Sulfamethoxazole abatement by photo-Fenton: Toxicity,inhibition and biodegradability assessment of intermediates

The objective of this work was to study the abatement of 200 mg L⁻¹ sulfamethoxazole (SMX) solution by means of photo-Fenton process. Biodegradability of the treated solutions was followed by the ratio biochemical oxygen demand at five days/chemical oxygen demand (BOD₅/COD) and toxicity by Microtox^® and inhibition tests. Experiments with different initial concentration of H₂O₂ were carried out. The initial amount of Fe²⁺ and pH of the solution were set at 10 mg L⁻¹ and 2.8 respectively. The temperature of the reactor was kept constant in all the experiments (25 ± 0.8 °C). Photo-Fenton process is thought to be a successful treatment step to improve the biodegradability of wastewater containing SMX. The complete antibiotic removal was achieved for a H₂O₂ dose over 300 mg L⁻¹. Biodegradability (BOD₅/COD) rose from zero (SMX solution) to values higher than 0.3 (treated solutions). Toxicity and inhibition tests pointed out in the same direction: oxidized intermediates for initial H₂O₂ dose over 300 mg L⁻¹ showed no toxicity effects on pure bacteria and no inhibition on activated sludge activity.     

Investigation of a sewage-integrated technology combining an expanded granular sludge bed (EGSB) and an electrochemical reactor in a pilot-scale plant

A sewage-integrated treatment system (SITS) for the treatment of municipal wastewater, consisting of an expanded granular sludge bed (EGSB) reactor to remove soluble organic matter and an electrochemical (EC) reactor to oxidize the NH₃-N, was evaluated. The performance of the EGSB reactor was monitored for 12 months in a pilot-scale plant. Iron shavings were added to the EGSB reactor on the sixtieth day to improve the removal efficiency of the chemical oxygen demand (COD), suspended solids (SS) and total phosphorus (TP). After the iron shavings were added, the effluent COD, SS and TP decreased from 104 to 46 mg L⁻¹, 21 to 8.6 mg L⁻¹ and 3.62 to 1.36 mg L⁻¹, respectively. Moreover, in the EC reactor, which was equipped with IrO₂/Ti anodes, the NH₃-N and total nitrogen (TN) concentrations decreased from 25 to 12 mg L⁻¹ and 29 to 15 mg L⁻¹, respectively. The NH₃-N was directly oxidized to N₂, resulting in no secondary pollution. The results demonstrated the possibility of removing carbon and nutrients in a SITS with high efficiency. The system runs efficiently and with a flexible operation, making it suitable for low-strength wastewater. The results and parameters presented here can provide references for the practical project.     

Treatment of Terasil Red R Dye Wastewater using H2O2/pyridine/Cu(II) System

The H₂O₂/pyridine/Cu(II) advanced oxidation system was used to assess the efficiency of the treatment of a 1 g L⁻¹ Terasil Red R dye solution. This system was found to be capable in reducing the concentration of chemical oxygen demand (COD) of the dye solution up to 90%, and achieving 99% in decolorization at the optimal concentration of 5.5 mM H₂O₂, 38 mM pyridine and 1.68 mM Cu(II). The final concentration of COD was recorded at 117 mg L⁻¹ and color point at 320 PtCo. Full 2⁴ factorial design and the response surface methodology using central composite design (CCD) were utilized in the screening and optimization of this study. Treatment efficiency was found to be pH independent. The amount of sludge generation was in the range of 100–175 mg L⁻¹ and the sludge produced at the optimal concentration was 170 mg L⁻¹.     

