Gallic acid degradation in aqueous solutions by UV/H2O2 treatment, Fenton's reagent and the photo-Fenton system

Gallic acid (3,4,5-trihydroxybenzoic acid) is a major pollutant present in the wastewater generated in the boiling cork process, as well as in other wastewaters from food manufacturing industries. Its decay in aqueous solutions has been studied by the action of several oxidation systems: monochromatic UV radiation alone and combined with hydrogen peroxide, Fenton's reagent and the combination Fenton's reagent with UV radiation (photo-Fenton system). The influence of the pH is discussed and the quantum yields are determined in the UV radiation system. Also, the influence of operating variables (initial concentrations of H2O2 and Fe(II), and pH) is established in the Fenton's reaction. The apparent pseudo-first-order rate constants are evaluated in all the experiments conducted in order to compare the efficiency of each one of the processes. Increases in the degradation levels of gallic acid are obtained in the combined processes in relation to the single UV radiation system, due to reactions of the very reactive OH*. These improvements are determined in every process by calculating the partial contribution to the overall decomposition rate of the radical pathways. For the oxidant concentrations applied, the most effective process in removing gallic acid was found to be the photo-Fenton system. The rate constant for the reaction of gallic acid with OH was also determined by means of a competition kinetics model, being its value 11.0+/-0.1 x 10(9)l mol(-1)s(-1).     

Cross-linked quaternary chitosan as an adsorbent for the removal of the reactive dye from aqueous solutions

Adsorption of reactive orange 16 by quaternary chitosan salt (QCS) was used as a model to demonstrate the removal of reactive dyes from textile effluents. The polymer was characterized by infrared (IR), energy dispersive X-ray spectrometry (EDXS) analyses and amount of quaternary ammonium groups. The adsorption experiments were conducted at different pH values and initial dye concentrations. Adsorption was shown to be independent of solution pH. Three kinetic adsorption models were tested: pseudo-first-order, pseudo-second-order and intraparticle diffusion. The experimental data best fitted the pseudo-second-order model, which provided a constant velocity, k₂, of 9.18 × 10⁻⁴ g mg⁻¹ min⁻¹ for a 500 mg L⁻¹ solution and a value of k₂, of 2.70 × 10⁻⁵ g mg⁻¹ min⁻¹ for a 1000 mg L⁻¹ solution. The adsorption rate was dependent on dye concentration at the surface of the adsorbent for each time period and on the amount of dye adsorbed. The Langmuir isotherm model provided the best fit to the equilibrium data in the concentration range investigated and from the isotherm linear equation, the maximum adsorption capacity determined was 1060 mg of reactive dye per gram of adsorbent, corresponding to 75% occupation of the adsorption sites. The results obtained demonstrate that the adsorbent material could be utilized to remove dyes from textile effluents independent of the pH of the aqueous medium.     

Application of the hybrid complexation-ultrafiltration process for metal ion removal from aqueous solutions

Complexation-ultrafiltration process was investigated for mercury and cadmium removal from aqueous solutions by using poly(acrylic acid) sodium salt (PAASS) as a complexing agent. The kinetics of complexation reactions of PAASS with the metal ions were studied under a large excess PAASS and pH 5.5. It takes 25 and 50 min for mercury and cadmium to get the complexation equilibrium, respectively, and the reaction kinetics can be described by a pseudo-first-order equation. Effects of various operating parameters such as loading ratios, pH values, etc. on metal rejection coefficients (R) were investigated. In the process of concentration, membrane fluxes decline slowly and R values are about 1. The concentrated retentates were used further for the decomplexation. The decomplexation ratio of mercury-PAASS complex is about 30%, whereas that of cadmium-PAASS complex reaches 93.5%. After the decomplexation, diafiltration experiments were carried out at pH 2.5. Cadmium can be diafiltrated satisfactorily from the retentate, but for mercury it is the contrary. Selective separation of the both metal ions was studied from a binary solution at pH 5. When mercury, cadmium and PAASS concentrations are 30, 30 and 40 mg L(-1), respectively, mercury is retained by ultrafiltration while almost all cadmium passes through the membrane.     

