Kinetic features of chromium(VI) reduction and phenol degradation in aqueous solution by treatment in atmospheric-pressure air direct-current discharge

The kinetics of the processes of simultaneous reduction of Cr(VI) and degradation of phenol during the treatment of their aqueous solutions with different initial concentrations using an atmosphericpressure air direct-current discharge have been studied. The solution served as the discharge cathode. It has been shown that the discharge treatment leads to a decrease in the concentration of both Cr(VI) and phenol. Phenol additives accelerate the Cr(VI) reduction process and make it irreversible. The phenol degradation and Cr(VI) reduction kinetics are described well (R² > 0.99) by the pseudo-first-order rate equation in phenol and Cr(VI) concentrations, respectively. The apparent rate constants of the processes have been determined, the energy efficiency of the processes has been evaluated, and possible mechanisms of the proceeding reactions have been discussed.     

Determination of Cr(VI) Using a Pulse Amperometric Method with an Ionophore‐Immobilized Membrane Electrode

A pulse amperometric method for the determination of Cr(VI) in aqueous solution has been investigated with an ionophore‐immobilized membrane electrode. The double potential step chronoamperometry was applied to measure the current for the facilitated transfer of Cr(VI) by the membrane with N,N,N′,N′‐tetrakis(3‐aminopropyl)‐1,4‐butanediamine (DABAm4) coated on a silver electrode. The current responses were stably detected by the pulse amperometry while voltage pulses, ΔE=?240 mV, of short duration of 50 ms were employed at the interval of 5 s. In the range of 1.65–81.3 μM, Cr(VI) in water could be selectively determined in the presence of various interfering anions below 100 μM without removal of Cr(VI) from the interferences using an ion exchange column.     

Cr(VI) Reduction by Microsecond Pin-to-Pin Discharges Generated in an Aqueous Solution

Plasma Chemistry and Plasma Processing - The total reduction of Cr(VI) by microsecond pin-to-pin electric discharge generated in aqueous solution has been reported. [Cr(VI)] and [H2O2] were...     

Preconcentration of total chromium on Dowex 50W-X8 resin loaded with 2-amino-benzenethiol

Application of Dowex 50W-X8 loaded with 2-amino-benzenethiol for preconcentration of total chromium (Cr(VI) and Cr(III)) in water samples and subsequent determination by inductively coupled plasma-atomic emission spectrometry was studied. The reagent 2-amino-benzenethiol loaded onto the resin effectively reduced Cr(VI) to Cr(III) and total chromium (both Cr(VI) and Cr(III)) formed chelate complex with the reagent in the Cr(III) valence state. Experimental parameters such as preconcentration time, solution flow rates, pH, and concentration of the eluent were optimized. The method has been applied for the determination of total chromium in seawater samples in the range of 0.1–200?µg?L^?1. A detection limit of 0.3?µg?L^?1 was achieved, and the relative standard deviation was about 5%.     

Extraction mechanism of Cr(VI) on the aqueous two-phase system of tetrabutylammonium bromide and (NH(4))(2)SO(4) mixture

An aqueous two-phase system of tetrabutylammonium bromide (TBAB) and (NH(4))(2)SO(4) mixture has been developed for the extractive preconcentration and separation of certain compounds. TBAB concentration in upper phase is much higher than that of bottom solution. This new aqueous two-phase system is proposed for the highly selective extraction of Cr(VI) from large amounts of Cr(3+). The Cr(VI) is found to be extracted into the TBAB-rich upper phase due to ion pair formation such as HCrO(4)(-) . TBAB(+). The Cr(VI) was sufficiently extracted into the upper phase in the pH range from 1 to 5. The proposed method has been applied to the determination of trace of Cr(VI) in wastewater samples with a coefficient of variation less than 3.2%. The recovery obtained was not lower than 90%. The determination limit for the Cr(VI) was found to be 60 mug l(-1) in 10 ml of sample solution.     

Reduction–Oxidation of Chromium Ions in Aqueous Solution by Treatment with Atmospheric-Pressure Direct-Current Discharge in Argon

Kinetic features of the oxidation–reduction processes of chromium ions in a potassium dichromate aqueous solution subjected to treatment in argon atmospheric-pressure dc discharge have been investigated in the discharge current range of 20–80 mA and the dichromate concentration range of 0.1–0.5 mmol/L. The solution served as the discharge cathode. It has been revealed that the discharge treatment stimulates the reduction reactions of Cr⁶⁺ to Cr³⁺ ions and the reverse reactions of oxidation of Cr³⁺ to Cr⁶⁺ ions; i.e., the oxidation–reduction reactions are reversible. The limiting degree of reduction of Cr⁶⁺ ions has been found to depend on the discharge current and the initial concentration of the solution. The apparent rate constants of oxidation and reduction have been determined, and the energy efficiency of the process has been evaluated. The data are compared with the results obtained earlier for a discharge in air.     

