Electrochemical sulfide removal from synthetic and real domestic wastewater at high current densities

Hydrogen sulfide generation is the key cause of sewer pipe corrosion, one of the major issues in water infrastructure. Current abatement strategies typically involve addition of various types of chemicals to the wastewater, which incurs large operational costs. The transport, storage and application of these chemicals also constitute occupational and safety hazards. In this study, we investigated high rate electrochemical oxidation of sulfide at Ir/Ta mixed metal oxide (MMO) coated titanium electrodes as a means to remove sulfide from wastewater. Both synthetic and real wastewaters were used in the experiments. Electrochemical sulfide oxidation by means of indirect oxidation with in-situ produced oxygen appeared to be the main reaction mechanism at Ir/Ta MMO coated titanium electrodes. The maximum obtained sulfide removal rate was 11.8 ± 1.7 g S m⁻² projected anode surface h⁻¹ using domestic wastewater at sulfide concentrations of ≥30 mg L⁻¹ or higher. The final products of the oxidation were sulfate, thiosulfate and elemental sulfur. Chloride and acetate concentrations did not entail differences in sulfide removal, nor were the latter two components affected by the electrochemical oxidation. Hence, the use of electrodes to generate oxygen in sewer systems may constitute a promising method for reagent-free removal of sulfide from wastewater.     

Long-term field test of an electrochemical method for sulfide removal from sewage

Corrosion caused by hydrogen sulfide leads to significant costs for the rehabilitation or replacement of corroded sewer pipes. Conventional methods to prevent sewer corrosion normally involve the dosing of significant amounts of chemicals with the associated transport and storage costs as well as considerable maintenance and control requirement. Recently, a novel chemical free method for sulfide abatement based on electrochemical sulfide oxidation was shown to be highly effective for the removal of sulfide from synthetic and real sewage. Here, we report on the electrochemical removal of sulfide using Ta/Ir and Pt/Ir coated titanium electrodes under simulated sewer conditions during field trials. The results showed that sulfide can successfully be removed to levels below the normal target value at the end of a simulated rising main (i.e. <1 mg/L). A coulombic efficiency for dissolved oxygen generation of ∼60% was obtained and was independent of the current density. Scaling of the electrode and the membrane was observed in the cathode compartment and as a result the cell potentials increased over time. The cathode potentials returned to their original potential after switching the polarity every two days, but a more frequent switching would be needed to reduce the energy requirements of the system. Accelerated lifetime experiments indicated that a lifetime of 6.0 ± 1.9 years can be expected under polarity switching conditions at a pH of 14 and significantly longer at lower pH values. As operating the system without switching simplifies construction as well as operation, the choice whether to switch or not will in practice depend on operational cost (higher/lower energy) versus capital cost (reactor and peripherals). Irrespective of the approach, our study demonstrates that electrochemical sulfide control in sewer systems may be an attractive new option.     

Spontaneous electrochemical removal of aqueous sulfide

Most of the existing sulfide removal processes from wastewaters and waste gases require substantial amounts of energy inputs. Here we present an electrochemical method by means of a fuel cell that removes sulfide while producing energy. A lab scale fuel cell was operated at ambient temperature and neutral pH, which was capable of removing aqueous sulfide continuously for 2 months at a rate of 0.62 ± 0.1 kg S m⁻³ d⁻¹ of net anodic compartment (NAC) (0.28 ± 0.05 kg S m⁻³ d⁻¹ of total anodic compartment, TAC). During continuous operation, on average, the power generated was 12 ± 2 W m⁻³ NAC (5 ± 1 W m⁻³ TAC), with a maximum capacity of the cell of 166 W m⁻³ NAC (74 W m⁻³ TAC). Potassium ferricyanide was used as cathodic electron acceptor. Elemental sulfur was identified as the predominant final oxidation product that was deposited on the anode. In this abiotic fuel cell, the sulfide oxidation rate was not diminished by the presence of an organic electron donor (acetate) during batch experiments while the acetate concentration remained unchanged. This is particularly important for selective sulfide removal from wastewater where organics are essential for downstream nutrient removal. Elemental sulfur deposited on the anode appeared to limit the operation of the fuel cell after 3 months of operation, necessitating periodic removal of the accumulated sulfur from the electrode.     

