Activity and stability of bifunctional perovskite/carbon-based electrodes for the removal of antipyrine by electro-Fenton process.

Bifunctional perovskite/carbon-black(CB)/polytetrafluoroethylene(PTFE) electrodes for electro-generation and catalytic decomposition of hydrogen peroxide to oxidizing hydroxyl radicals have been fabricated. These electrodes were tested for electroFenton (EF) removal of antipyrine (ANT) as a model antipyretic and analgesic drug. The influence of the binder loading (20 and 40 wt % PTFE) and type of solvent (1,3-dipropanediol and water) was studied for the preparation of CB/PTFE electrodes. The electrode prepared with 20 wt % PTFE and water exhibited a low impedance and remarkable H2O2 electro-generation (about 1 g/L after 240 min, a production rate of ca. 6.5 mg/h·cm2). The incorporation of perovskite on CB/PTFE electrodes was also studied following two different methods: i) direct deposition on the CB/PTFE electrode surface and ii) addition in the own CB/PTFE/water paste used for the fabrication. Physicochemical and electrochemical characterization techniques were used for the electrode's characterization. The dispersion of perovskite particles in the own electrode matrix (method ii) exhibited a higher EF performance than the immobilisation onto the electrode surface (method i). EF experiments at 40 mA/cm2 and pH 7 (non-acidified conditions) showed ANT and TOC removals of 30% and 17%, respectively. The increase of current intensity up to 120 mA/cm2 achieved the complete removal of ANT and 92% of TOC mineralisation in 240 min. The bifunctional electrode also proved high stability and durability after 15 h of operation.

Critical review of technologies for the on-site treatment of hospital wastewater: From conventional to combined advanced processes.

This review aims to assess different technologies for the on-site treatment of hospital wastewater (HWW) to remove pharmaceutical compounds (PhCs) as sustances of emerging concern at a bench, pilot, and full scales from 2014 to 2020. Moreover, a rough characterisation of hospital effluents is presented. The main detected PhCs are antibiotics and psychiatric drugs, with concentrations up to 1.1 mg/L. On the one hand, regarding the presented technologies, membrane bioreactors (MBRs) are a good alternative for treating HWW with PhCs removal values higher than 80% in removing analgesics, anti-inflammatories, cardiovascular drugs, and some antibiotics. Moreover, this system has been scaled up to the pilot plant scale. However, some target compounds are still present in the treated effluent, such as psychiatric and contrast media drugs and recalcitrant antibiotics (erythromycin and sulfamethoxazole). On the other hand, ozonation effectively removes antibiotics found in the HWW (>93%), and some studies are carried out at the pilot plant scale. Even though, some families, such as the X-ray contrast media, are recalcitrant to ozone. Other advanced oxidation processes (AOPs), such as Fenton-like or UV treatments, seem very effective for removing pharmaceuticals, Antibiotic Resistance Bacteria (ARBs) and Antibiotic Resistance Genes (ARGs). However, they are not implanted at pilot plant or full scale as they usually consider extra reactants such as ozone, iron, or UV-light, making the scale-up of the processes a challenging task to treat high-loading wastewater. Thus, several examples of biological wastewater treatment methods combined with AOPs have been proposed as the better strategy to treat HWW with high removal of PhCs (generally over 98%) and ARGs/ARBs (below the detection limit) and lower spending on reactants. However, it still requires further development and optimisation of the integrated processes.

Advanced bio-oxidation of fungal mixed cultures immobilized on rotating biological contactors for the removal of pharmaceutical micropollutants in a real hospital wastewater.

Hospital wastewater represents an important source of pharmaceutical active compounds (PhACs) as contaminants of emerging concern for urban wastewater treatment plants. This work evaluates a fungal biological treatment of a hospital effluent before discharging in the municipal sewer system. This treatment was performed in rotating biological contactors (RBCs) covered with wooden planks in order to promote the attachment of the fungal biomass. These bioreactors, initially inoculated with Trametes versicolor as white rot fungi, have created biofilms of a diversified population of fungal (wood-decaying fungi belonging to Basidiomycota and Ascomycetes) and bacterial (Beta-proteobacteria, Firmicutes, and Acidobacteria) microorganisms. The mixed fungal/bacterial community achieved a stable performance in terms of carbon, nitrogen, and phosphorous reductions for 75 days of continuous operation. Moreover, a remarkable removal of pharmaceutical micropollutants was accomplished especially for antibiotics (98.4 ± 0.7, 83 ± 8% and 76 ± 10 for azithromycin, metronidazole and sulfamethoxazole, respectively). Previous studies have proven a high efficiency of fungi for the removal of microcontaminants as a result of advanced bio-oxidation processes mediated by oxidizing hydroxyl radicals. This study evidences the development of a stable fungal-bacterial mixed culture over wooden-modified RBCs for in-situ removal of pharmaceutical compounds of hospital wastewater under non-sterile conditions and non-strict temperature control, avoiding periodical fungal inoculation due to destabilization and displacement of fungal cultures by indigenous wastewater bacteria.