Étude de l’élimination du Cr(VI) par l’oxyde mixte obtenu par calcination de l’hydroxyde double lamellaire MgAl

A magnesium aluminium hydrotalcite-like compound (HT) containing carbonate anions in the interlayer space and with a final Mg/Al ratio of 2 was synthesized by the co-precipitation method. The obtained material was characterized by powder X-ray diffraction (XRD), Fourier-Transform–Infrared spectroscopy (FT–IR), thermal analysis (ATG/ATD), and surface area measurements (BET). The interaction of the clay with Cr(VI) has been studied by ultraviolet–visible (UV–vis) spectroscopy. The calcined hydrotalcite (HT-C) showed the highest capacity of removal of chromium ions, and their sorption capacities for Cr(VI) are 4.85 mmol/g. The effect of various parameters on the preparation conditions for the removal of chromium, such as the contact time, the amount of sorbent, the initial concentration of Cr(VI), and the pH values of aqueous solution were also investigated to identify their influence on Cr(VI) sorption. The characterization of the calcined hydrotalcite (HT-C) after interaction with Cr(VI) ions by FT–IR spectroscopy showed that Cr(VI) was adsorbed and intercalated by the solid.     

Speciation of Cr(III) and Cr(VI) in water after preconcentration of its 1,5-diphenylcarbazone complex on amberlite XAD-16 resin and determination by FAAS

A simple and sensitive method for the speciation, separation and preconcentration of Cr(VI) and Cr(III) in tap water was developed. Cr(VI) has been separated from Cr(III) and preconcentrated as its 1,5-diphenylcarbazone complex by using a column containing Amberlite XAD-16 resin and determined by FAAS. Total chromium has also been determined by FAAS after conversion of Cr(III) to Cr(VI) by oxidation with KMnO₄. Then, Cr(III) has been calculated by subtracting Cr(VI) from the total. The effect of acidity, amount of adsorbent, eluent type and flow rate of the sample solution on to the preconcentration procedure has been investigated. The retained Cr(VI) complex was eluated with 10 ml of 0.05 mol l⁻¹ H₂SO₄ solution in methanol. The recovery of Cr(VI) was 99.7±0.7 at 95% confidence level. The highest preconcentration factor was 25 for a 250 ml sample volume. The detection limit of Cr(VI) was found as 45 μg l⁻¹. The adsorption capacity of the resin was found as 0.4 mg g⁻¹ for Cr (VI). The effect of interfering ions has also been studied. The proposed method was applied to tap water samples and chromium species have been determined with the relative error <3%.     

Speciation Analysis of Cr(III) and Cr(VI) after Solid Phase Extraction Using Modified Magnetite Nanoparticles

A new solid phase extraction (SPE) method has been developed for the speciation of Cr(III) and Cr(VI). This method is based on the adsorption of Cr(VI) on modified alumina‐coated magnetite nanoparticles (ACMNPs). Total chromium in different samples was determined as Cr(VI) after oxidation of Cr(III) to Cr(VI) using H₂O₂. The chromium concentration has been determined by flame atomic absorption spectrometric (FAAS) technique and amount of Cr(III) was calculated by substracting the concentration of Cr(VI) from total chromium concentration. The effect of parameters such as pH, amount of adsorbent, contact time, sample volume, eluent type, H₂O₂ concentration and cetyltrimethylammonium bromide (CTAB) concentration as modifier on the quantitative recovery of Cr(VI) were investigated. Under the optimal experimental conditions, the preconcentration factor, detection limit, linear range and relative standard deviation (RSD) of Cr(VI) were 140 (for 350 mL of sample solution), 0.083 ng mL^?1, 0.1‐10.0 ng mL^?1 and 4.6% (for 5.0 ng mL^?1, n = 7), respectively. This method avoided the time‐consuming column‐passing process of loading large volume samples in traditional SPE through the rapid isolation of CTAB@ACMNPs with an adscititious magnet. The proposed method was successfully applied to the determination and speciation of chromium in different water and wastewater samples and suitable recoveries were obtained.     