A combined treatment approach using Fenton's reagent and zero valent iron for the removal of arsenic from drinking water

Studies on the development of an arsenic remediation approach using Fenton's reagent (H2O2 and Fe(II)) followed by passage through zero valent iron is reported. The efficiency of the process was investigated under various operating conditions. Potable municipal water and ground water samples spiked with arsenic(III) and (V) were used in the investigations. The arsenic content was determined by ICP-QMS. A HPLC-ICPMS procedure was used for the speciation and determination of both As(III) and (V) in the processed samples, to study the effectiveness of the oxidation step and the subsequent removal of the arsenic.The optimisation studies indicate that addition of 100 microl of H2O2 and 100 mg of Fe(II) (as ferrous ammonium sulphate) per litre of water for initial treatment followed by passing through zero valent iron, after a reaction time of 10 min, is capable of removing arsenic to lower than the US Environmental Protection Agency (EPA) guideline value of 10 microg/l, from a starting concentration of 2 mg/l of As(III). Using these suggested amounts, several experiments were carried out at different concentrations of As(III). Residual hydrogen peroxide in the processed samples can be eliminated by subsequent chlorination, making the water, thus, processed, suitable for drinking purposes. This approach is simple and cost effective for use at community levels.     

Removal of heavy metal ions from aqueous solutions using carbon aerogel as an adsorbent

The removal of Cd(II), Pb(II), Hg(II), Cu(II), Ni(II), Mn(II) and Zn(II) by carbon aerogel has been found to be concentration, pH, contact time, adsorbent dose and temperature dependent. The adsorption parameters were determined using both Langmuir and Freundlich isotherm models. Surface complexation and ion exchange are the major removal mechanisms involved. The adsorption isotherm studies clearly indicated that the adsorptive behaviour of metal ions on carbon aerogel satisfies not only the Langmuir assumptions but also the Freundlich assumptions, i.e. multilayer formation on the surface of the adsorbent with an exponential distribution of site energy. The applicability of the Lagergren kinetic model has also been investigated. Thermodynamic constant (K(ad)), standard free energy (DeltaG(0)), enthalpy (DeltaH(0)) and entropy (DeltaS(0)) were calculated for predicting the nature of adsorption. The results indicate the potential application of this method for effluent treatment in industries and also provide strong evidence to support the adsorption mechanism proposed.     

Untreated coffee husks as biosorbents for the removal of heavy metals from aqueous solutions

The objective of this work was to propose an alternative use for coffee husks (CH), a coffee processing residue, as untreated sorbents for the removal of heavy metal ions from aqueous solutions. Biosorption studies were conducted in a batch system as a function of contact time, initial metal ion concentration, biosorbent concentration and pH of the solution. A contact time of 72 h assured attainment of equilibrium for Cu(II), Cd(II) and Zn(II). The sorption efficiency after equilibrium was higher for Cu(II) (89-98% adsorption), followed by Cd(II) (65-85%) and Zn(II) (48-79%). Even though equilibrium was not attained in the case of Cr(VI) ions, sorption efficiency ranged from 79 to 86%. Sorption performance improved as metal ions concentrations were lowered. The experimental sorption equilibrium data were fitted by both Langmuir and Freundlich sorption models, with Langmuir providing the best fit (R2>0.95). The biosorption kinetics was determined by fitting first and second-order kinetic models to the experimental data, being better described by the pseudo-second-order model (R2>0.99). The amount of metal ions sorbed increased with the biosorbent concentration in the case of Cu(II) and Cr(VI) and did not present significant variations for the other metal ions. The effect of the initial pH in the biosorption efficiency was verified in the pH range of 4-7, and the results showed that the highest adsorption capacity occurred at distinct pH values for each metal ion. A comparison of the maximum sorption capacity of several untreated biomaterial-based residues showed that coffee husks are suitable candidates for use as biosorbents in the removal of heavy metals from aqueous solutions.     

Detoxification and/or increase of the biodegradability of aqueous solutions of dimethoate by means of solar photocatalysis

Different methods have been used to measure changes in biodegradability/toxicity of aqueous solutions of the pesticide Laition (a commercial formula of methidathion) when it is treated by means of TiO₂ photocatalysis: short time biological oxygen demand (BOD_st) was used to determine the instantaneous biodegradability of the sample; BOD₅ was also chosen to determine biodegradability, employing in this case the manometric method; the BOD₅/COD ratio was also calculated. Finally, the Zahn–Wellens test was employed to evaluate the long-term biodegradation of the effluents. The inhibition of the respiration of activated sludge in the presence of toxic pollutants was used to test the toxicity of the treated sample. An alternative method based on the decrease of BOD₅ of a very biodegradable mixture (glucose + glutamic acid) upon addition of the toxic solution was also employed. Similar trends were obtained with all methods and allowed us to distinguish between two periods: At the beginning of the reaction, there is a decrease in the concentration of dimethoate to reach complete abatement of this pesticide; this produces a nearly complete detoxification of the solution and a very significant increase of biodegradability (BOD₅/COD ratio reached values close to 0.5 and important increase of BOD₅ and BOD_st were observed). Beyond this point, slow mineralization is detected, but further improvement of the biodegradability cannot be achieved.     