Electrochemical sulfide removal and recovery from paper mill anaerobic treatment effluent

Sulfide can be removed from wastewater and recovered as elemental sulfur using an electrochemical process. Recently, we demonstrated this principle of product recovery on synthetic feeds. Here, we present a lab scale electrochemical reactor continuously removing sulfide from the effluent of an anaerobic treatment process operated on paper mill wastewater. The effluent contained 44 ± 7 mg of sulfide-S L⁻¹. Sulfide was reduced to 8 ± 2 mg-S L⁻¹, at a removal rate of 0.845 ± 0.133 kg-S m⁻³ of total anodic compartment (TAC) d⁻¹. The removed sulfide was recovered (75 ± 4% recovery) as pure concentrated alkaline sulfide/polysulfide solution, from which solid elemental sulfur was obtained. The electrochemical sulfide removal was not affected by different soluble constituents or particulate materials present in the wastewater. However, over time sulfide removal decreased due to biological sulfur reduction using the organics present in the wastewater. Therefore, a periodic switching strategy between anode and cathode was developed. Biofilm formation was avoided as the pH of the cathode solution increased to inhibitory levels during cathodic operation, while still allowing full recovery of the sulfur as end product.     

Electrocatalytic characterization and dye degradation of Nano-TiO2 electrode films fabricated by CVD

A 20-40 nm anatase-titania film on a titanium electrode was fabricated using chemical vapor deposition (CVD). The film was characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and atomic force microscopy (AFM). The CVD deposition time and number of deposition coatings were evaluated to establish the appropriate film fabrication parameters. Results indicate that two coatings at a deposition time of 6 h each produced the best nano-TiO₂ electrode films (NTEFs) with an even distribution of ca. 20 nm diameter nanoparticles in the anatase lattice. The NTEF was tested as an electrocatalytic anode to investigate the degradation efficiency in treating methyl orange dye wastewater. A high removal efficiency of methyl orange dye and total organic carbon (TOC) of 97 and 56%, respectively; was achieved using a current density of 20 mA cm^− 2 for 160 min. Cyclic voltammetry showed that the electrochemical degradation reaction rate at the NTEF surface was predominately driven by molecular diffusion. The electrocatalytic decomposition rate of organic pollutants at the NTEF is controlled by mass transport, which was associated with the nanostructure of the electrocatalytic electrode.     

The effect of electrode material on the generation of oxidants and microbial inactivation in the electrochemical disinfection processes

Electrochemical disinfection has gained increasing attention as an alternative for conventional drinking water treatment due to its high effectiveness and environmental compatibility. The most common method of electrochemical disinfection is the use of electro-generated oxidants, such as active chlorine and reactive oxygen species, as disinfectants. This study examined the role of electrode material on the generation of oxidants, and elucidated the different reaction pathways for generating individual oxidants by employing boron-doped diamond (BDD), Ti/RuO₂, Ti/IrO₂, Ti/Pt-IrO₂, and Pt as anode materials. The efficiency of OH production, as determined by para-chlorobenzoic acid (pCBA) degradation, was in the order of BDD ? Ti/RuO₂ ≈ Pt. No significant production of OH was observed at Ti/IrO₂ and Ti/Pt-IrO₂. The OH was found to play a key role in O₃ generation at BDD, but not at the other electrodes. The production of active chlorine was in the order of Ti/IrO₂ > Ti/RuO₂ > Ti/Pt-IrO₂ > BDD > Pt. The large difference in this order from that of ROS was attributed to the difference in the electrocatalytic activity of each electrode material toward the production of active chlorine, as evidenced by linear sweep voltammetry (LSV) measurements. In addition, the characteristics of microbial inactivation as a function of electrode material were examined under the presence of an inert electrolyte, using Escherichia coli as an indicator microorganism.     

