Treatment of opium alkaloid containing wastewater in sequencing batch reactor (SBR)—Effect of gamma irradiation

Aerobic biological treatment of opium alkaloid containing wastewater as well as the effect of gamma irradiation as pre-treatment was investigated. Biodegradability of raw wastewater was assessed in aerobic batch reactors and was found highly biodegradable (83–90% degradation). The effect of irradiation (40 and 140 kGy) on biodegradability was also evaluated in terms of BOD₅/COD values and results revealed that irradiation imparted no further enhancement in the biodegradability. Despite the highly biodegradable nature of wastewater, further experiments in sequencing batch reactors (SBR) revealed that the treatment operation was not possible due to sludge settleability problem observed beyond an influent COD value of 2000 mg dm^?3. Possible reasons for this problem were investigated, and the high molecular weight, large size and aromatic structure of the organic pollutants present in wastewater was thought to contribute to poor settleability. Initial efforts to solve this problem by modifying the operational conditions, such as SRT reduction, failed. However, further operational modifications including addition of phosphate buffer cured the settleability problem and influent COD was increased up to 5000 mg dm^?3. Significant COD removal efficiencies (>70%) were obtained in both SBRs fed with original and irradiated wastewaters (by 40 kGy). However, pre-irradiated wastewater provided complete thebain removal and a better settling sludge, which was thought due to degradation of complex structure by radiation application. Degradation of the structure was observed by GC/MS analyses and enhancement in filterability tests.     

Amperometric determination of chemical oxygen demand using boron-doped diamond (BDD) sensor

A new application of boron-doped diamond (BDD) electrode was developed for detecting chemical oxygen demand (COD) by amperometric method. The effects of some basic experimental parameters including pH and applied potential on the response of the BDD electrode were investigated and the optimal operating conditions were obtained. In the COD tests of standard samples, a wide linear range of 20–9000 mg l⁻¹ COD and a low detection limit of 7.5 mg l⁻¹ COD were well established with the present approach. Additionally, the BDD sensor was successfully employed to determine the COD of real samples from various chemical or pharmaceutical wastewaters and the performance still kept stable after over 400 measurements. The results obtained indicated that, as compared with the conventional COD determination techniques, the proposed sensor was an environmentally friendly method with the advantages of short analysis period, simplicity, and no requirement of complicated sample pretreatment even for a sample containing relatively high concentration of organic pollutants.     

Effective bioelectrocatalysis of bilirubin oxidase on electrochemically reduced graphene oxide

Graphene oxide (GO) was applied for construction of an effective biocathode based on bilirubin oxidase (BOD). Separation of small-sized GO sheets together with the BOD immobilisation protocol has detrimental effects on the bioelectrocatalytic reduction of oxygen. When BOD was deposited on electrochemically reduced GO (ErGO) only a negligible current density j = 2.6 μA cm^− 2 was observed. Current density dramatically increased to a value of 46 μA cm^− 2 once BOD was in-situ mixed with as-received GO directly on a glassy carbon electrode (GCE) with subsequent electrochemical reduction of the BOD/GO composite. When this protocol was tested with small-sized GO flakes separated simply using centrifugation, the fabricated biocathode exhibited j = 120 μA cm^− 2. A current density further increased to j = 280 μA cm^− 2 when BOD and purified GO were incubated ex-situ for 4 h, followed by the BOD/GO composite collection by centrifugation, its deposition on the GCE and electrochemical reduction. Moreover, oxygen reduction current increased steeply with a steady-state current density achieved at high potential (≈ 500 mV), close to the onset potential of oxygen reduction (≈ 580 mV).     