Utilization of landfill leachate parameters for pretreatment by Fenton reaction and struvite precipitation—A comparative study

This paper reports results of laboratory studies on two pretreatment methods, struvite precipitation using aeration with H₃PO₄ and Fenton oxidation. These methods utilized specific properties of the leachate: high magnesium content (172 mg L⁻¹) for struvite precipitation and a high iron concentration (56 mg L⁻¹) for Fenton treatment. Struvite precipitation (H₃PO₄, 700 mg L⁻¹) removed 36% of NH₃-N and 24% of SCOD. Fenton treatment (at pH 3.5) required 650 mg L⁻¹ of H₂O₂ and removed 66% of SCOD. The effect of each pretreatment on the returned activated sludge (RAS) was evaluated using respirometry. Both methods reduced the inhibitory effect of the leachate and substantially increased biokinetic parameters. The BOD₅/SCOD ratio increased from 0.63 for raw leachate to 0.82 (struvite) and 0.88 (Fenton). Estimation of capital and operational costs of the total leachate treatment indicated that aeration with struvite precipitation, followed by biological treatment, would be the preferred option.     

Fluoride removal performance of glass derived hydroxyapatite

A novel sodium calcium borate glass derived hydroxyapatite (G-HAP) with different ranges of particle size was prepared by immersion sodium calcium borate glass in 0.1 M K₂HPO₄ solution by the ratio of 50 g L⁻¹ for 7 days. The unique advantage of G-HAP for the adsorption of fluoride ions in solutions was studied. The effects of size and quantity of particles, pH value and adsorption time on adsorption performance were investigated. The maximum adsorption capacity was 17.34 mg g⁻¹ if 5 g L⁻¹, <100 μm G-HAP was added to a solution with an initial pH value of 6.72 and the adsorption time was 12 h. The results showed that the micro-G-HAP could immobilize F⁻ in solution more effectively than commercial nano-HAP, which makes potential application of the G-HAP in removing the fluoride ions from wastewater. The adsorption kinetics and isotherms for F⁻ could be well fitted by a second order kinetic model and Freundlich isotherm model respectively, which could be used to describe the adsorption behavior. The mechanism of G-HAP in immobilizing F⁻ from aqueous solutions was investigated by the X-ray diffraction (XRD), infrared spectra (IR) and scanning electron microscopy (SEM).     

Zinc recovery and waste sludge minimization from chromium passivation baths

This work reports the feasibility of applying emulsion pertraction technology (EPT) aiming at zinc recovery and waste minimization in the zinc electroplating processes that include Cr (III) passivation. The assessment consists of firstly the lifetime extension of the passivation baths by selective removal of the tramp ions zinc and iron, and secondly, the recovery of zinc for further reuse. Spent passivation baths from a local industry were tested, being the major metallic content: Cr³⁺ 9000 mg L⁻¹, Zn²⁺ 12,000 mg L⁻¹, Fe³⁺ 100 mg L⁻¹. Working in a Liqui-Cel hollow fiber membrane contactor and using the extractant bis(2,4,4-trimethylpentyl) phosphinic acid, reduction of zinc and iron concentrations below 60 mg L⁻¹ and 2 mg L⁻¹, respectively were obtained, while trivalent chromium, the active metal that generates the passivation layer, was retained in the baths. Zinc was selectively transferred to an acidic stripping phase that in the experimental time reached a concentration of 157,000 mg L⁻¹. Zinc recovery by electrowinning from the acidic stripping phase without any pretreatment of the electrolyte solution provided a purity of 98.5%, matching the lower commercial zinc grade. As a result of the extension of the life time of the passivation bath, significant environmental advantages are derived such as minimization of the volume of hazardous wastes and savings in the consumption of raw materials.     