Waste calcite sludge as an adsorbent for the removal of cadmium, copper, lead, and zinc from aqueous solutions

Sludge residues, an industrial waste material for the removal of cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) from aqueous solutions were investigated using batch method. Batch mode experiments were carried out as a function of solution pH, adsorbent dosage, initial concentration, and contact time. The results indicated that the adsorbent showed good sorption potential and maximum metal removal was observed at pH ≥?3. Within 120?min of operation, about 63.7, 95.2, 99.9, and 88.2% of Cd²⁺, Cu²⁺, Pb²⁺, and Zn²⁺ ions were removed from the solutions, respectively. Sorption curves were well fitted to the Langmuir and Freundlich models. The adsorption capacities for Cd²⁺, Cu²⁺, Pb²⁺, and Zn²⁺ ions at optimum conditions were 121.2, 1067.8, 566.4, and 534.2?mg?g^?1, respectively. The kinetics of Cd²⁺, Cu²⁺, Pb²⁺, and Zn²⁺ adsorption from aqueous solutions was analyzed by fitting the experimental data to pseudo-first- and pseudo-second-order kinetic models. However, the pseudo-first-order kinetics model provided much better R ² values and the rate constant was found to be 0.001?min^?1 for Cd²⁺, Cu²⁺, Pb²⁺, and Zn²⁺ ions. The results revealed that sludge residues can adsorb considerable amount of Cd²⁺, Cu²⁺, Pb²⁺, and Zn²⁺ ions and it could be an economical method for the removal of these ions from aqueous systems.     

Analysis of the interaction between polymer and surfactant in aqueous solutions for chemical-enhanced oil recovery

Most petroleum reservoirs are subjected to Improved and Enhanced Oil Recovery (IOR and EOR) processes following secondary recovery. EOR involves the application of external forces and substances to improve the chemical and physical interactions in hydrocarbon reservoirs in order to improve preferable recovery conditions. The process of chemical flooding with solutions of polymers and surfactants can be used for developing oil exploitation. Studying the interaction between surfactants and polymers is indispensable for successful oil recovery. The interaction between non-ionic and anionic surfactants and polymers in ternary mixtures was examined at different concentrations and temperatures by dynamic light scattering and gel permeation chromatography. The hydrodynamic size of surfactant-polymer composites was higher than the particle size of individual components indicating a formation of associates. The size of associates was increased by increasing the concentration of the surfactants and the temperature. It could be supposed that the polymer formed a mixed micelle with the surfactants. Gel permeation chromatography has confirmed the increase in molecular weight of the associate formed by surfactants and polymers.     

Assessment of integrated binary process by coupling photocatalysis and photo-Fenton for the removal of cephalexin from aqueous solution

A novel concept of integrated process by coupling photocatalysis and photo-Fenton especially in fixed mode has been presented in the current study for the removal of recalcitrant pharmaceuticals like cephalexin (CEX) from aqueous solution in reduced treatment time. Waste materials like foundry sand (FS) was used as a substitute for iron along with TiO₂. The parametric optimization was carried out in slurry mode using Box–Behnken design model (BBD) and response surface methodology. For fixed-bed studies, support materials of varying shapes (hollow circular disk, rectangular slabs, spherical beads) were prepared using clay in conjunction with FS for TiO₂ immobilization. Different supports were compared on the basis of degradation efficiency, exposed surface area of catalyst as well as their recyclability capacity for the degradation of CEX. Iron was leaching by default from the supports during the degradation process which contributed simultaneously to photo-Fenton process along with photocatalysis. Spherical beads with 0.0265 m² exposed surface area of catalyst and better recyclability efficiency (10 cycles) yielded best degradation efficiency (80%) of CEX after 240 min of treatment time. The presence of iron along with TiO₂ on the surface of beads was confirmed through TGA, SEM/EDS, XRD, DRS and FTIR. The mineralization of CEX was validated through quantification of nitrite, nitrate and sulfate ions along with reduction in COD. A tentative pathway for the degradation of CEX was also proposed based on the identification of intermediates through GC–MS analysis.     

Radiation doses and hazards from processing of crude oil at the Tema oil refinery in Ghana

Processing of crude oil has been carried out in Ghana for more than four decades without measures to assess the hazards associated with the naturally occurring radionuclides in the raw and processed materials. This study investigates the exposure of the public to (226)Ra, (232)Th and (40)K in crude oil, petroleum products and wastes at the Tema oil refinery in Ghana using gamma-ray spectrometry. The study shows higher activity concentrations of the natural radionuclides in the wastes than the crude oil and the products with estimated hazard indices less than unity. The values obtained in the study are within recommended limits for public exposure indicating that radiation exposure from processing of the crude oil at the refinery does not pose any significant radiological hazard but may require monitoring to establish long-term effect on both public and workers.     