Electrochemical oxidation of reverse osmosis concentrate on mixed metal oxide (MMO) titanium coated electrodes

Reverse osmosis (RO) membranes have been successfully applied around the world for wastewater reuse applications. However, RO is a physical separation process, and besides the clean water stream (permeate) a reverse osmosis concentrate (ROC) is produced, usually representing 15-25% of the feed water flow and containing the organic and inorganic contaminants at higher concentrations. In this study, electrochemical oxidation was investigated for the treatment of ROC generated during the reclamation of municipal wastewater effluent. Using laboratory-scale two-compartment electrochemical systems, five electrode materials (i.e. titanium coated with IrO₂-Ta₂O₅, RuO₂-IrO₂, Pt-IrO₂, PbO₂, and SnO₂-Sb) were tested as anodes in batch mode experiments, using ROC from an advanced water treatment plant. The best oxidation performance was observed for Ti/Pt-IrO₂ anodes, followed by the Ti/SnO₂-Sb and Ti/PbO₂ anodes. The effectiveness of the treatment appears to correlate with the formation of oxidants such as active chlorine (i.e. Cl₂/HClO/ClO⁻). As a result, electro-generated chlorine led to the abundant formation of harmful by-products such as trihalomethanes (THMs) and haloacetic acids (HAAs), particularly at Ti/SnO₂-Sb and Ti/Pt-IrO₂ anodes. The highest concentration of total HAAs (i.e. 2.7 mg L⁻¹) was measured for the Ti/SnO₂-Sb electrode, after 0.55 Ah L⁻¹ of supplied specific electrical charge. Irrespective of the used material, electrochemical oxidation of ROC needs to be complemented by a polishing treatment to alleviate the release of halogenated by-products.     

Advanced treatment of biologically pretreated coking wastewater by electrochemical oxidation using boron-doped diamond electrodes

Electrochemical oxidation is a promising technology to treatment of bio-refractory wastewater. Coking wastewater contains high concentration of refractory and toxic compounds and the water quality usually cannot meet the discharge standards after conventional biological treatment processes. This paper initially investigated the electrochemical oxidation using boron-doped diamond (BDD) anode for advanced treatment of coking wastewater. Under the experimental conditions (current density 20-60 mA cm⁻², pH 3-11, and temperature 20-60 °C) using BDD anode, complete mineralization of organic pollutants was almost achieved, and surplus ammonia-nitrogen (NH₃-N) was further removed thoroughly when pH was not adjusted or at alkaline value. Moreover, the TOC and NH₃-N removal rates in BDD anode cell were much greater than those in other common anode systems such as SnO₂ and PbO₂ anodes cells. Given the same target to meet the National Discharge Standard of China, the energy consumption of 64 kWh kgCOD⁻¹ observed in BDD anode system was only about 60% as much as those observed in SnO₂ and PbO₂ anode systems. Further investigation revealed that, in BDD anode cell, organic pollutants were mainly degraded by reaction with free hydroxyl radicals and electrogenerated oxidants (S₂O₈²⁻, H₂O₂, and other oxidants) played a less important role, while direct electrochemical oxidation and indirect electrochemical oxidation mediated by active chlorine can be negligible. These results showed great potential of BDD anode system in engineering application as a final treatment of coking wastewater.     

Occurrence of androgens and progestogens in wastewater treatment plants and receiving river waters: Comparison to estrogens

Research has shown that exposure to androgens and progestogens can cause undesirable biological responses in the environment. To date, however, no detailed or direct study of their presence in wastewater treatment plants has been conducted. In this study, nine androgens, nine progestogens, and five estrogens were analyzed in influent and final effluent wastewaters in seven wastewater treatment plants (WWTPs) of Beijing, China. Over a period of three weeks, the average total hormone concentrations in influent wastewaters were 3562 (Wujiacun WWTP)-5400 ng/L (Fangzhuang WWTP). Androgens contributed 96% of the total hormone concentrations in all WWTP influents, with natural androgen (androsterone: 2977 ± 739 ng/L; epiandrosterone: 640 ± 263 ng/L; and androstenedione: 270 ± 132 ng/L) being the predominant compounds. The concentrations of synthetic progestogens (megestrol acetate: 41 ± 25 ng/L; norethindrone: 6.5 ± 3.3 ng/L; and medroxyprogesterone acetate: 6.0 ± 3.2 ng/L) were comparable to natural ones (progesterone: 66 ± 36 ng/L; 17α,20β-dihydroxy-4-progegnen-3-one: 4.9 ± 1.2 ng/L; 21α-hydroxyprogesterone: 8.5 ± 3.0 ng/L; and 17α-hydroxyprogesterone: 1.5 ± 0.95 ng/L), probably due to the wide and relatively large usage of synthetic progestogens in medical therapy. In WWTP effluents, androgens were still the dominant class accounting for 60% of total hormone concentrations, followed by progestogens (24%), and estrogens (16%). Androstenedione and testosterone were the main androgens detected in all effluents. High removal efficiency (91-100%) was found for androgens and progestogens compared with estrogens (67-80%), with biodegradation the major removal route in WWTPs. Different profiles of progestogens in the receiving rivers and WWTP effluents were observed, which could be explained by the discharge of a mixture of treated and untreated wastewater into the receiving rivers.     

