Sustainable Chromium (VI) Removal from Contaminated Groundwater Using Nano-Magnetite-Modified Biochar via Rapid Microwave Synthesis

This study developed a nano-magnetite-modified biochar material (m-biochar) using a simple and rapid in situ synthesis method via microwave treatment, and systematically investigated the removal capability and mechanism of chromium (VI) by this m-biochar from contaminated groundwater. The m-biochar was fabricated from reed residues and magnetically modified by nano-Fe₃O₄. The results from scanning electron microscopy (SEM) and X-ray diffraction (XRD) characterisations confirmed the successful doping of nano-Fe₃O₄ on the biochar with an improved porous structure. The synthesised m-biochar exhibited significantly higher maximum adsorption capacity of 9.92 mg/g compared with that (8.03 mg/g) of the pristine biochar. The adsorption kinetics followed the pseudo-second-order model and the intraparticle diffusion model, which indicated that the overall adsorption rate of Cr(VI) was governed by the processes of chemical adsorption, liquid film diffusion and intramolecular diffusion. The increasing of the pH from 3 to 11 significantly affected the Cr(VI) adsorption, where the capabilities decreased from 9.92 mg/g to 0.435 mg/g and 8.03 mg/g to 0.095 mg/g for the m-biochar and pristine biochar, respectively. Moreover, the adsorption mechanisms of Cr(VI) by m-biochar were evaluated and confirmed to include the pathways of electrostatic adsorption, reduction and complexation. This study highlighted an effective synthesis method to prepare a superior Cr(VI) adsorbent, which could contribute to the effective remediation of heavy metal contaminations in the groundwater.     

Adsorption of carbonyl sulfide on modified activated carbon under low-oxygen content conditions

Activated carbon sorbents impregnated with KOH, Fe(NO₃)₃, Cu(NO₃)₂, Zn(NO₃)₂ or Co(NO₃)₂ and their applications in catalytic oxidation reaction of COS were investigated. The results showed that the activated carbon modified with 10 % (mass percentage) KOH enhanced the adsorption ability significantly. And it was also found that the oxygen content and temperature were the two most important factors in the COS adsorption. Further investigation on the pore structures of the samples with X-ray photoelectron spectroscopy indicated that an adsorption/oxidation process happened in the KOH modified activated carbon in which the major existing forms of sulfur were SO₄ ^2? and S species. The oxidation of COS suggested that KOH in the micropores may play a catalytic role during the adsorption. On the other hand, we found that the desorption activation energy from KOHW was higher than that from AC by the CO₂-TPD spectra, which indicated the adsorption of CO₂ on KOH impregnated activated carbon was stronger. The strong adsorption could be attributed to the basic groups on the activated carbon surface. In conclusion, the activated carbon impregnated with KOH promises a good candidate for COS adsorbent.     

Reductive immobilization of <Superscript>79</Superscript>Se by iron canister under simulated repository environment

To understand the fate of ⁷⁹Se in a repository-like environment, the interactions between iron canister surface with dissolved selenite (SeO₃ ²⁻) and selenate (SeO₄ ²⁻) in anaerobic solutions have been investigated. Se(IV) immobilization on iron surface was observed to be about 100 times faster than that of Se(VI) at same conditions. An iron surface coated with a FeCO₃ layer corrosion product is more reactive than a polished iron to immobilize Se(IV) and Se(VI). The reacted iron surfaces were analysed by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS), X-ray diffraction (XRD), Raman spectrometry and micro-X-ray Absorption Spectroscopy (XAS). The result show that Se(IV) and Se(VI) were reduced and precipitated. The dominating phase was found to be FeSe_2.     