Desalination of whey by electrodialysis and ion exchange resins: analysis of both processes with regard to sustainability by calculating their cumulative energy demand

Desalination of whey is an important process in food technology and can be done either by electrodialysis (ED) or by ion exchange (IE) resins. The aim of the present paper is an assessment of the cumulative energy demand of both processes for a technical plant including production of the regeneration agents for the ion exchangers and treatment of waste water. A flow of 45 m³ per day of nanofiltered whey, which is three times concentrated and partially desalted, is assumed as feed for the plant. Data for the assessment was obtained from own laboratory experiments to be reported here, as well as from commercial plants. Applying IE, the final whey product is desalted to a degree of 99%. The IE process yields 3.7 m³ of waste water with 36.3 kg ash and an organic charge of 26 kg chemical oxygen demand (COD)/m³ feed whey. The energy demand of IE amounts to 0.15 kWh for pumping, 25.33 kWh for the production of the regenerants, and 9.75 kWh for the reduction of the organic charge/m³ whey. With ED, the final whey product is desalted to only 90%. ED yields 1.25 m³ of waste water with 8.1 kg ash and an organic charge of 8.4 kg COD/m³ whey. The energy demand of ED amounts to 4.2 kWh for pumping, 5.38 kWh for the electric current through the ED cells, and 3.16 kWh for the reduction of the organic charge/m³ whey.     

Flow injection analysis system with electrochemical detection for the simultaneous determination of nanomolar levels of acetaminophen and codeine

A simple, rapid and low-cost electroanalytical method is proposed for the determination of acetaminophen (ACP) and codeine (COD) at nanomolar levels in pharmaceutical and biological samples. The analytical procedure is based on a flow injection analysis system coupled to electrochemical detection, which was multiple pulse amperometry (FIA-MPA). Boron-doped diamond was used as the working electrode for electrochemical detection. The electrode was subjected to a cathodic pretreatment and was selected in this work due its good electrochemical performance. By applying the FIA-MPA method, after a number of optimization assays, the analgesics were simultaneously determined at excellent linear concentration ranges. The analytical curves ranged from 80 nmol L⁻¹ to 100 µmol L⁻¹ for ACP and from 50 nmol L⁻¹ to 10 µmol L⁻¹ for COD, and the obtained limits of detection were 30 nmol L⁻¹ and 35 nmol L⁻¹ for ACP and COD, respectively. The practical applicability of the electroanalytical method was evaluated from the ACP and COD determination in two sample matrices: commercial pharmaceutical samples and biological fluids. In the case of pharmaceutical formulation samples, the obtained results were statistically similar to those obtained using a reference chromatographic method. In addition, these drugs were simultaneously quantified in biological fluid samples of urine and human serum with excellent recovery percentages.     

Wastewater treatment using gamma irradiation: Tétouan pilot station,Morocco

The increasing demand on limited water supplies has accelerated the wastewater reuse and reclamation. We investigated gamma irradiation effects on wastewater by measuring differences in the legislated parameters, aiming to reuse the wastewater. Effluents samples were collected at the urban wastewater treatment station of Tetouan and were irradiated at different doses ranging from 0 to 14 kGy using a Co⁶⁰ gamma source. The results showed an elimination of bacterial flora, a decrease of biochemical and chemical oxygen demand, and higher conservation of nutritious elements. The results of this study indicated that gamma irradiation might be a good choice for the reuse of wastewater for agricultural activities.     

Electrochemical degradation of tramadol hydrochloride: Novel use of potentiometric carbon paste electrodes as a tracer

The electrochemical removal of tramadol hydrochloride from aqueous solutions has been investigated under several operating conditions using a Pb/PbO₂ electrode. The optimum conditions of the treatment process are: current density of 1000 mA/cm⁻², pH ≈6, temperature of 10 °C and initial tramadol hydrochloride concentration of 100 mg/L. The time of electrolysis is 25 min for degradation rate of tramadol hydrochloride and chemical oxygen demeaned (COD) removal is 22 h. The results were obtained by UV–Vis spectrophotometer and the presently designed electrode was coincident.     

Energy-efficient chlorine production by gas-phase HCl electrolysis with oxygen depolarized cathode

For the first time, gas-phase electrolysis of HCl to chlorine was conducted in a fuel cell type reactor with an oxygen depolarized cathode. Very low cell voltages below − 1 V at industrially relevant current densities of 4 kA m^− 2 were obtained. Compared to technical HCl electrolysis processes, this leads to a reduction in electrical energy demand of approximately 30%. The temperature and the relative humidity (rH) of the cathode inlet gas were identified as key parameters controlling the overall performance of the system.     