Speciation of Cr(III) and Cr(VI) in Environmental Samples after Solid Phase Extraction on Amberlite XAD–2000

A method for speciation of Cr(III) and Cr(VI) in real samples has been developed. Cr(VI) has been separated from Cr(III) and preconcentrated as its pyrrolidinedithiocarbamate (APDC) complex by using a column containing Amberlite XAD–2000 resin and determined by FAAS. Total chromium has also been determined by FAAS after conversion of Cr(III) to Cr(VI) by oxidation with KMnO₄. Cr(III) has been calculated by subtracting Cr(VI) from the total. The effect of pH, flow‐rate, adsorption and batch capacity and effect of various metal cations and salt anions on the sorption onto the resin were investigated. The adsorption is quantitative in the pH range of 1.5–2.5, and Cr(VI) ion was desorbed by using H₂SO₄ in acetone. The recovery of Cr(VI) was 97 ± 4 at a 95% confidence level. The highest preconcentration factor was 80 for a 200 mL sample volume. The adsorption and batch capacity of sorbent were 7.4 and 8.0 mg g^?1 Cr(VI), respectively, and loading half time was 5.0 min. The detection limit of Cr(VI) is 0.6 μg/L. The procedure has been applied to the determination and speciation of chromium in stream water, tap water, mineral spring water and spring water. Also, the proposed method was applied to total chromium preconcentration in microwave digested moss and rock samples with satisfactory results. The developed method was validated with CRM‐TMDW‐500 (Certified Reference Material Trace Metals in Drinking Water) and BCR‐CRM 144R s (Certified Reference Material Sewage Sludge, Domestic Origin) and the results obtained were in good agreement with the certified values. The relative standard deviations were below 6%.     

Separation,preconcentration and speciation of chromium by solid phase extraction on immobilised ferron

A sensitive and simple method for determination of chromium species after separation and preconcentration by solid phase extraction (SPE) has been developed. For the determination of the total concentration of chromium in solution, Cr(VI) was efficiently reduced to Cr(III) by addition of hydroxylamine and Cr(III) was preconcentrated on a column of immobilised ferron on alumina. The adsorbed analyte was then eluted with 5?mL of hydrochloric acid and was determined by flame atomic absorption spectrometery. The speciation of chromium was affected by first passing the solution through an acidic alumina column which retained Cr(VI) and then Cr(III) was preconcentrated by immobilised ferron column and determined by FAAS. The concentration of Cr(VI) was determined from the difference of concentration of total chromium and Cr(III). The effect of pH, concentration of eluent, flow rate of sample and eluent solution, and foreign ions on the sorption of chromium (III) by immobilised ferron column was investigated. Under the optimised conditions the calibration curve was linear over the range of 2–400?µg?L^?1 for 1000?mL preconcentration volume. The detection limit was 0.32?µg?L^?1, the preconcentration factor was 400, and the relative standard deviation (%RSD) was 1.9% (at 10?µg?L^?1; n?=?7). The method was successfully applied to the determination of chromium species in water samples and total chromium in standard alloys.     

SURFACTANT MEDIATED POLYMERIZATION KINETICS OF ACRYLAMIDE USING CR(VI)-CYCLOHEXANONE REDOX SYSTEM

The effect of organized surfactants on the kinetics of acrylamide (AM) polymerization have been studied over a temperature range of 25–45°C using Cr (VI)-cyclohexanone (CH) redox system as initiator. The rate of polymerization, R_p(obs), as well as, the percentage of the monomer conversio were found to be increased with increasing the concentration of the anionic surfactant (SDS), above its CMC. But the cationic surfactant (CTAB) reduced the rate considerably at higher concentration, while non-ionic surfactant (TX-100) played no role on the rate. The effect of [Cr(VI)], [CH], [AM], [H+], and ionic strength on the rates have also been examined. The presence of 0.015M SDS decreased the overall activation energy of the polymerization by 6.28 k.Cal/ mole as compared to that in the absence of a surfactant. On increasing the SDS concentration, the viscosity average molecular weight was also found to increase. For the polymerization process, a mutable mechanistic scheme has been pro-posed.     

水溶液中六价铬在碳纳米管上的吸附

针对用碳纳米管对水溶液中六价铬的吸附净化进行了研究, 考察了溶液浓度、溶液pH值、共存的三价铬离子等因素对吸附行为的影响. 实验结果表明, 碳纳米管在室温下对于六价铬的吸附量随着平衡浓度的增大而升高, 在铬浓度为493.557 mg•L−1时碳纳米管吸附量达到最大值为532.215 mg•g−1; 六价铬的浓度在300~700 mg•L−1的范围内, 碳纳米管对铬的吸附量变化不大；大于700 mg•L−1时, 随着铬的平衡浓度的升高碳纳米管对铬的吸附量降低, 铬浓度为961.074 mg•L−1时, 碳纳米管吸附量降至194.631 mg•g−1. 在pH值为2~7的范围内, 碳纳米管对六价铬的吸附量随着溶液pH值的减小而增大; 而在碱性条件下, pH值对碳纳米管吸附六价铬的影响不大. 溶液中存在三价铬时, 碳纳米管对六价铬的吸附量明显降低, 表明三价铬与六价铬有竞争吸附. 此外, 活性炭的对比吸附实验表明, 在低浓度时, 譬如在六价铬浓度为190 mg•L−1吸附时, 碳纳米管对铬的吸附量约为活性炭的6倍；而在高浓度下, 譬如六价铬浓度为493 mg•L−1时, 碳纳米管对铬的吸附量约为活性炭的2倍.     