Tailoring biochar by PHP towards the oxygenated functional groups (OFGs)-rich surface to improve adsorption performance

In this work, a modification method of H₃PO₄ plus H₂O₂ (PHP) was introduced to targetedly form abundant oxygenated functional groups (OFGs) on biochar, and methylene blue (MB) was employed as a model pollutant for adsorption to reflect the modification performance. Results indicated that parent biochars, especially derived from lower temperatures, substantially underwent oxidative modification by PHP, and OFGs were targetedly produced. Correspondingly, approximately 21.5-fold MB adsorption capacity was achieved by PHP-modified biochar comparing with its parent biochar. To evaluate the compatibility of PHP-modification, coefficient of variation (CV) based on MB adsorption capacity by the biochar from various precursors was calculated, in which the CV of PHP-modified biochars was 0.0038 comparing to 0.64 of the corresponding parent biochars. These results suggested that the PHP method displayed the excellent feedstock compatibility on biochar modification. The maximum MB adsorption capacity was 454.1 mg/g when the H₃PO₄ and H₂O₂ fraction in PHP were 65.2% and 7.0%; the modification was further intensified by promoting temperature and duration. Besides, average 94.5% H₃PO₄ was recovered after 10-batch modification, implying 1.0 kg H₃PO₄ (85%) in PHP can maximally modify 2.37 kg biochar. Overall, this work offered a novel method to tailor biochar towards OFGs-rich surface for efficient adsorption.     

Effect of various environmental factors on the adsorption of U(VI) onto biochar derived from rice straw

Herein, we used biochar pyrolyzed from rice straw to adsorb uranium (U) from aqueous solutions. The adsorption of U(VI) on biochar was strongly dependent on pH but independent on ionic strength. HA/FA enhanced the sorption at pH <6.8 while inhibited the sorption at pH >6.8. The sorption reached equilibrium within 3 h, which was not mediated by pH. The adsorption process was spontaneous and endothermic, and enhanced at higher temperature. However, the influence of temperature was negligible at low initial U(VI) concentrations. Therefore, biochar derived from rice straw may be a promising adsorbent for the removal of U(VI).

     

Solvent Extraction of Selenate and Chromate Using a Diaminocalix[4]arene

The extraction of Se(VI) and Cr(VI) using a diammoniumcalix[4]arene was investigated. A study of parameters such as ligand concentration, pH or diluent was carried out and allowed to specify the stoichiometry of the extracted species. It was shown that Se(VI) is extracted into CHCl₃ as (LH₂ ²⁺, Cl^-, HSeO₄ ^-) and ((LH₂ ²⁺)₂, 2Cl^-, SeO₄ ^2-)species at pH 2.6. An increase of pH or an addition of 5% or 10% decanol in CHCl₃ favors the extraction of SeO₄ ^2- over HSeO₄ ^- but leads to a drastic decrease of seleniumextraction. Cr(VI) was shown to be extracted as(LH₂ ²⁺, Cl^-, HCrO₄ ^-) at pH 2.6 and probably as (LH⁺, HCrO₄ ^-) for higher pH.     

Removal, preconcentration and determination of Mo(VI) from water and wastewater samples using maghemite nanoparticles

Removal and recovery of Mo(VI) from aqueous solutions were investigated using maghemite (γ-Fe₂O₃) nanoparticles. Combination of nanoparticle adsorption and magnetic separation was used to the removal and recovery of Mo(VI) from water and wastewater solutions. The nanoscale maghemite with mean diameter of 50 nm was synthesized by reduction coprecipitation method followed by aeration oxidation. Various factors influencing the adsorption of Mo(VI), e.g. pH, temperature, initial concentration, and coexisting common ions were studied. Adsorption reached equilibrium within <10 min and was independent of initial concentration of Mo(VI). Studies were performed at different pH values to find out the pH at which maximum adsorption occurred. The maximum adsorption occurred at pHs between 4.0 and 6.0. The Langmuir adsorption capacity (q_max) was found to be 33.4 mg Mo(VI)/g of the adsorbent. The results showed that nanoparticle (γ-Fe₂O₃) is suitable for the removal of Mo(VI), as molybdate, from water and wastewater samples. The adsorbed Mo(VI) was then desorbed and determined spectrophotometrically using bromopyrogallol red as a complexation reagent. This allows the determination of Mo(VI) in the range 1.0–86.0 ng mL⁻¹.     