Application of a Fenton process for the pretreatment of an iron-containing oily sludge: A sustainable management for refinery wastes.

The feasibility of a Fenton-type process for the pretreatment of an oily refinery sludge has been explored taking advantage of the iron contained in the own sludge. This process reduces the content of total petroleum hydrocarbons (TPHs) accompanied by an increase in the total organic carbon concentration in the liquid phase. The effect of the temperature and the hydrogen peroxide loading was thoroughly studied in this work being the oxidant concentration the most critical parameter. Under 60 °C and 90 g/L of initial hydrogen peroxide concentration, the Total Organic Carbon (TOC) of the liquid phase was increased up values of 1336 mg/L and with a remarkable contribution of acetic acid as final oxidized compound (396 mgC/L). Additionally, nitrogen and phosphorous compounds were also dissolved in the aqueous phase achieving values of 250 mg/L and 7 mg/L for total Kjeldahl nitrogen and total phosphorous, respectively. Respirometry assays of the aqueous phase after the Fenton pretreatment have evidenced an increase of biodegradability up to 49% which makes this phase suitable for further biological processing in the refinery scheme. The reduction of the content of TPHs (61%) of the oily sludge, has also improved the settleability of the treated effluent (reducing the capillary suction time (CST) in ca. 88%).

Comprehensive characterization of an oily sludge from a petrol refinery: A step forward for its valorization within the circular economy strategy.

Refinery treatment plants produce large quantities of oily sludge during the petroleum refining processes. The hazardousness associated with the disposal of these wastes, make necessary the development of innovative technologies to handle it adequately, linked to the concepts of circular economy and environmental sustainability. This work provides for the first time a methodology for the deep characterization of this kind of wastes and consequently new insights regarding its valorization. A review of works dealing with the characterization of this type of wastes has been addressed evidencing the complexity and variability of these effluents. The oily sludge under study contains a high concentration of Chemical Oxygen Demand of 196 g COD/L, a Total Kjeldahl Nitrogen of 2.8 g TKN/kg, a phosphorous content as PO43- of 7 g/kg, as well as a great presence of heavy metals in a different range of concentrations. This sludge is composed of three different phases: oily, aqueous and solid. The oily and the solid phases present high percentages of carbon content (84 and 26%, respectively), related to the presence of alkanes ranged from n-C9 to n-C44. Therefore, it could be possible their valorization by the synthesis of catalyst and/or adsorbents. A dark fermentation process could be also proposed for the oily phase to obtain H2 as an alternative energy source. Finally, the aqueous phase contains low carbon and nutrients concentration. A previous thermal pre-treatment applied to the oily sludge might increase nutrient and organic loading in the aqueous phase due to solid destruction, making this aqueous effluent suitable for a further conventional biological treatment.

Trametes versicolor immobilized on rotating biological contactors as alternative biological treatment for the removal of emerging concern micropollutants.

White rot fungi have been studied for the removal of micropollutants of emerging concern from wastewater during the last decade. However, several issues need to be overcome for its plausible implementation at full-scale installations such as the addition of supplementary substrates, the partial re-inoculation of fresh fungi or the use of extended hydraulic retention times. This work proposes the immobilization of Trametes versicolor on rotating biological contactors at bench scale (flowrates of 10 L/d and reactor capacity of 10 L) for the treatment of different urban wastewater. This type of bioreactor achieved remarkable reductions of the total organic carbon loading of the wastewater (70-75%) in a wide range of C:N and C:P ratios with limited addition of supplementary substrates, non-refreshment of the fungal biomass and only 1-day of hydraulic retention. The addition of gallic acid as quinone-like mediator and quelated iron and manganese complexes increased the removal of pharmaceutical micropollutants mediated by the so-called advanced bio-oxidation process. The immobilization of Trametes versicolor on rotating biological contactors also showed a remarkable stabilization of the fungi during the continuous treatment of different urban wastewater under non-sterile conditions. Thus, this system is a sound alternative for biological urban wastewater treatment with pharmaceutical removal because overcome all the problems usually associated with the water treatment technologies based on white rot fungi that makes difficult the scaling-up of the process and its implementation in full scale wastewater treatment plants.

Treatment of a wastewater from a pesticide manufacture by combined coagulation and Fenton oxidation.

The treatment of a non-biodegradable agrochemical wastewater has been studied by coupling of preliminary coagulation-flocculation step and further Fenton oxidation. High percentages of chemical oxygen demand (COD) removal (up to 58 %) were achieved in a first step using polyferric chloride as coagulant. This reduced significantly the amount of H2O2 required in the further Fenton oxidation. Using the stoichiometric amount relative to COD around 80 % of the remaining organic load was mineralized. The combined treatment allowed achieving the regional discharge limits of ecotoxicity at a cost substantially lower than the solution used so far where these wastewaters are managed as hazardous wastes.

