Adsorptive features of banana (Musa paradisiaca) stalk-based activated carbon for malachite green dye removal

Chemically prepared activated carbon derived from banana stalk (BSAC) was used as an adsorbent to remove malachite green (MG) dye from aqueous solution. BSAC was characterised using thermogravimetric analyser, Brunauer Emmett Teller, Fourier transform infrared spectrometry, scanning electron microscopy, pH_pzc, elemental analysis and Boehm titration. The effectiveness of BSAC in adsorbing MG dye was studied as a function of pH, contact time, temperature, initial dye concentration and repeated desorption–adsorption processes. pH_pzc of BSAC was 4.5 and maximum dye adsorption occurred at pH 8.0. The rate of dye adsorption by BSAC was very fast initially, attaining equilibrium within 120 min following a pseudo-second-order kinetic model. Experimental data were analysed by Langmuir, Freundlich and Dubinin–Raduschevich isotherms. Equilibrium data fitted best into the Langmuir model, with a maximum adsorption capacity of 141.76 mg·g^?1. Δ G ⁰ values were negative, indicating that the process of MG dye adsorption onto BSAC was spontaneous. The positive values of Δ H ⁰ and Δ S ⁰ suggests that the process of dye adsorption was endothermic. The regeneration efficiency of spent BSAC was studied using 0.5 M HCl, and was found to be in the range of 90.22–95.16% after four cycles. This adsorbent was found to be both effective and viable for the removal of MG dye from aqueous solution.     

Removal of Remazol Brilliant Violet-5R dye using periwinkle shells

The purpose of this research is to obtain optimal processing conditions for the adsorption of Remazol Brilliant Violet-5R (RBV-5R) dye onto activated carbon prepared from periwinkle shells (PSAC) by chemical activation with KOH using response surface methodology. Central composite design (CCD) was used to determine the effects of three preparation variables; CO₂ activation temperature, CO₂ activation time and KOH:char impregnation ratio (IR) on two responses; percentage RBV-5R dye removal and PSAC yield. Based on the CCD, two quadratic models were developed for percentage RBV-5R dye removal and PSAC yield, respectively. The most influential factor on each experimental design response was identified from the analysis of variance (ANOVA). The optimum conditions for the adsorption of RBV-5R dye onto PSAC were CO₂ activation temperature of 811 °C, CO₂ activation time of 1.70 h and IR of 3.0, resulting in 81.28% RBV-5R dye removal and 28.18% PSAC yield. PSAC prepared under optimum conditions was mesoporous with a Brunauer–Emmett–Teller surface area of 1894 m²·g^?1, total pore volume of 1.107 cm³·g^?1 and average pore diameter of 2.32 nm. The surface morphology and functional groups of the activated carbon were respectively determined from the scanning electron microscopy and Fourier transform infrared analysis.     

Fluorescence studies of dye displacement from DNA by chromium(III) complexes: Evidence for cation induced DNA condensations

The interactions of 10 different chromium(III) complexes with isolated calf thymus DNA have been analysed by studying the electronic and fluoresence spectra of intercalated ethidiumbromide. Triply charged cationic complexes including: [Cr(urea)₆]Cl₃.3H₂O, [Cr(1,10‐phenanthroline)₃](ClO₄)₃.2H₂O, [Cr(2,2'‐bipyridyl)₃] (ClO₄)₃.2H₂O, [Cr(ethylendiamine)₃]Cl₃.3.5H₂O and [Cr(NH₃)₆](NO₃)₃ displaced the dye from DNA. Similar effects were observed in experiments using the non‐intercalating dye bisbenzimidazole ("Hoechst 33258"). However, singly charged cationic, anionic and uncharged chromium(III) complexes such as: cis‐[Cr(1,10‐phenanthroline)₂Cl₂]Cl.2H₂O, cis‐[Cr(2,2'‐bipyridyl)₂Cl₂]Cl.2H₂O, [Cr(glutathione)₂]Na₂, [Cr(cysteine)₂]Na.2H₂O and [Cr(glycine)₃] were unable to displace both ethidiumbromide and bisbenzimidazole from DNA. There was no evidence for the formation of co‐ordinate bonds between chromium(III) and DNA for any of the above complexes. The charge and type of ligand are important in controlling the interaction of chromium(III) with isolated DNA in vitro. Our findings indicate that the outer sphere interaction of a chromium(III) complex with DNA is weak and unlikely to be the mechanism by which chromate causes DNA impairments in vivo and in vitro.     