Inorganic speciation of As(III, V), Se(IV, VI) and Sb(III, V) in natural water with GF-AAS using solid phase extraction technology

The paper presents a procedure for the multi-element inorganic speciation of As(III, V), Se(IV, VI) and Sb(III, V) in natural water with GF-AAS using solid phase extraction technology. Total As(III, V), Se(IV, VI) and Sb(III, V) were determined according to the following procedure: titanium dioxide (TiO₂) was used to adsorb inorganic species of As, Se and Sb in sample solution; after filtration, the solid phase was prepared to be slurry for determination. For As(III), Se(IV) and Sb(III), their inorganic species were coprecipitated with Pb-PDC, dissolved in dilute nitric acid, and then determined. The concentrations of As(V), Se(VI) and Sb(V) can be calculated by the difference of the concentrations obtained by the above determinations. For the determination of As(III), Se(IV) and Sb(III), palladium was chosen as a modifier and pyrolysis temperature was 800 °C. Optimum conditions for the coprecipitation were listed for 100 ml of sample solution: pH 3.0, 15 min of stirring time, 40.0 μg l⁻¹ Pb(NO₃)₂ and 150.0 μg l⁻¹ APDC. The proposed method was applied to the determination of trace amounts of As(III, V), Se(IV, VI) and Sb(III, V) in river water and seawater.     

Synthesis of chitosan resin possessing 3,4-diamino benzoic acid moiety for the collection/concentration of arsenic and selenium in water samples and their measurement by inductively coupled plasma-mass spectrometry

A chitosan resin functionalized with 3,4-diamino benzoic acid (CCTS-DBA resin) was newly synthesized by using a cross-linked chitosan (CCTS) as base material. The adsorption behavior of trace amounts of elements on the CCTS-DBA resin was examined by the pretreatment with a mini-column and measurement of the elements by inductively coupled plasma-Mass spectrometry (ICP-MS). Arsenic(V) could be retained on the CCTS-DBA resin at pH 3 as an oxoanion of H₂AsO₄⁻. Selenium(VI) is strongly adsorbed at pH 2 and pH 3 as an oxoanion of SeO₄²⁻, while selenium(IV) as HSeO₃⁻ is adsorbed on the resin at pH 3. The sorption capacities are 82, 64, and 88 mg g⁻¹resin for As(V), Se(IV), and Se(VI), respectively. The effect of common anions and cations on the adsorption of As(V), Se(IV), and Se(VI) were studied; there was no interference from such anionic matrices as chloride, sulfate, phosphate, and nitrate up to 20 ppm, as well as from such artificial river water matrices as Na, K, Mg, and Ca after passing samples through the mini-column containing the resin. The CCTS-DBA resin was applied to the collection of arsenic and selenium species in bottled drinking water, tap water, and river water.     

Heterometallic Uranyl (Hydroxyethyl)iminodiacetic Acid (Heidi) Complexes: Molecular Models for U(VI) Uptake in Complex Media

Amidoximated absorbents (AO-PAN) effectively remove U(VI) from aqueous solution, but previous studies reported more variability for complex natural waters that contain additional confounding ions and molecules. Ternary phases containing U(VI), M(III) (M=Fe(III), Al(III), Ga(III)), and organic molecules exist under these conditions and cause heterogeneous U(VI) uptake on AO-PAN. The goal of the current study is to provide additional insights into the structural features ternary complexes using N-(2-hydroxyethyl)-iminodiacetic acid (HEIDI) as the model organic chelator and explore the relevance of these species on U(VI) capture. Three model compounds ([(UO₂)(Fe)₂(μ₃-O)(C₆NO₅H₈)₂(H₂O)₄] ( UFe₂ ), ([(UO₂)(Al)₂(μ₂-OH)(C₆NO₅H₈)₂(H₂O)₃] ( UAl₂ ) and [(UO₂)(Ga)₂(μ₂-OH)(C₆NO₅H₈)₂(H₂O)₃] ( UGa₂ )) were characterized by single-crystal X-ray diffraction. Raman spectra of the model compounds were compared with solution data and the ternary phases were noted in the case of Al(III) and Ga(III), but not in the Fe(III) system. U(VI) adsorption onto AO-PAN was not impacted by the presence of HEIDI or the trivalent metal species.     