A pilot study of three-stage biological–chemical treatment of landfill leachate applying continuous ferric sludge reuse in Fenton-like process

This pilot study describes a three-stage continuous process for treating landfill leachate containing significant concentrations of recalcitrant organic substances. The proposed technological scheme consisted of an activated sludge pre-treatment combined with a Fenton-like process enhanced by continuous sludge reuse and followed by an activated sludge post-oxidation. Biological pre-treatment removed >99, 86, >99, 83 and 86 % of BOD₇, COD, NH₄ ⁺–N, phenols and the sum of lignin and tannins, respectively. Operational conditions in the ferric sludge-catalysed Fenton-like process stage were carefully adjusted in order to maintain the efficacy and practicability of combined treatment scheme. Although the application of ferric sludge as a catalyst in the Fenton-like oxidation reduced COD removal efficiency by 32 % as compared to the conventional Fenton process, lower process efficiency was compensated by reducing the water exchange ratio to 50 % without increasing the consumption of reagents. Moreover, an intermittent addition (added to every second treatment cycle) of fresh ferrous iron catalyst at a H₂O₂/Fe²⁺ w/w ratio of 20/1 increased the BOD₇/COD ratio from 0.04 to 0.32 and resulted in 60 % COD removal. A cyclic addition (added to every treatment cycle) of the same amount of catalyst increased the BOD₇/COD ratio from 0.09 to 0.32, and a 10 % higher COD removal efficiency as compared to intermittent catalyst addition was achieved. Finally, biological post-treatment of the leachate resulted in more than 95 % removal of each measured parameter. Overall, the combined technological scheme with continuous ferric sludge reuse in the Fenton-like stage proved promising alternative for landfill leachate treatment.     

The effect of pure iron in a nanocrystalline grain size on the corrosion inhibitor behavior of sodium benzoate in near-neutral aqueous solution

The effect of grain size reduction on the electrochemical and corrosion behavior of iron with different grain sizes (32–750 nm) produced by direct and pulsed current electrodeposition were characterized using Tafel polarization curves and electrochemical impedance spectroscopy. The grain size of deposits was determined by X-ray diffraction analysis and scanning electron microscopy. The tests were carried out in an aqueous electrolyte containing 30 mg L⁻¹ NaCl + 70 mg L⁻¹ Na₂SO₄. Results obtained suggested that the inhibition effect and corrosion protection of sodium benzoate inhibitor in near-neutral aqueous solutions increased as the grain size decreased from microcrystalline to nanocrystalline. The improvement on the inhibition effect is attributed to the increase of the surface energy.     

Integrated photochemical and biological treatment of a commercial textile surfactant: Process optimization,process kinetics and COD fractionation

The biodegradability of surfactants is a frequent and complex issue arising both at domestic as well as industrial treatment facilities. In the present experimental study, the integrated photochemical (H₂O₂/UV-C) and biochemical (activated sludge) treatment of a commercial grade nonionic/anionic textile surfactant formulation was investigated. Photochemical baseline experiments have shown that once the initial pH and H₂O₂ dose were optimized, practically complete COD removal (COD_o = 500 ± 30 mg L⁻¹) could be achieved. Once the COD was elevated to values being typical for the textile fabric preparation stage, treatment efficiency was seriously retarded provided that the photochemical treatment conditions remained constant. Moreover, a definite relationship existed between H₂O₂ consumption and COD removal for H₂O₂/UV-C advanced oxidation of the textile surfactant. In the second part of the study, COD abatement was modeled for the biodegradation of untreated and photochemically pretreated textile surfactant formulation according to their COD fractions. Results have indicated that the readily biodegradable and rapidly hydrolysable COD fractions of the textile surfactant solution could be appreciably increased upon exposure to an optimum H₂O₂ concentration (60 mM; i.e. 2.1 g H₂O₂ (g COD_o)⁻¹) and extended UV-C irradiation times (i.e. 90 and 120 min).     

