Nanofiltration combined with ozone-based processes for the removal of antineoplastic drugs from wastewater effluents.

Over the past years, there has been an increasing concern about the occurrence of antineoplastic drugs in water bodies. The incomplete removal of these pharmaceuticals from wastewaters has been confirmed by several scientists, making it urgent to find a reliable technique or a combination of techniques capable to produce clean and safe water. In this work, the combination of nanofiltration and ozone (O3)-based processes (NF + O3, NF + O3/H2O2 and NF + O3/H2O2/UVA) was studied aiming to produce clean water from wastewater treatment plant (WWTP) secondary effluents to be safely discharged into water bodies, reused in daily practices such as aquaculture activities or for recharging aquifers used as abstraction sources for drinking water production. Nanofiltration was performed in a pilot-scale unit and O3-based processes in a continuous-flow column. The peroxone process (O3/H2O2) was considered the most promising technology to be coupled to nanofiltration, all the target pharmaceuticals being removed at an extent higher than 98% from WWTP secondary effluents, with a DOC reduction up to 92%. The applicability of the clean water stream for recharging aquifers used as abstraction sources for drinking water production was supported by a risk assessment approach, regarding the final concentrations of the target pharmaceuticals. Moreover, the toxicity of the nanofiltration retentate, a polluted stream generated from the nanofiltration system, was greatly decreased after the application of the peroxone process, which evidences the positive impact on the environment of implementing a NF + O3/H2O2 process.

Antineoplastic drugs in urban wastewater: Occurrence, nanofiltration treatment and toxicity screening.

Antineoplastic drugs are pharmaceuticals that have been raising concerns among the scientific community due to: (i) their increasing prescription in the fight against the disease of the twentieth century (cancer); (ii) their recalcitrance to conventional wastewater treatments; (iii) their poor environmental biodegradability; and (iv) their potential risk to any eukaryotic organism. This emerges the urgency in finding solutions to mitigate the entrance and accumulation of these hazardous chemicals in the environment. Advanced oxidation processes (AOPs) have been taken into consideration to improve the degradation of antineoplastic drugs in wastewater treatment plants (WWTPs), but the formation of by-products that are more toxic or exhibit a different toxicity profile than the parent drug is frequently reported. This work evaluates the performance of a nanofiltration pilot unit, equipped with a Desal 5DK membrane, in the treatment of real WWTP effluents contaminated (without spiking) with eleven pharmaceuticals, five of which were never studied before. Average removals of 68 ± 23% were achieved for the eleven compounds, with decreasing risks from feed to permeate for aquatic organisms from receiving waterbodies (with the exception of cyclophosphamide, for which a high risk was estimated in the permeate). Aditionally, no significative impact on the growth and germination of three different seeds (Lepidium sativum, Sinapis alba, and Sorghum saccharatum) were determined for permeate matrix in comparison to the control.

Degradation of Neonicotinoids and Caffeine from Surface Water by Photolysis.

Along with rapid social development, the use of insecticides and caffeine-containing products increases, a trend that is also reflected in the composition of surface waters. This study is focused on the phototreatment of a surface water containing three neonicotinoids (imidacloprid, thiamethoxam, and clothianidin) and caffeine. Firstly, the radiation absorption of the target pollutants and the effect of the water matrix components were evaluated. It was observed that the maximum absorption peaks appear at wavelengths ranging from 246 to 274 nm, and that the water matrix did not affect the efficiency of the removal of the target pollutants. It was found that the insecticides were efficiently removed after a very short exposure to UV irradiation, while the addition of hydrogen peroxide was needed for an efficient caffeine depletion. The electrical energy per order was estimated, being the lowest energy required (9.5 kWh m-3 order-1) for the depletion of thiamethoxan by indirect photolysis, and a concentration of hydrogen peroxide of 5 mg dm-3. Finally, a preliminary evaluation on the formation of by-products reveals that these compounds play a key role in the evolution of the ecotoxicity of the samples, and that the application of direct photolysis reduces the concentration of these intermediates.

Light-emitting diodes effect on Aspergillus species in filtered surface water: DNA damage, proteome response and potential reactivation.

DNA damage and changes in proteome response can occur as a consequence of UV light exposure. The emerging light-emitting diodes (LEDs) can be acquired with different wavelengths. In this study, LEDs that emit at 255 nm and 265 nm were selected to test the DNA damage and proteome response after inactivation of A. fumigatus, A. niger and A. terreus spiked into filtered surface water. Additionally, photoreactivation and dark repair studies were performed to evaluate the potential ability of the spores to recover after UV exposure. Results showed that both LEDs were able to induce the formation of cyclobutane pyrimidine dimers in A. fumigatus and A. terreus whereas, for A. niger, the formation of cyclobutane pyrimidine dimers was only detected when the LEDs that induced inactivation (that emit at 265 nm) were used. Proteome response showed that UV radiation treatment triggered different types of stress response, mainly concerning the protection from oxidative stress by A. fumigatus and A. terreus. Photoreactivation was detected for all the species except A. niger and, no dark repair was observed.

Detection of anticancer drugs in wastewater effluents: Grab versus passive sampling.