Boron-doped diamond anodic treatment of olive mill wastewaters: Statistical analysis, kinetic modeling and biodegradability

The electrochemical treatment of olive mill wastewaters (OMW) over boron-doped diamond (BDD) electrodes was investigated. A factorial design methodology was implemented to evaluate the statistically important operating parameters, amongst initial COD load (1000-5000 mg/L), treatment time (1-4 h), current intensity (10-20 A), initial pH (4-6) and the use of 500 mg/L H₂O₂ as an additional oxidant, on treatment efficiency; the latter was assessed in terms of COD, phenols, aromatics and color removal. Of the five parameters tested, the first two had a considerable effect on COD removal. Hence, analysis was repeated at more intense conditions, i.e. initial COD values up to 10,000 mg/L and reaction times up to 7 h and a simple model was developed and validated to predict COD evolution profiles. The model suggests that the rate of COD degradation is zero order regarding its concentration and agrees well with an electrochemical model for the anodic oxidation of organics over BDD developed elsewhere. The treatability of the undiluted effluent (40,000 mg/L COD) was tested at 20 A for 15 h yielding 19% COD and 36% phenols' removal respectively with a specific energy consumption of 96 kW h/kg COD removed. Aerobic biodegradability and ecotoxicity assays were also performed to assess the respective effects of electrochemical treatment.     

Biodegradability enhancement of a pesticide-containing bio-treated wastewater using a solar photo-Fenton treatment step followed by a biological oxidation process

This work proposes an efficient combined treatment for the decontamination of a pesticide-containing wastewater resulting from phytopharmaceutical plastic containers washing, presenting a moderate organic load (COD = 1662-1960 mg O₂ L⁻¹; DOC = 513-696 mg C L⁻¹), with a high biodegradable organic carbon fraction (81%; BOD₅ = 1350-1600 mg O₂ L⁻¹) and a remaining recalcitrant organic carbon mainly due to pesticides. Nineteen pesticides were quantified by LC-MS/MS at concentrations between 0.02 and 45 mg L⁻¹ (14-19% of DOC). The decontamination strategy involved a sequential three-step treatment: (a) biological oxidation process, leading to almost complete removal of the biodegradable organic carbon fraction; (b) solar photo-Fenton process using CPCs, enhancing the bio-treated wastewater biodegradability, mainly due to pesticides degradation into low-molecular-weight carboxylate anions; (c) and a final polishing step to remove the residual biodegradable organic carbon, using a biological oxidation process. Treatment performance was evaluated in terms of mineralization degree (DOC), pesticides content (LC-MS/MS), inorganic ions and low-molecular-weight carboxylate anions (IC) concentrations. The estimated phototreatment energy necessary to reach a biodegradable wastewater, considering pesticides and low-molecular-weight carboxylate anions concentrations, Zahn-Wellens test and BOD₅/COD ratio, was only 2.3 kJ_UV L⁻¹ (45 min of photo-Fenton at a constant solar UV power of 30 W m⁻²), consuming 16 mM of H₂O₂, which pointed to 52% mineralization and an abatement higher than 86% for 18 pesticides. The biological oxidation/solar photo-Fenton/biological oxidation treatment system achieved pesticide removals below the respective detection limits and 79% mineralization, leading to a COD value lower than 150 mg O₂ L⁻¹, which is in agreement with Portuguese discharge limits regarding water bodies.     