Permselective and Preconcentration Properties of a Surfactant‐Intercalated Clay Modified Electrode

This work is focused on the voltammetric examination of the ion exchange properties of a smectite type clay, before and after its modification by the replacement of its native interlamellar cations (Na⁺, K⁺, Ca²⁺) by hexadecyltrimethylammonium cations (HDTMA⁺). The raw clay and its organically modified form were first characterized by X‐ray diffraction (XRD) and N₂ adsorption–desorption isotherms (BET method) that confirmed the modification via an intercalation process. These materials were subsequently coated onto glassy carbon surfaces, and the resulting modified electrodes were evaluated for the uptake of [Ru(NH₃)₆]³⁺ and [Fe(CN)₆]^3? ions used as redox probes. Some experimental parameters affecting the incorporation of the probes within the film, including the ionic strength, the surfactant loading and the solution pH are thoroughly examined, in order to highlight the mechanism of the process. The possibility of using the surfactant‐intercalated clay modified electrode as an electrochemical sensor for [Fe(CN)₆]^3? is also evaluated.     

Highly efficient removal of diazinon pesticide from aqueous solutions by using coconut shell-modified biochar

This study evaluates the adsorption of diazinon from aqueous solutions onto coconut shell-modified biochar using a batch system. The amount of dosage and initial pH are the main parameters being studied to obtain maximum adsorption capacity of the probe molecules. The carbonized coconut shell biochar (BC1), activated coconut shell biochar (BC2), chemically modified phosphoric acid (BC3) and sodium hydroxide coconut shell biochar (BC4) were prepared and tested as variables in the adsorption experiment. The characteristic of biochar via SEM, EDX and BET analysis revealed the large porous of surface morphology and slight changes in the composition with high surface area (405.97 – 508.07 m²/g) by following the sequence of BC3 > BC2 > BC4. Diazinon removal percentage as high as 98.96% was achieved at pH 7 with BC3 as adsorbent dosing at 5.0 g/L. The high coefficient of determination, R² with a small value of ERRSQ and χ² error analysis present the BC1 (0.9971) and BC2 (0.9999) are best fitted with Freundlich isotherm indicates multilayer sorption onto heterogeneous surface whereby the Langmuir isotherm model is the best fitting is described of monolayer adsorption process onto the homogenous surface of BC3 and BC4. The results indicated the maximum adsorption capacity (q_m) was achieved by BC3 with 10.33 mg/g, followed by BC2 (9.65 mg/g) in accordance to the Langmuir isotherm while Freundlich isotherm showed the highest adsorption capacity (k_F) with 1.73 mg/g (L/mg)^1/n followed by BC4 with 0.63 mg/g (L/mg)^1/n at favorable adsorption isotherm (1 ≤ n ≤ 10). Thus, the results obtained depicted that BC2 and BC3 are highly efficient adsorbents and both exhibit great potential in removing diazinon from aqueous solutions.     

Synthesis of mesoporous maghemite with high surface area and its adsorptive properties

Mesoporous maghemite (γ-Fe₂O₃) with high surface area was prepared by the thermal decomposition of Fe–urea complex ([Fe(CON₂H₄)₆](NO₃)₃) with the aid of cetyltrimethyl ammonium bromide (CTAB), and its adsorption ability for the removal of fluoride was investigated. X-ray diffraction (XRD), nitrogen adsorption–desorption measurements, transmission electron micrograph (TEM) observations, and magnetic measurements show that the γ-Fe₂O₃ has a mesoporous structure and its crystallite size, specific surface area, and magnetic properties can be controlled by varying the content of CTAB in [Fe(CON₂H₄)₆](NO₃)₃. The maximum adsorption capacity of the mesoporous γ-Fe₂O₃ for fluoride is estimated to be 7.9 mg/g, which suggests that the mesoporous γ-Fe₂O₃ is an excellent adsorbent for fluoride.     