Removal of acid yellow 36 using Box–Behnken designed photoelectro-Fenton: a study on removal mechanisms

Photoelectro-Fenton was applied for the removal of acid yellow 36 (AY36) from synthetic aqueous solution using iron electrodes. A Box–Behnken design was used for optimization of the effects of pH, H₂O₂ concentration, current density, and reaction time. Individual effects of these variables were more important than their interaction effects. The derived model was in good agreement with the experimental results. Total organic carbon was determined in solution and sludge in order to clarify the removal mechanism. Increase of H₂O₂ concentration and current density led to domination of oxidation and coagulation mechanisms, respectively. The effects of scavenging and inhibiting agents were also investigated: (1) presence of alcohols can reduce the efficiency through competition with dye for reaction with hydroxyl radicals; (2) anions (NO₃^?, HCO₃^?, and H₂PO₄^?) scavenged hydroxyl radicals and reduced decolorization of AY36.     

Spectrophotometry determination of Congo red in river water samples using nanosilver

A spectrophotometric procedure for the anionic diazo dye Congo red was proposed based on nanosilver catalyzed oxidation by potassium iodate in a hydrochloric acid medium. The calibration graph is linear for 0.8–240?mg?L^?1, and the detection limit is 0.6?mg?L^?1. Most foreign ions do not interfere with the determination, except for Cu(II), Fe(III), and Cr(VI). The interferences of Cu(II) and Fe(III) could be eliminated by masking with ethylene diamine tetraacetate, and that of Cr(VI) by reducing to Cr(III) with ascorbic acid. The typical features of this procedure are that it is sensitive for Congo red, and the determination could be carried out at room temperature. It had been used for the determination of Congo red in the Ganjnameh river water sample.     

Visible light sensitive activated carbon-metal oxide (TiO2, WO3, NiO,and SnO) nano-catalysts for photo-degradation of methylene blue: a comparative study

Four composites of metal oxide doped with activated carbon with a metal oxide weight of 20% were prepared using mechano-mixing method. The nano-catalysts were characterized by N₂-adsorption–desorption, X-ray diffraction analysis, transmission electron microscopy, Fourier-transform infrared spectroscopy, UV-diffuse reflectance, and photoluminescence spectroscopy. Photo-catalytic degradation of methylene blue dye under UV 254 nm and visible light was examined. In general, prepared catalysts are more active for degradation of dye under visible light than UV, reaching 96% within 180?min irradiation using the SnO catalyst. Photo-degradation of methylene blue followed pseudo first order reaction mechanism with a rate constant of 14.8?×?10^?3?min^?1, and the time required for removal of 50% of dye was 47?min.     

Organochlorine levels in human blood from residents in areas of limited pesticide use in Sudan

Ninety-nine human blood samples were collected from the riverine region of northern Sudan and the traditional and mechanized rain-fed areas of western and eastern Sudan, representing areas of limited pesticide use in Sudan. Blood samples were analyzed for organochlorine pesticides by gas liquid chromatography (GLC) followed by electron-capture detection (ECD). p,p′-DDE (a metabolite of DDT), heptachlor epoxide, β-hexachlorocyclohexane (β-HCH), and dieldrin were detected in all locations surveyed. The level of total organochlorine burden was highest in the traditional rain-fed area, followed by the mechanized rain-fed area, and the riverine area. A highly significant correlation was observed between total organochlorine blood burden and the age of the donors (r = 0.608**).     