Novel modeling concept for evaluating the effects of cadmium and copper on heterotrophic growth and lysis rates in activated sludge process

A new modeling concept to evaluate the effects of cadmium and copper on heterotrophic growth rate constant (μ_H) and lysis rate constant (b_H) in activated sludge was introduced. The oxygen uptake rate (OUR) was employed to measure the constants. The results indicated that the μ_H value decreased from 4.52 to 3.26 d⁻¹ or by 28% when 0.7 mg L⁻¹ of cadmium was added. Contrarily the b_H value increased from 0.31 to 0.35 d⁻¹ or by 11%. When adding 0.7 mg L⁻¹ of copper, the μ_H value decreased to 2.80 d⁻¹ or by 38%. The b_H value increased to 0.42 d⁻¹ or by 35%. After regression, the inhibitory effect was in a good agreement with non-competitive inhibition kinetic. The inhibition coefficient values for cadmium and copper were 1.82 and 1.21 mg L⁻¹, respectively. The relation between the b_H values and heavy metal concentrations agreed with exponential type well. The heavy metal would enhance b_H value. Using these data, a new kinetic model was established and used to simulate the degree of inhibition. It was evident that not only the inhibitory effect on μ_H but also that the enhancement effect on b_H should be considered when heavy metal presented.     

Synthesis,characterization and flocculation activity of novel Fe(OH)3–polyacrylamide hybrid polymer

A novel Fe(OH)₃–polyacrylamide inorganic–organic hybrid polymer (FHPAM) was synthesized via free radical solution polymerization initiated by a redox initiation system ((NH₄)₂S₂O₈–NaHSO₃) in an aqueous medium. Reaction parameters influencing the intrinsic viscosity and the yield of the hybrid polymer, such as initiator concentration, monomer mass fraction, temperature and reaction time were investigated and optimized. The results show that the maximum intrinsic viscosity and up to 94% yields of the hybrid polymer can be achieved using initiator concentration of 0.3% with acrylamide monomer mass fraction of 20% under solution polymerization at 40 °C for 7 h. The physicochemical properties of this hybrid flocculant were characterized with TEM, FTIR spectra, TGA, and conductivity. It was found that a chemical bond exists between Fe(OH)₃ colloid and polyacrylamide chains in the FHPAM. The application of the hybrid polymer for the treatment of 2.5 g L⁻¹ kaolin suspension indicates that it had an excellent flocculation capacity and its flocculation efficiency was much better than that of commercial available polyacrylamide (PAM) and polymeric ferric sulfate (PFS). The optimal conditions for the flocculation treatment of kaolin suspension were the FHPAM dosage of 40 mg L⁻¹ at pH 7.0. The thermodynamic parameters for the flocculation process were calculated based on a statistical model. Interpretation of the results was given.     

Optimizing preparation of the TiO2 thin film reactor using the Taguchi method

In this study, titanium dioxide thin film was prepared using the modified chemical vapor deposition. The parameters employed to control the preparation of the catalyst include the temperature of water bath, the Ti(OC₃H₇)₄/H₂O ratio, the flow rate of carrier gas, the oxidation temperature, the oxidation time, the calcination temperature, the rotating speed of furnace, and the speed of geared motor. The orthogonal arrays in the design of experimental method proposed by Taguchi were adopted to conduct the multiple-factor experiment. The conversion rate of salicylic acid in the aqueous or heterogeneous phase photocatalysis experiment was employed to identify the optimal conditions for assembly. The results indicated that a higher conversion ratio of the organic substance could be achieved under catalytic oxidation temperature of 400 °C, calcination temperature of 550 °C, and spraying speed of 30 rpm and the optimal experimental conditions obtained in this study were irradiation with intensity of 2.9 mW cm⁻² on salicylic acid at concentration of 250 mg L⁻¹ by both agitation and aeration processes (dissolved oxygen level = 8.2 mg O₂ L⁻¹) at pH 5, which could achieve optimal hydroxyl radical yield of 5.1 × 10⁻¹⁷ M.     