Fe–N/C nanofiber electrocatalysts with improved activity and stability for oxygen reduction in alkaline and acid solutions

Fe–N/C nanofiber (Fe–N/CNF) electrocatalysts were prepared by impregnating electrospun polyacrylonitrile nanofibers with iron nitrate (Fe(NO₃)₃) solution and subsequent heat treatment, exhibiting improved activity and stability during oxygen reduction reaction (ORR) both in 0.1 M KOH (pH?=?13) and 0.5 M H₂SO₄ (pH?=?0) electrolyte solutions. Higher treatment temperature and NH₃ atmosphere were preferred by the Fe–N/CNF catalysts, and especially the concentration of Fe(NO₃)₃ solution exerted great effects on the surface morphology, structure, and thus electrocatalytic performance of the catalysts. The Fe–N/CNFs prepared using 0.5 wt% Fe(NO₃)₃ solution showed relatively higher ORR activity in alkaline and acid solutions and better stability especially in 0.5 M H₂SO₄ solution than the catalyst without Fe, probably because Fe could promote the graphitization of the polymer-converted carbon species, enhancing the resistance to electrochemical oxidation and thus the stability of the Fe–N/CNF catalysts.     

Remediation of Cd2+ in aqueous systems by alkali-modified (Ca) biochar and quantitative analysis of its mechanism

Co-pyrolysis of straw and Ca(OH)₂ is a feasible modification method to improve the adsorption capacity of biochar for Cd. However, few studies have quantitatively analyzed the contribution of different adsorption mechanisms of alkali-modified biochar. In this study, the alkali-modified (Ca) biochar were prepared by co-pyrolyzing lime (Ca(OH)₂) and soybean straw (SBB) or rape straw (RSB) at 450 °C. The adsorption mechanism was investigated by a series of experiments and was provided by quantitative analysis. The maximum adsorption capacities of Cd²⁺ by Ca-SBB and Ca-RSB were calculated to be 78.49 mg g^?1 and 49.96 mg g^?1, which were 1.56 and 1.48 times higher than SBB (50.40 mg g^?1) and RSB (33.79 mg g^?1), respectively. Compared with the original biochar (SBB, RSB), alkali-modified biochar (Ca-SBB and Ca-RSB) were found to have faster adsorption kinetics and lower desorption efficiencies. The mechanism study indicated that Ca(OH)₂ modification effectively enhanced the contribution of ion exchange and decreased the contribution of functional groups complexation. After Ca(OH)₂ modification, precipitation and ion exchange mechanisms dominated Cd^2 + absorption on Ca-SBB, accounting for 49.85% and 34.94% of the total adsorption, respectively. Similarily ion exchange and precipitation were the main adsorption mechanism on Ca-RSB, accounting however for 61.91% and 18.47% of total adsorption, respectively. These results suggested that alkali-modified biochar has great potential to adsorp cadmium in wastewater.     

Oximidobenzotetronic acid as a reagent for the separation and gravimetric determination of palladium and cobalt

Oximidobenzotetronic acid is recommended for the separation and gravimetric determination of palladium and cobalt An ethanolic solution of the reagent quantitatively precipitates palladium(II) from solutions which are 0.75 N in acid up to pH 5.1, the complex is weighed as Pd(C₉H₅NO₄)₂. Cobalt(II) can be determined in the filtrate after the precipitation of palladium. With 0.5 N acid solutions, no interference was found from Pt(IV), Ir(IV), Rh(III), Ru(III), Os(IV), Au(III), Ag(I), Cu(II), Fe(III), Ni(II), Hg(II). Pb(II), Bi(III), Cd(II), As(V), Se(VI), Te(IV), Mo(VI), Sb(III), Al(III), Cr(III), Zn(II), Ti(IV), Zr(IV). acetate, oxalate, citrate, tartrate, phosphate and fluoride.     