Coupling membrane separation and photocatalytic oxidation processes for the degradation of pharmaceutical pollutants.

The coupling of membrane separation and photocatalytic oxidation has been studied for the removal of pharmaceutical pollutants. The retention properties of two different membranes (nanofiltration and reverse osmosis) were assessed. Comparable selectivity on the separation of pharmaceuticals were observed for both membranes, obtaining a permeate stream with concentrations of each pharmaceutical below 0.5 mg L(-)(1) and a rejected flux highly concentrated (in the range of 16-25 mg L(-)(1) and 18-32 mg L(-)(1) of each pharmaceutical for NF-90 and BW-30 membranes, respectively), when an initial stream of six pharmaceuticals was feeding to the membrane system (10 mg L(-)(1) of each pharmaceutical). The abatement of concentrated pharmaceuticals of the rejected stream was evaluated by means of heterogeneous photocatalytic oxidation using TiO2 and Fe2O3/SBA-15 in presence of hydrogen peroxide as photo-Fenton system. Both photocatalytic treatments showed remarkable removals of pharmaceutical compounds, achieving values between 80 and 100%. The nicotine was the most refractory pollutant of all the studied pharmaceuticals. Photo-Fenton treatment seems to be more effective than TiO2 photocatalysis, as high mineralization degree and increased nicotine removal were attested. This work can be considered an interesting approach of coupling membrane separation and heterogeneous photocatalytic technologies for the successful abatement of pharmaceutical compounds in effluents of wastewater treatment plants.

Catalytic wet hydrogen peroxide oxidation of a petrochemical wastewater.

Continuous Catalytic Wet Hydrogen Peroxide Oxidation (CWHPO) for the treatment of a petrochemical industry wastewater has been studied on a pilot plant scale process. The installation, based on a catalytic fixed bed reactor (FBR) coupled with a stirred tank reactor (STR), shows an interesting alternative for the intensification of a continuous CWHPO treatment. Agglomerated SBA-15 silica-supported iron oxide (Fe(2)O(3)/SBA-15) was used as Fenton-like catalyst. Several variables such as the temperature and hydrogen peroxide concentration, as well as the capacity of the pilot plant for the treatment of inlet polluted streams with different dilution degrees were studied. Remarkable results in terms of TOC reduction and increased biodegradability were achieved using 160 degrees C and moderate hydrogen peroxide initial concentration. Additionally, a good stability of the catalyst was evidenced for 8 hours of treatment with low iron leaching (less than 1 mg/L) under the best operating conditions.

Heterogeneous catalytic wet peroxide oxidation systems for the treatment of an industrial pharmaceutical wastewater.

The aim of this work was to assess the treatment of wastewater coming from a pharmaceutical plant through a continuous heterogeneous catalytic wet peroxide oxidation (CWPO) process using an Fe(2)O(3)/SBA-15 nanocomposite catalyst. This catalyst was preliminary tested in a batch stirred tank reactor (STR), to elucidate the influence of significant parameters on the oxidation system, such as temperature, initial oxidant concentration and initial pH of the reaction medium. In that case, a temperature of 80 degrees C using an initial oxidant concentration corresponding to twice the theoretical stoichiometric amount for complete carbon depletion and initial pH of ca. 3 allow TOC degradation of around 50% after 200 min of contact time. Thereafter, the powder catalyst was extruded with bentonite to prepare pellets that could be used in a fixed bed reactor (FBR). Results in the up-flow FBR indicate that the catalyst shows high activity in terms of TOC mineralization (ca. 60% under steady-state conditions), with an excellent use of the oxidant and high stability of the supported iron species. The activity of the catalyst is kept constant, at least, for 55h of reaction. Furthermore, the BOD(5)/COD ratio is increased from 0.20 to 0.30, whereas the average oxidation stage (AOS) changed from 0.70 to 2.35. These two parameters show a high oxidation degree of organic compounds in the outlet effluent, which enhances its biodegradability, and favours the possibility of a subsequent coupling with a conventional biological treatment.

Catalytic wet peroxidation of phenol in a fixed bed reactor.

Iron-containing mesostructured materials (Fe-SBA-15) are suitable for continuous treatment of phenolic aqueous solutions by means of catalytic wet peroxide oxidation (CWPO) in a packed-bed reactor. These materials were successfully extruded, crushed and sieved with a particle size ranging from 1 to 1.6 mm using mineral clay and methyl cellulose as binders. Non-significant changes have been found in the textural and structural properties of the extruded material in comparison to the parent powder Fe-SBA-15 material. Activity of extruded catalyst in terms of phenol degradation and TOC reduction has been monitored in a continuous mode. The increase of residence time enhances significantly the TOC degradation. The catalyst stability, taking into account the loss of iron species from the catalyst into the aqueous solution, has also been examined. The catalytic results of Fe-SBA-15 material in comparison to a homogeneous catalytic test prove the relevant role of the solid catalyst in the oxidation process.