive anions and cations have been studied under batch and column conditions. Due to amphoteric properties, anion exchange performance of hydrous zirconium oxide is pH dependent. Media exhibits high affinity towards arsenic in a broad pH range, with high adsorption capacity at pH < 8. It was shown that silicate and phosphate ions are arsenic's main competitors affecting media adsorption capacity. Presence of transition metal cations in <1 ppm does not affect 302-HZO capacity on arsenic, whereas alkaline-earth cations improve arsenic removal. The possibility for significant increase of 302-HZO adsorption capacity on arsenic at pH > 8 by using “solid acidifier” technique is discussed. Results of 302-HZO field trials are presented.     

Preparation of nanospinels NiMnxFe2−xO4 using sol–gel method and their applications on removal of azo dye from aqueous solutions

In this paper, nanospinels NiMn_xFe_2−xO₄ (x = 0.05, 0.1, 0.3, 0.5, 0.7, and 1) were prepared by sol–gel method in the presence of nitrate–metal–ethylene glycol (EG) polymerized complex. The nanospinels were characterized using thermogravimetry analysis (TGA), X-ray powder diffraction (XRD), Fourier infrared spectroscopy (FTIR), and transmission electron microscope (TEM). The adsorption of an azo dye, reactive blue 5 (RB5), from water was determined using the prepared nanospinels. The effect of operational parameters such as the initial dye concentration, the concentration of nanospinels, temperature, and pH on the degradation of dye was investigated. The adsorption process follows second-order kinetics and Arrhenius behavior. Two common models, the Langmuir and Freundlich isotherms were used to investigate the interaction of dye and nanospinels. The isotherm evaluations revealed that the Freundlich model provides better fit to the experimental data than that of the Langmuir model. The photocatalytic degradation of RB5 at pH 1 under UV irradiation was examined. The results showed that the degradation of RB5 dye follows merely an adsorption process.     

Removal of phosphate from polluted water by lanthanum doped vesuvianite

The adsorption capacities of vesuvianite and lanthanum doped vesuvianite were studied. The effects of different mass ratios of La/vesuvianite at different contact times, pHs, and temperatures on adsorption capacity were also studied. It was found that lanthanum doped vesuvianite exhibited higher adsorption capacity than undoped one due to the reaction of bounded lanthanum with phosphate. The adsorption capacity of lanthanum doped vesuvianite for phosphate removal increased with the increase of La/vesuvianite mass ratio. The Freundlich and Langmuir models were used to simulate the sorption equilibrium, and the results indicate that the Langmuir model had a better correlation with the experimental data than the Freundlich model did. When the initial phosphate concentration was 1 mg P/L, the adsorptive capacity rate would be 1.32 mg P/g lanthanum doped vesuvianite (La/vesuvianite mass ratio ≥0.14) at pH between 6 and 9 after 40 h. The concentrations of residual lanthanum ions in solution at different conditions were measured. Lanthanum doped vesuvianite was also used for the removal of phosphate in a polluted river water and it could be easily recycled once without losing its activity to a greater extent.     

Use of rice straw as biosorbent for removal of Cu(II), Zn(II), Cd(II) and Hg(II) ions in industrial effluents

Adsorption experiments were carried out using waste rice straw of several kinds as a biosorbent to adsorb Cu(II), Zn(II), Cd(II) and Hg(II) ions from aqueous solutions at room temperature. To achieve the best adsorption conditions the influence of pH and contact time were investigated. The isotherms of adsorption were fitted to the Freundlich equation. Based on the experimental data and Freundlich model, the adsorption order was Cd(II) > Cu(II) > Zn(II) > Hg(II) on the rice straw. This quick adsorption process reached the equilibrium before 1.5 h, with maximum adsorptions at pH 5.0. Thermodynamic aspects of the adsorption process were investigated. The biosorbent material was used in columns for the removal of ions Cu, Zn, Cd and Hg of real samples of industrial effluent and its efficiency was studied.     