铬(VI)-谷胱甘肽配合物诱导小牛胸腺DNA变性的新表征方法

本文采用电化学方法对铬(VI)-谷胱甘肽(GSH)配合物诱导DNA变性进行表征，同时运用原子力显微镜(AFM)对DNA损伤变性过程进行可视化探测。结果表明：在pH=5.6的HAc-NaAc缓冲溶液中，DNA溶液中加入Cr(VI)-GSH配合物后进行循环伏安扫描，+0.20 V和0.00 V(vs SCE)处出现一对新的氧化还原峰，该氧化还原峰随Cr(VI)-GSH配合物浓度增加峰电流上升。DNA热变性和表面活性剂SDS变性实验进一步证明了该峰为DNA变性后的氧化还原峰，且变性DNA的峰信号在修饰电极上比裸金电极上更为灵敏。电化学动力学表明在30 min内配合物诱导DNA变性的程度随时间的上升而增加，并通过AFM观察了配合物作用下DNA断链的过程。     

Adsorption-reduction performance of tea waste and rice husk biochars for Cr(VI) elimination from wastewater

In the current study tea waste and rice husk biochars were used for the elimination of Cr(VI) from wastewater with the objectives to study the effect of pH (3–10), shaking time (0.016–24 h), sorbent dose (0.1–1.3 g L⁻¹) and initial concentration of Cr(VI) (10–250 mg L⁻¹). The Cr(VI) sorption was studied under various factors in which solution pH played a main role and at pH 5.2, maximum 99.3% and 96.8% Cr(VI) were removed by tea waste biochar (TWB) and rice husk biochar (RHB), respectively. In comparison, 197.5 mg g⁻¹ and 195.24 mg g⁻¹ Cr(VI) were sorbed by TWB and RHB, respectively with 120 mg L⁻¹ initial Cr(VI) concentration. In contact time study, after 2 h, equilibrium was achieved for both biochars which indicated that the Cr(VI) elimination from aqueous medium is a fast process. Kinetic and isotherm modeling data showed that pseudo-second order model and Langmuir (monolayer sorption) models provided the best fit for sorption of Cr(VI) onto both biochars. The –OH, COO– and –NH₂ functional groups were involved in the sorption of Cr(VI) onto biochars according to FTIR. Biochars produced from both biomass effectively removed Cr(VI) from polluted water, however in comparison sorption capacity of TWB was slightly higher than RHB. It was concluded that TWB and RHB could provide a cost-effective and viable option for elimination of Cr(VI) from wastewater.     

Amperometric Determination of Cr(III) and Cr(VI) by Flow Injection Analysis

Speciation of Cr(III) and Cr(VI) can be attained by flow injection analysis with amperometric detection. Cr(VI) is reduced in an acidic medium to Cr(III) with a glassy carbon electrode at —0.1 V vs. Ag/AgCl and the current is recorded. Cr(III) is oxidised on-line to Cr(VI) with alkaline hydrogen peroxide solution. From the difference of the total chromium and Cr(VI), the amount of Cr(III) was obtained. A linear calibration curve for Cr(VI) was obtained for the concentration ranges 0.01-5.0ppm of Cr(VI) and we have calculated the limit of determination to be about 0.5ppb. We have studied the degree of reproducibility obtained using the solid electrodes under various conditions. The influence of flow rate, coil length, interfenences and the extent of reaction were studied.     