Strong adsorption of chlorotetracycline on magnetite nanoparticles

In this work, environmentally friendly magnetite nanoparticles (Fe₃O₄ MNPs) were used to adsorb chlorotetracycline (CTC) from aqueous media. Fe₃O₄ MNPs exhibit ultrahigh adsorption ability to this widely used antibiotic. The adsorption behavior of CTC on Fe₃O₄ MNPs fitted the pseudo-second-order kinetics model, and the adsorption equilibrium was achieved within 10 h. The maximum Langmuir adsorption capacity of CTC on Fe₃O₄ (476 mg g⁻¹) was obtained at pH 6.5. Thermodynamic parameters calculated from the adsorption data at different temperature showed that the adsorption reaction was endothermic and spontaneous. Low concentration of NaCl and foreign divalent cations hardly affected the adsorption. Negative effect of coexisting humic acid (HA) on CTC adsorption was also observed when the concentration of HA was lower than 20 mg L⁻¹. But high concentration of HA (>20 mg L⁻¹) increased the CTC adsorption on Fe₃O₄ MNPs. The matrix effect of several environmental water samples on CTC adsorption was not evident. Fe₃O₄ MNPs were regenerated by treatment with H₂O₂ or calcination at 400 °C in N₂ atmosphere after separation from water solution by an external magnet. This research provided a high efficient and reusable adsorbent to remove CTC selectively from aqueous media.     

Effects of Y2O3 addition on microwave dielectric characteristics of Al2O3 ceramics

Microwave dielectric characteristics of alumina ceramics with yttria addition were investigated. The sintering temperature was lowered, and the dielectric constant (ε_r) did not remarkably change by adding yttria. The microwave dielectric loss (tan δ) increased from 8.4 × 10^− 5 to 2.2 × 10^− 4, due to the presence of Al₅Y₃O₁₂ secondary phase. The grain size had significant effects on the dielectric loss, and there was an optimum grain size where the dielectric loss reached the minimum.     

The biochemical response to different Cr and Cd concentrations in soils amended with organic wastes

The effects of adding municipal solid waste (MSW) or poultry manure (PM) on the biochemical properties of a soil polluted with Cr and Cd were studied. Soil was mixed with Cr(NO₃)₃ and Cd(NO₃)₂ to give three concentrations (0, 100, and 250 mg Cr kg⁻¹ and 0, 100, and 250 mg Cd kg⁻¹) in the soil, which was then treated with MSW at a rate of 10% or PM at a rate of 7.6%. The pH and biochemical parameters were measured at 0 and 120 days. An unamended and no-polluted soil was used as control. Compared with the non-polluted soil, for the 250 mg Cd kg⁻¹ treatment the microbial biomass-C, dehydrogenase, urease, β-glucosidase, phosphatase, and arylsulphatase activities decreases 23%, 26.2%, 36%, 34.8%, 18.4%, and 15.8%, respectively, whereas for 250 mg Cr kg⁻¹ treatment the biochemical parameters were slightly lowest than for 250 mg Cd kg⁻¹ treatment. For 250 mg Cr kg⁻¹ soil + 250 mg Cd kg⁻¹ soil treatment, the inhibition percentages of the biochemical parameters increased. After the application of organic wastes in Cr + Cd polluted soil, the inhibition of biochemical properties was greater with the MSW amendment than with PM, possibly due to its higher humic acid concentration.     

Treatment of anaerobic sludge digester effluents by the CANON process in an air pulsing SBR

The CANON (Completely Autotrophic Nitrogen removal Over Nitrite) process was successfully developed in an air pulsing reactor type SBR fed with the supernatant from an anaerobic sludge digester and operated at moderately low temperatures (18–24 °C). The SBR was started up as a nitrifying reactor, lowering progressively the dissolved oxygen concentration until reaching partial nitrification. Afterwards, an inoculation with sludge containing Anammox biomass was carried out. Nitrogen volumetric removal rates of 0.25 g N L⁻¹ d⁻¹ due to Anammox activity were measured 35 d after inoculation even though the inoculum constituted only 8% (w/w) of the biomass present in the reactor and it was poorly enriched in Anammox bacteria. The maximal nitrogen removal rate was of 0.45 g N L⁻¹ d⁻¹. By working at a dissolved oxygen concentration of 0.5 mg L⁻¹ in the bulk liquid, nitrogen removal percentages up to 85% were achieved.     