TiO2/Nafion film based electrochemiluminescence for detection of dissolved oxygen

TiO₂ nanocrystals had been modified on the surface of the glassy carbon electrode (GCE) with the help of Nafion. The electrochemiluminescence (ECL) behavior of the TiO₂/Nafion GCE in aqueous solution was investigated. A possible mechanism about the ECL of TiO₂ had also been proposed. The ECL intensity was linear with the dissolved oxygen concentration in the range of 0.30–10.00 mg/L with a detection limit of 0.12 mg/L. The developed method can be applied to detect the dissolved oxygen concentration or biochemical oxygen demand (BOD).     

Operation of industrial-scale electron beam wastewater treatment plant

Textile dyeing processes consume large amount of water, steam and discharge filthy and colored wastewater. A pilot scale e-beam plant with an electron accelerator of 1 MeV, 40 kW had constructed at Daegu Dyeing Industrial Complex (DDIC) in 1997 for treating 1,000 m³ per day. Continuous operation of this plant showed the preliminary e-beam treatment reduced bio-treatment time and resulted in more significant decreasing TOC, COD_Cr, and BOD₅. Convinced of the economics and efficiency of the process, a commercial plant with 1 MeV, 400 kW electron accelerator has constructed in 2005. This plant improves the removal efficiency of wastewater with decreasing the retention time in bio-treatment at around 1 kGy. This plant is located on the area of existing wastewater treatment facility in DDIC and the treatment capacity is 10,000 m³ of wastewater per day. The total construction cost for this plant was USD 4 M and the operation cost has been obtained was not more than USD 1 M per year and about USD 0.3 per each m³ of wastewater.     

Direct electrochemical conversion of bilirubin oxidase at carbon nanotube-modified glassy carbon electrodes

We report on direct electron transfer reactions of bilirubin oxidase at multi-walled carbon nanotube (MWCNT) modified glassy carbon electrodes (GCE). The bioelectrocatalytic oxygen reduction was recorded using linear sweep voltammetry (LSV) with BOD in solution, adsorbed and covalently linked to the nanotubes. The MWCNT modification of GC electrodes strongly enhances the oxygen reduction compared to the signals at unmodified GCE. Under anaerobic conditions with a high protein concentration in solution a pair of redox peaks with a formal potential of 450 ± 15 mV vs Ag/AgCl, 1 M KCl (pH 7.4) was found with cyclic voltammetry. The redox conversion is indicated to be surface-controlled and pH-dependent (54.5 mV/pH). The quasi-reversible redox reaction might be attributed to the trinuclear T2/T3 cluster of BOD.     

Decomposition of persistent pharmaceuticals in wastewater by ionizing radiation

Pharmaceuticals in wastewater were treated by the combined method of activated sludge and ionizing radiation in laboratory scale. Oseltamivir, aspirin, and ibuprofen at 5 μmol dm^?3 in wastewater were decomposed by the activated sludge at reaction time for 4 h. Carbamazepine, ketoprofen, mefenamic acid, clofibric acid, and diclofenac were not biodegraded completely, but were eliminated by γ-ray irradiation at 2 kGy. The rate constants of the reactions of these pharmaceuticals with hydroxyl radicals were estimated by the competition reaction method to be 4.0–10×10⁹ mol^?1 dm³ s^?1. Decompositions of the pharmaceuticals in wastewater by ionizing radiation were simulated by use of the rate constants and the amount of total organic carbon as parameters. Simulation curves of concentrations of these pharmaceuticals as a function of dose described the experimental data, and the required dose for the elimination of them in wastewater by ionizing radiation can be estimated by this simulation.     

Mineralization of aqueous phenolate solutions: A combination of irradiation treatment and wet oxidation

Wet oxidation (high-temperature, high-pressure oxidation of organic wastes in aqueous solution) and radiation technology were combined in γ-ray and electron beam induced oxidation of 4×10^?4–1×10^?2 mol dm^?3 Na-phenolate solutions in a wide O₂ concentration (1–20 bar pressure) and absorbed dose (0–50 kGy) range. Most experiments were made in stainless steel high pressure autoclave equipped with magnetic stirrer. The rate of oxidation was followed by chemical oxygen demand and total organic carbon content measurements. The rate was similar in γ-ray and pulsed electron beam irradiation and increased with O₂ concentration in the liquid.     