Photocatalytic oxidation of the textile dye basic red 18 with irradiated titanium dioxide

One of the major problems of textile wastewater is the presence of dye materials, because colour is visible to the public even if the dye concentration is lower than other pollutants, and needs therefore to be removed from the wastewater before it is discharged. Techniques based on “advanced oxidative processes” such as photocatalysed oxidation seem to be very promising for industrial wastewater treatment, especially for decolourization of textile effluents. In this work, we describe the photocatalytic degradation of the textile dye Basic Red 18 (BR 18) in aqueous solution using two different types of TiO₂ as photocatalyst: Degussa P25 (80% anatase) and Framitalia (100% anatase). Photooxidation of BR 18 was followed by HPLC analysis, and kinetic parameters were evaluated in order to optimise the treatment procedure. The results obtained in this work showed that the colour became virtually zero and the chemical oxygen demand (COD) is strongly reduced at the end of the treatment. The obtained results are compared with the efficiency of decolourization using the H₂O₂/UV System. Finally, marine mussel test was used to evaluate the efficiency of photocatalytic oxidation with TiO₂ in terms of ecotoxicity. A significant reduction of cumulative mortality was observed for the treated effluent.     

Removal of Cu2+ and dye from wastewater using the heavy metal precipitant N,N-bis-(dithiocarboxy)piperazine

We found that a new heavy metal precipitant, disodium N,N-bis-(dithiocarboxy)piperazine, both precipitates Cu²⁺ ions removes the dye from wastewater. The precipitation was based on a coordination polymerization reaction while the removal of the dye could be mainly attributed to an hydrophobic adsorption at pH 7.     

Decolorization and degradation of acid dyes mediated by salt fractionated turnip ( Brassica rapa ) peroxidases

Peroxidases from turnip roots (524?U?g^?1 of vegetable) were highly effective in decolorizing acid dyes having wide spectrum chemical groups. Dye solutions, containing 40–170?mg?dye?L^?1, were treated by turnip peroxidases (TP) (specific activity of 122.0?U?mg^?1 proteins). These enzymes were able to decolorize most of the acid dyes in the presence of 2.0?mM 1-hydroxybenzotriazole (HOBT). Increasing concentration of enzyme and time in the absence of HOBT did not influence dye decolorization. The rate of decolorization was significantly enhanced when HOBT was added to the decolorizing solutions. The decolorization of all the used dyes was maximum at pH 5.0 and 40°C. Complex mixtures of dyes were significantly decolorized when treated with enzyme in the presence of HOBT (2.0?mM). Phytotoxicity test based on Allium cepa root growth inhibition has shown that majority of the TP-treated dye product were not more toxic than their parent dye. Kinetic parameters of the TP with various dyes showed that this enzyme has highest affinity for Acid Yellow 42. This study demonstrates that the peroxidase/mediator system was an effective biocatalyst for the treatment of industrial effluents from textile, dye manufacturing, dyeing and printing industries or complex mixtures of dyes.     

Diurnal variation of nitrogen cycling in coastal,marine sediments

A closed chamber technique was developed to determine the emission of microbially produced N₂O from an estuarine sediment. A diurnal variation was observed; maximum emissions of 0.4 to 4.0 mol N₂O–N m^-2 h^-1 were recorded at night whereas the rates were low or even negative, -0.4 to 0.4 mol N₂O–N m^-2 h^-1, during the day. The bacterial denitrification located in the uppermost centimeter was apparently the major source of the emitted N₂O. The diurnal emission pattern was thus inversely related to the O₂ availability at the sediment surface; in the dark, the lack of O₂ production by benthic photosynthesis allowed the denitrification to occur closer to the sediment-water interface and was likely to enhance the release of N₂O to the water. The daily averages for the emission were about 40 mol N₂O–N m^-2 d^-1 for three investigation periods in autumn (November), winter (February) and spring (April), whereas no significant emission was recorded in the NO ₃ ^- -depleted sediment in early summer (June). In this estuary, the N₂O emissions from the sediment were significant contributions to the overall release of N₂O to the atmosphere.     