Extraction of Cr (VI) by pickering emulsion liquid membrane using amphiphilic silica nanowires (ASNWs) as a surfactant

Pickering emulsion is the replacement of surfactants with solid, often nano-sized particles. The particle-stabilized emulsions have good thermodynamic and kinetic stability. Pickering emulsion liquid membrane (PELM) was prepared using mahua oil as a diluent, aliquat 336 (Trioctyl methylammonium chloride) as a carrier and amphiphilic silica nanowires (ASNWs) (10–40?ml ethanol addition) as a surfactant. Sodium hydroxide (NaOH) was used as stripping phase in the concentration range from 0.1 to 0.5?M for the extraction of hexavalent chromium [Cr (VI)] from aqueous solution. The variety of edible and non-edible oils was investigated for the stability of water in oil emulsion. Factors that influence silica-stabilized Pickering emulsions are pH, agitation speed, stripping phase concentration, the volume ratio of membrane to stripping phase (M/S), initial feed concentration, treat ratio(feed to emulsion volume ratio) and surfactant concentration for better PELM stability. And also, the extraction efficiency of Cr (VI) was investigated using aliquat as a carrier. The physicochemical properties of ASNWs were studied using Scanning Electron Microscopy (SEM), Fourier Transforms Infrared Spectroscopy (FTIR) and Dynamic Light Scattering (DLS) techniques. At an optimum condition, 99.69% of Cr (VI) removal from aqueous solution was obtained.     

Adsorption of metal anions of vanadium(V) and chromium(VI) on Zr(IV)-impregnated collagen fiber

The metal anions of vanadium (V) and chromium (VI) in aqueous solution can be effectively adsorbed by Zr(IV)-impregnated collagen fiber (ZrICF). The maximum adsorption capacity of V(V) takes place within the pH range of 5.0 to 8.0, while that of Cr(VI) is within the pH range of 6.0 to 9.0. When the initial concentration of metal ions was 2.00 mmol L⁻¹ and the temperature was 303 K, the adsorption capacity of V(V) on Zr-ICF was 1.92 mmol g⁻¹ at pH 5.0, and the adsorption capacity of Cr(VI) was 0.53 mmol g⁻¹ at pH 7.0. As temperature increased, the adsorption capacity of V(V) increased, while that of Cr(VI) was almost unchanged. The adsorption isotherms of the anionic species of V(V) and Cr(VI) can be fit by the Langmuir equation. The adsorption rate of V(V) follows the pseudo-first-order rate model, while the adsorption rate of Cr(VI) follows the pseudo-second-order rate model. Furthermore, ZrICF shows high adsorption selectivity to V(V) in the mixture solution of V(V) and Cr(VI). Practical applications of ZrICF could be expected in consideration of its performance in adsorption of V(V) and Cr(VI).     

Adsorption of Cr(VI) using activated neem leaves: kinetic studies

In the present study, adsorbent is prepared from neem leaves and used for Cr(VI) removal from aqueous solutions. Neem leaves are activated by giving heat treatment and with the use of concentrated hydrochloric acid (36.5 wt%). The activated neem leaves are further treated with 100 mmol of copper solution. Batch adsorption studies demonstrate that the adsorbent prepared from neem leaves has a significant capacity for adsorption of Cr(VI) from aqueous solution. The parameters investigated in this study include pH, contact time, initial Cr(VI) concentration and adsorbent dosage. The adsorption of Cr(VI) is found to be maximum (99%) at low values of pH in the range of 1-3. A small amount of the neem leaves adsorbent (10 g/l) could remove as much as 99% of Cr(VI) from a solution of initial concentration 50 mg/l. The adsorption process of Cr(VI) is tested with Langmuir isotherm model. Application of the Langmuir isotherm to the system yielded maximum adsorption capacity of 62.97 mg/g. The dimensionless equilibrium parameter, R _L, signifies a favorable adsorption of Cr(VI) on neem leaves adsorbent and is found to be between 0.0155 and 0.888 (0<R _L<1). The adsorption process follows second order kinetics and the corresponding rate constant is found to be 0.00137 g/(mg) (min).     

The interaction of cysteine with chromium(VI) ions under UV irradiation

In 0.1 M phosphate buffer (pH 7.2), the interaction of chromium(VI) with cysteine in the presence and absence of UV irradiation was studied by cyclic voltammetry and electronic spectroscopy techniques. The reduction of Cr(VI) by cysteine takes place through the formation of Cr(VI)-thioester intermediate. On the cyclic voltammograms of cysteine and Cr(VI) mixture, the peaks at -0.315 and -0.800 V were observed, and these peaks are corresponding to the reduction of Cr(VI)-thioester and thiyl radical, respectively. In the cysteine solution exposed to UV irradiation, the formation of free cystine was observed at -0.792 V. In the cysteine and Cr(VI) mixture exposed to UV irradiation, the peak current of thiyl radical increases while the peak current of Cr(VI)-thioester reaches a maximum at 15 min and then decreases by increasing UV irradiation time. The formation of the thioester in the reaction between Cr(VI) and cysteine in aqueous media has been studied by monitoring the decrease of Cr(VI) at 370 nm. It was observed that the reaction is catalyzed by the UV irradiation of the Cr(VI) and cysteine mixture.