Platinum nanoparticles supported on nitrobenzene-functionalised graphene nanosheets as electrocatalysts for oxygen reduction reaction in alkaline media

A systematic study on the electrocatalytic properties of Pt nanoparticles supported on nitrobenzene-modified graphene (Pt-NB/G) as catalyst for oxygen reduction reaction (ORR) in alkaline solution was performed. Graphene nanosheets were spontaneously grafted with nitrophenyl groups using 4-nitrobenzenediazonium salt. The electrocatalytic activity towards the ORR and stability of the prepared catalysts in 0.1 M KOH solution have been studied and compared with that of the commercial Pt/C catalyst. The results obtained show that the NB-modified graphene nanosheets can be good Pt catalyst support with high stability and excellent electrocatalytic properties. The specific activity of Pt-NB/G for O₂ reduction was 0.184 mA cm⁻², which is very close to that obtained for commercial 20 wt% Pt/C catalyst (0.214 mA cm⁻²) at 0.9 V vs. RHE. The Pt-NB/G hybrid material promotes a four-electron reduction of oxygen and can be used as a promising cathode catalyst in alkaline fuel cells.     

Analysis and identification of irradiated Spirulina powder by a three-step infrared macro-fingerprint spectroscopy

A three-step infrared (IR) macro-fingerprint method combining conventional IR spectra, and the secondary derivative spectra with two-dimensional infrared correlation spectroscopy (2D-IR), was developed to analyze Spirulina powder before and after gamma irradiation. In the IR spectra, most of the absorption peaks of samples irradiated at 1, 2.7, 6, and 10.4 kGy had lower intensities than the non-irradiated ones, whereas peaks at 1152, 1078, and 1051 cm⁻¹ were slightly enhanced with irradiation at 2.7, 6, and 10.4 kGy. Their second derivative spectra amplified the differences and revealed that irradiation affected the C=O band of carboxylic acid and esters, and the N–H band of proteins. The peaks at 1746 and 1741 cm⁻¹, and those at 1730 and 1725  cm⁻¹ became two broad peaks. Meanwhile, the three sharp peaks at 1548 cm⁻¹, 1544 cm⁻¹ and 1536 cm⁻¹ changed to two broad peaks at around 1547 and 1534 cm⁻¹ after irradiation at doses higher than 1 kGy. The characteristic IR bands from 1700 cm⁻¹ to 1600 cm⁻¹, which represent the C=O band in proteins, also have different shapes and intensities after irradiation. The finding indicated that irradiation affected the secondary structures of protein which was confirmed by curve fitting results. During the process of increasing the temperature from 50 to 210 °C, the ratio of amide I to II in absorption intensities in the 2D-IR spectra of the irradiated samples varied with different response for different samples. Saccharides in Spirulina powder had a higher thermostability than proteins, but the autopeaks of irradiated samples did show differences from the non-irradiated sample. The intensity of autopeaks at 1012 cm⁻¹ increased dramatically in the irradiated samples while that of peaks at 1053, 1071, and 1083 cm⁻¹ decreased after irradiation. Based on the three-step IR macro-fingerprint method, irradiated Spirulina powder samples were successfully and fast identified and discriminated.     

Radiation induced degradation of ketoprofen in dilute aqueous solution

The intermediates and final products of ketoprofen degradation were investigated in 0.4 mmol dm^?3 solution by pulse radiolysis and gamma radiolysis. For observation of final products UV?vis spectrophotometry and HPLC separation with diode array detection were used, and for identification MS was used. The reactions of ^?OH lead to hydroxycyclohexadienyl type radical intermediates, in their further reactions hydroxylated derivatives of ketoprofen form as final products. The hydrated electron is scavenged by the carbonyl oxygen and the electron adduct protonates to ketyl radical ^?OH is more effective in decomposing ketoprofen than hydrated electron. Chemical oxygen demand and total organic carbon content measurements on irradiated aerated solutions showed that using irradiation technology ketoprofen can be mineralised. The initial toxicity of the solution monitored by the Daphnia magna test steadily decreases with irradiation. Using 5 kGy dose no toxicity of the solution was detected with this test.     