Assessment of human adenovirus removal in a full-scale membrane bioreactor treating municipal wastewater

Human adenoviruses (HAdVs) in wastewater samples taken from four different treatment stages of a full-scale municipal wastewater treatment plant (i.e., incoming raw sewage, primary sedimentation effluent, membrane bioreactor (MBR) influent, and MBR effluent) were quantified by real-time PCR assays to further estimate removal efficiency of the HAdVs. Based on hexon gene sequence comparisons, HAdV species A, C, and F were consistently found in the wastewater samples. In general, all three identified HAdV species were detected in most of the wastewater samples using the real-time PCR assays. Overall HAdV concentrations were rather stable over the entire 8-month study period (January-August, 2008) (approximately 10⁶-10⁷ viral particles/L of wastewater for the raw sewage and primary effluent; 10⁸-10⁹ viral particles/L for the MBR influent; and, 10³-10⁴ viral particles/L for the MBR effluent). No significant seasonal differences were noticed for the HAdV abundances. Removal efficiencies of the viral particles in the full-scale MBR process were assessed and showed an average HAdV removal of 5.0 ± 0.6 logs over the study period. The removal efficiencies for F species (average log removal of 6.5 ± 1.3 logs) were typically higher (p-value <0.05) than those of the other two species (average of 4.1 ± 0.9 and 4.6 ± 0.5 logs for species A and C, respectively). These results demonstrate that the full-scale MBR system efficiently removed most HAdV from the wastewater leaving about 10³ viral particles/L in the MBR effluent.     

Hydrogen and methane production from swine wastewater using microbial electrolysis cells

The production of a useful and valuable product during swine wastewater treatment, such as hydrogen gas, could help to lower treatment costs. Hydrogen can theoretically be produced from wastewater by electrohydrogenesis in a microbial electrolysis cell (MEC) or by fermentation. Using a single-chamber MEC with a graphite-fiber brush anode, hydrogen gas was generated at 0.9-1.0 m³ m⁻³ day⁻¹ H₂ using a full-strength or diluted swine wastewater. COD removals ranged from 8 to 29% in 20-h tests, and from 69 to 75% in longer tests (184 h) using full-strength wastewater. The gas produced was up to 77 ± 11% hydrogen, with overall recoveries of up to 28 ± 6% of the COD in the wastewater as hydrogen gas. Methane was also produced at a maximum of 13 ± 4% of total gas volume. The efficiency of hydrogen production, based on the electrical energy needed (but excluding the energy in the wastewater) compared to the energy of the hydrogen gas produced, was as high as 190 ± 39% in 42-h batch tests with undiluted wastewater, but was lower in longer batch tests of 184 h (91 ± 6%). Hydrogen gas could not be recovered in fermentation tests using wastewater with a heat-treated inoculum. Hydrogen production was shown to be possible by fermentation when the wastewater was sterilized, but this process would not be practical or energy efficient. We therefore conclude from these tests that MECs are an effective method for hydrogen recovery from swine wastewater treatment, although the process needs to be further evaluated for reducing methane production, increasing the efficiency of converting the organic matter into current, and increasing recovery of hydrogen gas produced at the cathode.     

The impact of alum based advanced nutrient removal processes on phosphorus bioavailability

Because eutrophication is a widespread consequence of wastewater discharges, there is a strong impetus to develop new approaches to remove phosphorus (P) from wastewater treatment plant (WWTP) effluents. We examined the effluents from a pilot plant that is testing various alum based processes for achieving > 99% P removal, however, it is not known how these advanced P removal technologies affect the bioavailability of P (BAP). We tested how the percent BAP (%BAP) varied with different P removal levels using an algal growth bioassay methodology. This facility reduced total P concentrations from ≈ 500 μg L⁻¹ in the pilot plant influent to 19 ± 4 (±SD) μg L⁻¹ in the final effluent, and our results showed that as the level of P removal increased, the %BAP of the product declined sharply, r² = 0.98. Prior to alum treatment, the influent had an average %BAP of 79 ± 13%, and after three steps of alum-based removal the %BAP averaged 7 ± 4%. Thus, this alum based P removal process was very effective at sequestering the P forms that most readily stimulate algal growth. Further, our results show the final BAP of the effluent was only ≈ 50% of the “reactive” P concentration. These results have important implications for nutrient management and trading schemes.     