Adsorption of copper(II) onto sewage sludge-derived materials via microwave irradiation

The materials with adsorbent properties were produced from urban sewage sludge by two different procedures via microwave irradiation: (1) by one single pyrolysis stage (SC); (2) by chemical activation with ZnCl₂ (SZ). The BET, SEM and FT-IR have been used to evaluate the pore structural parameters and surface chemistry of the adsorbents, respectively. Subsequently they were used for adsorption of Cu(II) from aqueous solutions. The effects of various experimental parameters, such as pH, temperature were investigated in a batch-adsorption technique. The results showed that the adsorption of Cu(II) was maximal at pH 5.0. The kinetic study demonstrated that the adsorption process was followed the second-order kinetic equation. The experimental adsorption isotherm data were well fitted with Langmuir model and the maximum adsorption capacity of Cu(II) were found to be 3.88 and 10.56 mg/g for SC and SZ, respectively, in the solution of pH 5.0. Thermodynamic parameters such as changes in the enthalpy (ΔH⁰), entropy (ΔS⁰) and free energy (ΔG⁰) indicate that Cu(II) adsorption onto SC and SZ is an endothermic and spontaneous process in nature at 15-45 °C. These results indicate that the sewage sludge-derived material via microwave induced ZnCl₂ activation is an effective and alternative adsorbent for the removal of Cu(II) from aqueous solution.     

Nitrate removal from groundwater by cooperating heterotrophic with autotrophic denitrification in a biofilm-electrode reactor

An intensified biofilm-electrode reactor (IBER) combining heterotrophic and autotrophic denitrification was developed for treatment of nitrate contaminated groundwater. The reactor was evaluated with synthetic groundwater (NO₃⁻-N50 mg L⁻¹) under different hydraulic retention times (HRTs), carbon to nitrogen ratios (C/N) and electric currents (I). The experimental results demonstrate that high nitrate and nitrite removal efficiency (100%) were achieved at C/N = 1, HRT = 8 h, and I = 10 mA. C/N ratios were reduced from 1 to 0.5 and the applied electric current was changed from 10 to 100 mA, showing that the optimum running condition was C/N = 0.75 and I = 40 mA, under which over 97% of NO₃⁻-N was removed and organic carbon (methanol) was completely consumed in treated water. Simultaneously, the denitrification mechanism in this system was analyzed through pH variation in effluent. The CO₂ produced from the anode acted as a good pH buffer, automatically controlling pH in the reaction zone. The intensified biofilm-electrode reactor developed in the study was effective for the treatment of groundwater polluted by nitrate.     

Zincon-modified activated carbon for solid-phase extraction and preconcentration of trace lead and chromium from environmental samples

A new method that utilizes zincon-modified activated carbon (AC-ZCN) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III) and Pb(II) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES). The separation/preconcentration conditions of analytes were investigated, including effects of pH, the shaking time, the sample flow rate and volume, the elution condition and the interfering ions. At pH 4, the maximum adsorption capacity of Cr(III) and Pb(II) onto the AC-ZCN were 17.9 and 26.7 mg g⁻¹, respectively. The adsorbed metal ions were quantitatively eluted by 1 mL of 0.1 mol L⁻¹ HCl. Common coexisting ions did not interfere with the separation. According to the definition of IUPAC, the detection limits (3σ) of this method for Cr(III) and Pb(II) were 0.91 and 0.65 ng mL⁻¹, respectively. The relative standard deviation under optimum condition is less than 3.5% (n = 8). The method has been applied for the determination of Cr(III) and Pb(II) in biological materials and water samples with satisfactory results.     

Synthesis and characterization of a new layered magnesium zinc phosphate hydrate

A new layered magnesium zinc phosphate hydrate, MgZn(HPO₄)₂·H₂O, with a zinc phosphate framework isostructural with the one of Na₂Zn(HPO₄)₂·4H₂O, was prepared by the direct ambient pressure and temperature reaction between zinc 2,4-pentanedionate, phosphoric acid and hexahydrated magnesium chloride. The as-prepared sample is monoclinic (a = 8.780(7) Å, b = 13.240(7) Å, c = 11.123(0) Å and β = 116.21(2)°). The prepared solid undergoes two thermal transformations when it is heated from 110 to 600 °C. The first transformation is due to the release of intercalated water molecules and the second one is due to the HPO₄²⁻ → P₂O₇⁴⁻ transition.