Study of chromium(VI) adsorption onto modified activated carbons with respect to analytical application

Two different types of modification of activated carbon, by treatment with concentrated solution of HNO₃ and outgassing treatment at high temperature, were studied in order to obtain the most effective adsorption of chromium(VI) ions from water solution. The basic parameters affecting the adsorption capacity of Cr(VI) ions on modified activated carbons were studied in details and the effect of modifications of activated carbons has been determined by studying the initial runs of adsorption isotherms. The obtained Cr(VI) adsorption isotherms were well fitted in the Freundlich equation. The reduction of Cr(VI) to Cr(III) and further ion exchange mechanism of adsorption onto oxidizing activated carbon and surface precipitation to Cr(OH)₃ in case of outgassing activated carbon were found as the main adsorption mechanisms of Cr(VI) ions onto modified activated carbons. Presence of chlorides and nitrates in studied adsorption system strongly decreased the adsorption ability of Cr(VI) onto outgassing activated carbon and mechanism of this behavior is proposed.     

über die Alterung gemeinsam gef?llter AlFe(III)-Hydroxide

The ageing products formed in distilled water at pH 6,3 from hydroxide gels precipitated at pH 7 and 10 by addition of NaOH to solutions of Fe(NO₃)₃ and Al_0,03Fe_0,97(NO₃)₃ were studied.The ageing products were identified by X-ray and IR-spectroscopy. Ageing both at room temperature and by boiling for four hours were studied and shown to be strongly influenced by the pH at which the hydroxides are precipitated, even when immediately washed free of accompanying ions, resulting from different transformations taking place in the originally amorphous hydroxides.     

Sorption of Pb(Ⅱ) on Mg-Fe Layered Double Hydroxide

Mg‐Fe layered double hydroxide (LDH) with a Mg/Fe molar ratio of 3:1 was synthesized by using a coprecipitation method and the sorption removal of Pb(II) by the LDH sample from Pb(NO₃)₂ solution was investigated. It was found that Mg‐Fe LDH showed a good sorption ability for Pb(II) from Pb(NO₃)₂ solution, indicating that the use of LDH as a promising inorganic sorbent for the removal of heavy metal ions is possible. The sorption kinetics and the sorption isotherm of Pb(II) on the LDH sample obeyed the pseudo‐second order kinetic model and Aranovich‐Donohue equation, respectively. The sorption mechanism of Pb(II) on the LDH may be attributed to the surface‐induced precipitation and the chemical binding adsorption, and the removal ability arising from the surface‐induced precipitation is much higher than that from the chemical binding adsorption.     

Extraction and separation of Th(IV) and U(VI) from nitric acid media using PIA-8 and HDEHP

Extraction behavior of Th(IV) and U(VI) has been investigated with bis(2-ethylhexyl) phosphinic acid (PIA-8) and bis(2-ethylhexyl) phosphoric acid (HDEHP) from nitric acid media in toluene. The optimum conditions for extraction of these metals have been established by studying various parameters like acid concentration, pH, reagent concentration, diluents and shaking time. The extraction of Th(IV) was found to be quantitative with 0.3-2.5M HNO₃ by 2.5^.10^-2M HDEHP and in the pH range 0.1-2.5 with 2.3^.10^-2M PIA-8 in toluene. U(VI) was completely extracted in the acidic range of 0.1-2.0M HNO₃ with 2.2^.10^-2M HDEHP and in the pH range of 1.0-3.0 with 2.0^.10^-2M PIA-8 in toluene. The probable extracted species have been ascertained by log D-log c plot as UO₂ R₂ ^.2HR with both the reagents and Th (NO₃)₂R₂ ^.2HR with PIA-8 and Th (NO₃)₃R^.3HR with HDEHP, respectively. Temperature dependence of the extraction equilibrium is examined by the temperature variation method. Separation of U(VI) and Th(IV) was also carried out from commonly associated metals.