Sulfide-induced nitrate reduction in the sludge of an anaerobic digester of a zero-discharge recirculating mariculture system

The anaerobic digester is a vital component in a zero-discharge mariculture system as therein most of the organic matter is mineralized and nitrogen-containing compounds are converted to gaseous N₂. Although denitrification is a major respiratory process in this nitrate-rich treatment stage, also sulfate respiration takes place and may cause undesirable high sulfide concentrations in the effluent water. To examine the effect of sulfide on nitrate reduction, in situ depth profiles of inorganic nitrogen and sulfur compounds were determined. Additionally, nitrate reduction was examined as a function of ambient sulfide concentrations in sludge collected from different locations in the anaerobic reactor. Depth profiles showed high concentrations of nitrate and low concentrations of sulfide and ammonia in the aqueous layer of the reactor. A sharp decrease of nitrate and an increase in sulfide and ammonia concentrations was measured at the water-sludge interface. Nitrate reduction was highest in this interface zone with rates of up to 8.05 ± 0.57 μmol NO₃⁻ h⁻¹ g_(sludge)⁻¹. Addition of sulfide increased the nitrate reduction rate at all sludge depths, pointing to the important role of autotrophic denitrification in the anaerobic reactor. Dissimilatory nitrate reduction to ammonia (DNRA) was found to be low in all sludge layers but was enhanced when sludge was incubated at high sulfide concentrations. Although nitrate reduction rates increased as a result of sulfide addition to sludge samples, no differences in nitrate reduction rates were observed between the samples incubated with different initial sulfide concentrations. This as opposed to sulfide oxidation rates, which followed Michaelis-Menten enzymatic kinetics. Partial oxidation of sulfide to elemental sulfur instead of a complete oxidation to sulfate, could explain the observed patterns of nitrate reduction and sulfide oxidation in sludge incubated with different initial sulfide concentrations.     

Oxidation of organics in retentates from reverse osmosis wastewater reuse facilities

The use of membrane processes for wastewater treatment and reuse is rapidly expanding. Organic, inorganic, and biological constituents are effectively removed by reverse osmosis (RO) membrane processes, but concentrate in membrane retentates Disposal of membrane concentrates is a growing concern. Applying advanced oxidation processes (AOPs) to RO retentate is logical because extensive treatment and energy inputs were expended to concentrate the organics, and it is cheaper to treat smaller flowstreams. AOPs (e.g., UV irradiation in the presence of titanium dioxide; UV/TiO₂) can remove a high percentage of organic matter from RO retentates. The combination of AOPs and a simple biological system (e.g., sand filter) can remove higher levels of organic matter at lower UV dosages because AOPs produce biologically degradable material (e.g., organic acids) that have low hydroxyl radical rate constants, meaning that their oxidation, rather than that of the primary organic matter in the RO retentate, dictates the required UV energy inputs. At the highest applied UV dose (10 kWh m⁻3), the dissolved organic carbon (DOC) in the RO retentate decreased from ∼40 to 8 mg L⁻1, of which approximately 6 mg L⁻1 were readily biologically degradable. Therefore, after combined UV treatment and biodegradation, the final DOC concentration was 2 mg L⁻1, representing a 91% removal. These results suggest that UV/TiO₂ plus biodegradation of RO retentates is feasible and would significantly reduce the organic pollutant loading into the environment from wastewater reuse facilities.     

Phosphate removal in agro-industry: Pilot- and full-scale operational considerations of struvite crystallization

Pilot-scale struvite crystallization tests using anaerobic effluent from potato processing industries were performed at three different plants. Two plants (P1 & P2) showed high phosphate removal efficiencies, 89 ± 3% and 75 ± 8%, resulting in final effluent levels of 12 ± 3 mg PO₄³⁻-P L⁻¹ and 11 ± 3 mg PO₄³⁻-P L⁻¹, respectively. In contrast, poor phosphate removal (19 ± 8%) was obtained at the third location (P3). Further investigations at P3 showed the negative effect of high Ca²⁺/PO₄³⁻-P molar ratio (ca. 1.25 ± 0.11) on struvite formation. A full-scale struvite plant treating anaerobic effluent from a dairy industry showed the same Ca²⁺ interference. A shift in the influent Ca²⁺/PO₄³⁻-P molar ratio from 2.69 to 1.36 resulted in average total phosphorus removal of 78 ± 7%, corresponding with effluent levels of 14 ± 4 mg P_total L⁻¹ (9 ± 3 mg PO₄³⁻-P L⁻¹). Under these conditions high quality spherical struvite crystals of 2-6 mm were produced.     