Application of acidogenic fixed-bed reactor prior to anaerobic membrane bioreactor for sustainable slaughterhouse wastewater treatment

High rate anaerobic treatment systems such as anaerobic membrane bioreactors (AMBR) are less popular for slaughterhouse wastewater due to the presence of high fat oil and suspended matters in the effluent. This affects the performance and efficiency of the treatment system. In this work, AMBR has been tried for slaughterhouse wastewater treatment. After the start up period, the reactor was operated with an average organic loading rate (OLR) of 4.37 kg TCOD m⁻³ d⁻¹ with gradual increase to an average of 13.27 kg TCOD m⁻³ d⁻¹. At stable conditions, the treatment efficiency was high with an average COD and BOD₅ reduction of 93.7 and 93.96%, respectively. However, a reduction in the AMBR performance was shown with the increase of the OLR to 16.32 kg TCOD m⁻³ d⁻¹. The removal efficiencies of SCOD and BOD₅ were drastically decreased to below 53.6 and 73.3%, respectively. The decrease of the AMBR performance was due to the accumulation of VFAs. Thus, a new integrated system composed of a FBR for the acidogenesis step followed by the AMBR for methanogenesis step was developed. At high ORL, the integrated system improved the performance of the anaerobic digestion and it successfully overcame the VFA accumulation problem in the AMBR. The anaerobic treatment led to a total removal of all tested pathogens. Thus, the microbiological quality of treated wastewater fits largely with WHO guidelines.     

Photocatalytic treatment of 4-chlorophenol in aqueous ZnO suspensions: Intermediates,influence of dosage and inorganic anions

The photocatalytically driven removal of eco-persistent 4-chlorophenol from water using ZnO is reported here. Kinetic dependence of transformation rate on operating variables such as initial 4-chlorophenol concentration and photocatalyst doses was investigated. A complete degradation of 4-chlorophenol at 50 mg L⁻¹ levels was realised in 3 h. Analytical profiles on 4-chlorophenol transformation were consistent with the best-line fit of the pseudo zero-order kinetics. The addition of small amounts of inorganic anions as SO₄²⁻, HPO₄⁻, S₂O₈²⁻ and Cl⁻ revealed two anion types: active site blockers and rate enhancers. Fortunately, Cl⁻ and SO₄²⁻ commonly encountered in contaminated waters enhanced the rate of 4-chlorophenol degradation. The reaction intermediates and route to 4-chlorophenol mineralisation were elucidated by combined RP-HPLC and GC–MS methods. In addition to previously reported pathway products of 4-chlorophenol photo-oxidation catechol was detected. A radical mechanism involving o-hydroxylation is proposed to account for the formation of catechol.     

Removal of acid orange 7 by guava seed carbon: A four parameter optimization study

The preparation of carbon from waste materials is a recent and economic alternative for the removal of dyes. In this study four samples of carbon were obtained by thermal treatment at 1000 °C using as precursor the guava seed with different particle sizes. The Taguchi method was applied as an experimental design to establish the optimum conditions for the removal of acid orange 7 in batch experiments. The chosen experimental factors and their ranges were: pH (2–12), temperature (15–35 °C), specific surface area (50–600 m² g⁻¹) and adsorbent dosage (16–50 mg ml⁻¹). The orthogonal array L₉ and the larger the better response category were selected to determine the optimum removal conditions: pH 2, temperature 15 °C, S_esp 600 m² g⁻¹ and dosage 30 mg ml⁻¹. Under these conditions a total removal of acid orange 7 was achieved. Moreover, the most significant factors were the carbon specific surface area and the pH. The influence of the different factors on the adsorption of acid orange 7 from solution is explained in terms of electrostatic interactions by considering the dye species and the character of the surface.