Methods of improving efficiency of drilling operations for increasing oil and gas production in Ukraine

The paper reports the main outcome of theoretical research, engineering development, and industrial design efforts to elaborate and implement a complex of technological solutions, equipment, and advanced materials for the purpose of improving efficiency of drilling operations. The authors substantiate a rise in oil and gas production by recovering inactive wells, drilling slant and horizontal boreholes, reducting drilling costs.     

Use of Ponkan mandarin peels as biosorbent for toxic metals uptake from aqueous solutions

Waste Ponkan mandarin (Citrus reticulata) peel was used as biosorbent to extract Ni(II), Co(II) and Cu(II) 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 Langmuir equation. Based on the capacity of adsorption of the natural biosorbent to interact with the metallic ions, the following results were obtained 1.92, 1.37 and 1.31 mmol g(-1) for Ni(II), Co(II) and Cu(II), respectively, reflecting a maximum adsorption order of Ni(II)>Co(II)>Cu(II). The quick adsorption process reached the equilibrium before 5, 10 and 15 min for Ni(II), Co(II) and Cu(II), respectively, with maximum adsorptions at pH 4.8. In order to evaluate the Ponkan mandarin peel a biosorbent in dynamic system, a glass column was fulfilled with 1.00 g of this natural adsorbent, and it was fed with 5.00 x 10(-4)mol l(-1) of Ni(II) or Co(II) or Cu(II) at pH 4.8 and 3.5 ml min(-1). The lower breakpoints (BP(1)) were attained at concentrations of effluent of the column attained the maximum limit allowed of these elements in waters (>0.1 mg l(-1)) which were: 110, 100 and 130 bed volumes (V(effluent)/V(adsorbent)), for Ni(II), Co(II) and Cu(II), respectively. The higher breakpoints (BP(2)) were attained when the complete saturation of the natural adsorbent occurred, and the values obtained were: 740, 540 and 520 bed volumes for Ni(II), Co(II) and Cu(II), respectively.     

Separation factors for the crystallization of inorganic substances from aqueous solutions

A method is proposed for evaluating separation factors for the crystallization of inorganic substances from aqueous solutions. The method allows the interaction between components of mixed electrolyte solutions to be assessed using basic data for binary solutions of the impurity and major component.     

Evaluation of biodegradability and oxidation degree of hospital wastewater using photo-Fenton process as the pretreatment method

In this work, the photo-Fenton process was used for the pretreatment of hospital wastewater with the objective of improving its overall biodegradability and determining the degree of increased oxidation. The chemical oxygen demand (COD), 5-day biochemical oxygen demand (BOD5), total organic carbon (TOC) and toxicity towards the gram negative marine bioluminescent bacteria of the species V. fischeri were selected as the environmental sum parameters to follow the performance of this process. The enhancement of biodegradability, evaluated in terms of the BOD5/COD ratio, increased from 0.3 to 0.52 and the oxidation degree, calculated in terms of AOS, leveled up from -1.14 to +1.58 at the optimum conditions; a dosage ratio of COD:H2O2:Fe(II) at 1:4:0.1, and a reaction pH of 3. The reduction in the inhibition percentage from the toxicity test indicated the safe levels for micro-organisms in degrading the residual organic substance in this method. Almost total removal percentages of COD, BOD5, and TOC were found by a sequential activated sludge process for the pre-treated wastewater. Results obtained from this work indicated that the photo-Fenton process could be a suitable pretreatment method in reducing toxicity of pollutants and enhancing biodegradability of hospital wastewaters treated in a coupled photochemical-biological system.     

改性膨润土对溶液中Co2+、Mn2+的吸附研究

以膨润土为原材料,盐酸为改性剂,制备改性膨润土。研究了改性膨润土的制备条件,其对重金属Co2+、Mn2+的吸附性能及对苯二甲酸(PTA)工业中的副产品对甲苯甲酸对吸附的影响。实验结果表明,盐酸的最佳改性浓度为1.5mol/L,改性膨润土在40℃的吸附能力最好,可达到12～14mg/g,经过热力学分析得出,改性膨润土对钴离子、锰离子的吸附方式均符合Langmuir吸附模型,PTA工业中的副产品对甲苯甲酸对吸附没有影响。     

Determination of the apparent rate constants of the degradation of humic substances by ozonation and modeling of the removal of humic substances from the aqueous solutions with neural network