Heterogeneous photocatalytic removal of toluene from air on building materials enriched with TiO2

This paper reports the potential of heterogeneous photocatalysis as an advanced oxidation technology for removal of toluene from air using TiO₂ as a photocatalyst in building materials. First, the photocatalytic activity of two types of TiO₂ containing building materials, i.e. roofing tiles and corrugated sheets, has been investigated at ambient conditions (T=25.0 °C; relative humidity RH=47%; toluene inlet concentration [TOL]_in=17–35 ppbv). Toluene removal efficiencies up to 63% were observed at a gas residence time (τ) of 17 s. Second, the effect of RH (1–77%), [TOL]_in (23–465 ppmv) and τ (17–115 s) on toluene removal has been systematically investigated using TiO₂ containing roofing tiles as photocatalytic building materials. Results revealed lower toluene removal efficiencies at higher RH and [TOL]_in, whereas a positive effect was observed with increased τ. Under optimal conditions, toluene removal efficiencies up to 78±2% and elimination rates higher than 100 mg h⁻¹ m⁻² roofing tile were obtained. A decline in photocatalytic activity by a factor of 2 was observed after operation at gas residence times shorter than 69 s and [TOL]_in higher than 76 ppmv. Washing the building materials with deionized water, simulating rainfall, could partially (i.e. by a factor 1.3) regenerate the catalyst activity.     

Electro-oxidation of pistachio processing wastewater using Ti/Pt mesh-type anodes in batch system

In this study, the treatment of pistachio processing wastewater (PPW) by electro-oxidation method was investigated. Ti/Pt-plated electrodes were used for the anode material, and stainless steel electrodes were used for cathode material. Experimental studies were carried out in batch mode. Stirring speed, supporting electrolyte species and concentration, initial pH value, current density, temperature and dilution ratio were selected as experimental parameters effecting removal efficiency. In Ti/Pt electrode experimental studies on the optimum conditions, chemical oxygen demand (COD), total organic carbon (TOC) and total phenols (TP) removal efficiencies were obtained, respectively, as 99.98%, 70.74% and 100%, and energy consumption value was obtained as 297.5 kW-h/m³ (12.39 kW-h/kg COD, 51.29 kW-h/kg TOC and 64.68 kW-h/kg TP). As a result of the experimental studies, the PPW can be treated by electro-oxidation. Given the results of removal efficiency and energy consumption values, it was concluded the electro-oxidation using Ti/Pt anode very appropriate treatment of PPW.     

Simultaneous nitrification, denitrification and carbon removal in microbial fuel cells

Microbial fuel cells (MFCs) can use nitrate as a cathodic electron acceptor, allowing for simultaneous removal of carbon (at the anode) and nitrogen (at the cathode). In this study, we supplemented the cathodic process with in situ nitrification through specific aeration, and thus obtained simultaneous nitrification and denitrification (SND) in the one half-cell. Synthetic wastewater containing acetate and ammonium was supplied to the anode; the effluent was subsequently directed to the cathode. The influence of oxygen levels and carbon/nitrogen concentrations and ratios on the system performances was investigated. Denitrification occurred simultaneously with nitrification at the cathode, producing an effluent with levels of nitrate and ammonium as low as 1.0 ± 0.5 mg N L⁻¹ and 2.13 ± 0.05 mg N L⁻¹, respectively, resulting in a nitrogen removal efficiency of 94.1 ± 0.9%. The integration of the nitrification process into the cathode solves the drawback of ammonium losses due to diffusion between compartments in the MFC, as previously reported in a system operating with external nitrification stage. This work represents the first successful attempt to combine SND and organics oxidation while producing electricity in an MFC.