Simultaneous measurements of arsenic and sulfide using diffusive gradients in thin films technique (DGT)

Diffusive gradients in thin films technique (DGT) is a dynamically passive sampling technique which has been applied increasingly to the environmental monitoring field. In the preliminary period, the DGT with zirconium hydroxide-silver iodide as the binding phase (ZrO-AgI DGT) has been developed for the determination of sulfide (S(II)). On this basis, this paper developed its determination method for inorganic arsenite (As(III)) to further realize the simultaneous and high-resolution measurements of labile inorganic As and S(II) in sediments. ZrO-AgI binding gel had a strong ability in adsorbing and fixing As(III), showing a linear increase in the initial 12.5 min. After saturation of S(II) on ZrO-AgI binding gel, the adsorption rate and adsorption capacity of As(III) reduced by 8 and 14%, respectively. A stable elution rate (89.1 ± 2.2%) was obtained by extraction of As(III) on the binding gel using a mixture solution of 1.0 M NaOH and 1.0 M H₂O₂ (1:1). The DGT capacity of As(III) determined by the ZrO-AgI DGT was 23.6 μg cm^?2. DGT uptakes of As(III) were independent of pH (4.0–9.0) and ionic strength (0.01–100 mM), and they did not interfere with each other during the uptake process. Simultaneous measurements of labile As and S(II) in four sediment cores of Taihu Lake (China) with ZrO-AgI DGT showed that they had similarly vertical distributions in the top 16-mm layer in one core and in the whole profile up to the 35 mm depth in two cores. It likely reflected a simultaneous release of As and S(II) in sediments by synchronous reduction of As-hosted oxidized iron and sulfate, respectively. The simultaneous decreases of labile As and S(II) from their co-precipitation (e.g., As₂S₃) were not obvious in deeper sediment layer through the measurement with ZrO-AgI DGT.     

Complexation of iron by salicylic acid and its effect on atrazine photodegradation in aqueous solution

The photodegradation of atrazine and the photochemical formation of Fe(II) and H₂O₂ in aqueous solutions containing salicylic acid and Fe(III) were studied under simulated sunlight irradiation. Atrazine photolysis followed first-order reaction kinetics, and the rate constant (k) corresponding to the solution of Fe(III)-salicylic acid complex (Fe(III)-SA) was only 0.0153 h^?1, roughly one eighth of the k observed in the Fe(III) alone solution (0.115 h^?1). Compared with Fe(III) solution, the presence of salicylic acid significantly enhanced the formation of Fe(II) but greatly decreased H₂O₂ generation, and their subsequent product, hydroxyl radical (˙OH), was much less, accounting for the low rate of atrazine photodegradation in Fe(III)-SA solution. The interaction of Fe(III) with salicylic acid was analyzed using Fourier-transform infrared (FTIR) spectroscopy and UV-visible absorption, indicating that Fe(III)-salicylic acid complex could be formed by ligand exchange between the hydrogen ions in salicylic acid and Fe(III) ions.     

Evaluation of kinetics and energy consumption of the electrochemical oxidation of Acid Red 73 in aqueous media

A laboratory scale, undivided electrolysis cell with platinum anode and cathode was used for electrochemical oxidation of the azo dye Acid Red 73 in simulated wastewater. The influence of the supporting electrolyte, applied voltage, pH, initial dye concentration and temperature was studied, and decolorization was monitored by UV/Vis spectroscopy. Energy consumption, current efficiency and the electric energy per order have been also determined. With NaCl (1.5 g L^?1) as supporting electrolyte, at a voltage of 6 V, at neutral pH (6.9) and at 25 °C, the solution of the dye (50 mg L^?1) was completely decolorized within 15 min. The apparent activation energy for electrochemical decolorization was determined as ?1.9 kJ mol^?1.     