In this study, the degradation rate constants of humic substances by ozonation under the different empirical conditions such as ozone-air flow rate, ozone generation potential, pH, temperature, powdered activated carbon (PAC) dosage and HCO(3)(-) ions concentration were determined. The ozonation of humic substances in the semi-batch reactor was found to fit pseudo-first-order reaction. The values of apparent rate constant of humic substances degradation increased with the increase of initial ozone-air flow rates, ozone generation potential, pH, temperatures and PAC dosage, but decreased with the increase of HCO(3)(-) concentration of the solution. Using Arrhenius equation, the activation energy (E(a)) of the reaction was found as 1.96 kJ mol(-1). The reaction of ozonation of humic substances under the different temperatures was defined as diffusion control according to E(a). The model based on artificial neural network (ANN) could predict the concentrations of humic substances removal from aqueous solution during ozonation. A relationship between the predicted results of the designed ANN model and experimental data was also conducted. The ANN model yielded determination coefficient of (R(2)=0.995), standard deviation ratio (0.065), mean absolute error (4.057) and root mean square error (5.4967).     

Use of waste materials--Bottom Ash and De-Oiled Soya, as potential adsorbents for the removal of Amaranth from aqueous solutions

Bottom Ash, a power plan t waste material and De-Oiled Soya, an agriculture waste product were successfully utilized in removing trisodium 2-hydroxy-1-(4-sulphonato-1-naphthylazo)naphthalene-3,6-disulphonate--a water-soluble hazardous azo dye (Amaranth). The paper incorporates thermodynamic and kinetic studies for the adsorption of the dye on these two waste materials as adsorbents. Characterization of each adsorbent was carried out by I.R. and D.T.A. curves. Batch adsorption studies were made by measuring effects of pH, adsorbate concentration, sieve size, adsorbent dosage, contact time, temperature etc. Specific rate constants for the processes were calculated by kinetic measurements and a first order adsorption kinetics was observed in each case. Langmuir and Freundlich adsorption isotherms were applied to calculate thermodynamic parameters. The adsorption on Bottom Ash takes place via film diffusion process at lower concentrations and via particle diffusion process at higher concentrations, while in the case of De-Oiled Soya process only particle diffusion takes place in the entire concentration range.     

Development of an infrared hollow waveguide as a sensing device for detection of organic compounds in aqueous solutions

In this paper, a new detection method based on an infrared hollow waveguide is developed to detect semivolatile to nonvolatile organic compounds in aqueous solutions. The hollow waveguide is produced by chemical deposition of silver on the inner surface of a polyethylene tube. The surface of the silver layer is further coated with a hydrophobic film to attract organic compounds in aqueous solution. Samples were pumped through this hollow waveguide sampler and organic compounds were attracted onto the hydrophobic film. After removal of the residual water molecules in the hollow waveguide sampler, organic compounds can be sensed by conventional Fourier transform infrared (FT-IR) spectrometry. Theoretical aspects of this type of sampler are also presented. The derived analytical equations for this type of sampler were consistent with experimental data. Under the condition of constant hydrophobic film volume, high linearity (R(2) equal to 0.9993) between the concentration of analyte and the detected signal was obtained for concentrations in the range from 2.5 ppm to 50 ppb. By co-adding 100 scans with 4 cm(-)(1) resolution, the typical detection limit in this type of sensing method can be lower than 10 ppb. Several factors such as sampling flow rate, sampling time, and hydrophobic film volume were also investigated in this work.     

Application of natural zeolite for phosphorus and ammonium removal from aqueous solutions

Removal of both nutrients ammonium and phosphorus by natural zeolite has been studied in lab scale by using a mechanically stirred batch system (1000 ml). Zeolite, a mean particle size of 13 μm, was used as an adsorbent for the removal of ammonium and then as a seed material for the precipitation of calcium phosphate. A relationship was established between the uptake of ammonium by zeolite and the ratio of initial ammonium concentration to zeolite dosage. Ammonium uptake of zeolite was almost completed within initial 5 min of adsorption period. There is no pronounced effect of zeolite and ammonium, neither positive nor negative on the amount of calcium phosphate precipitation. The extent of the precipitation of phosphate increased with rising pH. It was also observed that when the system was allowed to relax at constant pH (i.e. under relatively low super saturations), a certain lag time was noted to elapse at the onset of the precipitation. At the pH 7.2, the amount of initial fast precipitation within 5 min and total precipitation within 120 min were around 34% and 93%, respectively. Precipitation of calcium phosphate on to ammonium-loaded zeolite was achieved at low super saturations (<pH 7.5) through secondary nucleation and crystal growth, leading to an increase in particle size.