Treatment of wastewater having estrogen activity by ionizing radiation

Decomposition of endocrine disrupting chemicals (EDCs) in wastewater was investigated by use of ⁶⁰Co γ-ray. Estrogen activities of wastewaters were estimated by the yeast two-hybrid assay based on human or medaka estrogen receptors. The dose required for the elimination of estrogen activity of wastewater below 1 ng dm⁻³ was about 200 Gy (J kg⁻¹). The elimination dose of the estrogen activity depended on the amounts of total organic carbons in wastewater. The economic cost of the treatment process of EDCs using electron beam was estimated at 17 yen m⁻³.     

An enzymatic glucose/O2 biofuel cell: Preparation,characterization and performance in serum

This study demonstrates a new kind of single-walled carbon nanotubes (SWNT)-based compartment-less glucose/O₂ biofuel cell (BFC) with glucose dehydrogenase (GDH) and bilirubin oxidase (BOD) as the anodic and cathodic biocatalysts, respectively, and with poly(brilliant creysl blue) (BCB) adsorbed onto SWNT nanocomposite as the electrocatalyst for the oxidation of NADH. The prepared GDH-polyBCB-SWNT bioanode exhibits an excellent electrocatalytic activity toward the oxidation of glucose biofuel; in 0.10 M phosphate buffer containing 20 mM NAD⁺ and 100 mM glucose, the oxidation of glucose commences at −0.25 V and the current reaches its maximum of 310 μA/cm² at −0.05 V vs. Ag/AgCl. At the BOD-SWNT biocathode, a high potential output is achieved for the reduction of O₂ due to the direct electron transfer property of BOD at the SWNTs. In 0.10 M phosphate buffer, the electrocatalytic reduction of O₂ is observed at a high potential of 0.53 V vs. Ag/AgCl with an electrocatalytic current plateau of ca. 28 μA/cm² at 0.45 V under ambient air and ca. 102 μA/cm² under O₂-saturated atmosphere. In 0.10 M phosphate buffer containing 10 mM NAD⁺ and 40 mM glucose under O₂-saturated atmosphere, the power density of the assembled SWNT-based glucose/O₂ BFC reaches 53.9 μW/cm² at 0.50 V. The performance and the stability of the glucose/O₂ BFC are also evaluated in serum. This study could offer a new route to the development of new kinds of enzymatic BFCs with a high performance and provide useful information on future studies on the enzymatic BFCs as in vivo power sources.     

A comparative study for treatment of white liquor by different applications of Fenton process

In this paper, the treatability of white liquor by conventional (CFP), modified (MFP) and electro-Fenton oxidation processes (EFP) was investigated depending on the COD parameter. Based on the experimental results, up to 62.4%, 58.4% and 54.9% COD removals by the CFP, MFP and EFP were achieved, respectively. It was observed that adjustment of initial pH to acidic values is not required in the CFP. The optimal operational conditions were found to be [Fe²⁺] = 500 mg/L, [H₂O₂] = 1000 mg/L at pH 7.3 (original pH) in the CFP, [Fe⁰] = 1250 mg/L, [H₂O₂] = 1000 mg/L at pH 3 in the MFP, and I = 1.0 A, [H₂O₂] = 1500 mg/L at pH 3 in the EFP, respectively. As a result, the CFP has been determined as a more efficient alternative treatment method.     

Evolution of microstructure and crack pattern in NiO thin films under 200 MeV Au ion irradiation

NiO thin films grown on Si (100) substrate by electron beam evaporation method and sintered at 700 °C were irradiated with 200 MeV Au¹⁵⁺ ions. The fcc structure of the sintered films was retained up to the highest fluence (1×10¹³ ions cm^?2) of irradiation. However the microstructure of the pristine film underwent a considerable modification with increasing ion fluence. 200 MeV Au ion irradiation led to compressive stress generation in NiO medium. The diameter of the stressed region created by 200 MeV Au ions along the ion path was estimated from the variation of stress with ion fluence and found to be ～11.6 nm. The film surface started cracking when irradiated at and above the fluence of 3×10¹² ions cm^?2. Ratio of the fractal dimension of the cracked surface obtained at 200 MeV and 120 MeV (Mallick et al., 2010a) Au ions was compared with the ratio of the radii of ion tracks calculated based on Coulomb explosion and thermal spike models. This comparison indicated applicability of thermal spike model for crack formation.