Use of the “Acetylene blockage” technique for assaying denitrification in a salt marsh

The acetylene blockage technique was evaluated for measurement of denitrification in salt-marsh sediments (near Halifax, Nova Scotia, Canada). N₂O in the gas phase of closed Spartina alterniflora marsh-sediment systems was analyzed with use of a thermal conductivity gas chromatograph sensitive to approximately 0.1 nmoles ml^-1 gas. No N₂O was detected for unfertilized sediment samples taken through the growing season and incubated in sealed buckets with 10% C₂H₂. For sediment samples amended with nitrate and for enrichments, initial rates of N₂O evolution were higher in the presence of 10% C₂H₂ than in the absence of C₂H₂, but after longterm incubation N₂O was consumed in some samples containing C₂H₂ as well as in samples without C₂H₂. In addition, total gaseous nitrogen (N₂ and N₂O) production in the absence of C₂H₂ was higher than in the presence of C₂H₂. Acetylene appears to be an inconsistent inhibitor of N₂O reduction in salt-marsh sediments. The usefulness of the acetylene-denitrification technique in this habitat is, therefore, questionable.     

Thermodynamics of chromium(III) adsorption onto a cation exchanger derived from saw dust of Jack wood

A novel cation exchanger, polymethacrylic acid-grafted saw dust (SD) with spacer group (SP) containing carboxylate functional group at the chain end (SDGPMA-SP-COOH) was prepared from saw dust of Jack wood, and its adsorption equilibrium and thermodynamics of Cr(III) ions were studied at different initial concentrations and temperatures at pH 7.0 using batch technique. Thermodynamic parameters such as change in standard free energy, ΔG ⁰, standard enthalpy, ΔH ⁰ and standard entropy, ΔS ⁰ were determined. The values of isosteric heat of adsorption (ΔH _x ) remain constant at different surface loading of Cr(III) indicating homogeneous surface sites and the absence of lateral interaction between adsorbed ions.     

Spectrophotometric determination of trifluralin in commercial formulations and agricultural samples using factorial design

A simple spectrophotometric method was developed for determination of trifluralin in commercial formulation and food samples. The method was based on the hydrolysis of trifluralin with sodium hydroxide to form 2,6-dinitro-4-trifluoromethylaniline. The resultant aniline group was diazotized with nitrate in acidic media and the diazotized product was coupled with β-naphthol to form red colored product having λ_max 550 nm. The reaction conditions were optimized for hydrolysis as well as for the diazotization reaction. The Beer’s law was obeyed over the range of 0.2–17 μg mL⁻¹ with molar absorptivity of 1.5 × 10⁴ L mol⁻¹ cm⁻¹. The relative standard deviation was found to be 3.6%. A two level factorial design of 2³ was used for optimization of all parameters. The influence of different factors and their interactions on the final azo dye formation were also studied from these factorial designs. The method has been applied successfully for the analysis of commercial formulations and agricultural samples. The recovery for the determination of trifluralin was found to be in the range 95–97%.     

Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication     

Spatial variations in the N2O emissions and denitrification potential of riparian buffer strips in a contaminated urban river

Spatial variations in the N₂O emissions and denitrification potential of riparian buffer strips (RBS) in a polluted river were examined. The river received large pollutant inputs from urban runoff and wastewater discharge, resulting in impaired water quality in the river and downstream reservoir. The potential for nitrogen removal by RBS was evaluated by measuring in situ N₂O emission fluxes in static closed chambers and sediment denitrification potentials with acetylene inhibition techniques. The results showed that N₂O emission fluxes decreased from the upstream (16.39 μg/(m²·h)) to downstream (0.30 μg/(m²·h)) sites and from the water body to upland sites. The trend in decreasing N₂O emission fluxes in the downstream direction was mainly associated with sediment/soil textures (clay loam→sandy soil) and sediment/soil water contents and was also related to the vegetation along the RBS and nutrients in the sediments/soils. The correlation coefficient was highest (r=0.769) between the N₂O emission flux and sediment/soil water content. Sediment/soil denitrification potentials under N-amended and ambient conditions were higher (highest 32.86 mg/(kg·h)) for the upstream sites, which were consistent with in situ N₂O flux rates.