The occurrence of six anticancer drugs was evaluated in wastewater effluents. Several grab samples from wastewater effluent were collected throughout a year. Capecitabine, cyclophosphamide and ifosfamide were detected at concentrations ranging from 8 to 46 ng·L-1. Capecitabine was detected in all the sampling events whereas cyclophosphamide and ifosfamide were detected less frequently. Additionally, the suitability of using pharmaceutical-polar organic chemical integrative samplers (POCIS) to monitor the target drugs in wastewater effluents was assessed. Capecitabine, ifosfamide and cyclophosphamide were detected with POCIS and showed a linear uptake over 15 days. The sampling rates, determined in situ, were used to estimate time-weighted average concentrations. A good correlation was found between the concentration of capecitabine detected with POCIS deployed during five days (32 ± 1 ng·L-1) and the average concentrations obtained in grab samples. The use of passive samplers has advantages over grab samples: easier analysis, less time and costs associated with the analytical method. Passive samplers also provide a time-weighted information about the concentration of pollutants in the aquatic environment. However, information may be lost when the concentration of the target compounds in wastewater effluents is low and the passive samplers are deployed for a short time.

Stability of Polymeric Membranes to UV Exposure before and after Coating with TiO2 Nanoparticles.

The combination of photocatalysis and membrane filtration in a single reactor has been proposed, since the photocatalytic treatment may degrade the pollutants retained by the membrane and reduce fouling. However, polymeric membranes can be susceptible to degradation by UV radiation and free radicals. In the present study, five commercial polymeric membranes were exposed to ultraviolet (UV) radiation before and after applying a sol-gel coating with TiO2 nanoparticles. Membrane stability was characterized by changes in hydrophilicity as well as analysis of soluble substances and nanoparticles detached into the aqueous medium, and by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and energy-dispersive X-ray spectrometry (EDS) for structural, morphological, and elemental distribution analysis, respectively. The TiO2 coating conferred photocatalytic properties to the membranes and protected them during 6 h of UV radiation exposures, reducing or eliminating chemical and morphological changes, and in some cases, improving their mechanical resistance. A selected commercial nanofiltration membrane was coated with TiO2 and used in a hybrid reactor with a low-pressure UV lamp, promoting photocatalysis coupled with cross-flow filtration in order to remove 17α-ethinylestradiol spiked into an aqueous matrix, achieving an efficiency close to 100% after 180 min of combined filtration and photocatalysis, and almost 80% after 90 min.

Solvent-Free Process for the Development of Photocatalytic Membranes.

This work described a new sustainable method for the fabrication of ceramic membranes with high photocatalytic activity, through a simple sol-gel route. The photocatalytic surfaces, prepared at low temperature and under solvent-free conditions, exhibited a narrow pore size distribution and homogeneity without cracks. These surfaces have shown a highly efficient and reproducible behavior for the degradation of methylene blue. Given their characterization results, the microfiltration photocatalytic membranes produced in this study using solvent-free conditions are expected to effectively retain microorganisms, such as bacteria and fungi that could then be inactivated by photocatalysis.

Production of mycotoxins by filamentous fungi in untreated surface water.

Several research studies reported that mycotoxins and other metabolites can be produced by fungi in certain matrices such as food. In recent years, attention has been drawn to the wide occurrence and identification of fungi in drinking water sources. Due to the large demand of water for drinking, watering, or food production purposes, it is imperative that further research is conducted to investigate if mycotoxins may be produced in water matrices. This paper describes the results obtained when a validated analytical method was applied to detect and quantify the presence of mycotoxins as a result of fungi inoculation and growth in untreated surface water. Aflatoxins B1 and B2, fumonisin B3, and ochratoxin A were detected at concentrations up to 35 ng/L. These results show that fungi can produce mycotoxins in water matrices in a non-negligible quantity and, as such, attention must be given to the presence of fungi in water.

Assessment of a New Silicon Carbide Tubular Honeycomb Membrane for Treatment of Olive Mill Wastewaters.

Extremely high removals of total suspended solids and oil and grease were obtained when olive mill wastewaters were filtered using new silicon carbide tubular membranes. These new membranes were used at constant permeate flux to treat real olive mill wastewaters at pilot scale. The filtration conditions were evaluated and optimized in terms of the selection of the permeate flux and flux maintenance strategies employed-backpulsing and backwashing-in order to reduce fouling formation. The results obtained reveal that the combination of backpulses and backwashes helps to maintain the permeate flux, avoids transmembrane pressure increase and decreases the cake resistance. Moreover, membrane cleaning procedures were compared and the main agents responsible for fouling formation identified. Results also show that, under total recirculation, despite an increased concentration of pollutants in the feed stream, the quality of the permeate is maintained. Membrane filtration using silicon carbide membranes is an effective alternative to dissolved air flotation and can be applied efficiently to remove total suspended solids and oil and grease from olive mill wastewaters.

Comparison of UV photolysis, nanofiltration, and their combination to remove hormones from a drinking water source and reduce endocrine disrupting activity.

A sequential water treatment combining low pressure ultraviolet direct photolysis with nanofiltration was evaluated to remove hormones from water, reduce endocrine disrupting activity, and overcome the drawbacks associated with the individual processes (production of a nanofiltration-concentrated retentate and formation of toxic by-products). 17ß-Estradiol, 17α-ethinylestradiol, estrone, estriol, and progesterone were spiked into a real water sample collected after the sedimentation process of a drinking water treatment plant. Even though the nanofiltration process alone showed similar results to the combined treatment in terms of the water quality produced, the combined treatment offered advantage in terms of the load of the retentate and decrease in the endocrine-disrupting activity of the samples. Moreover, the photolysis by-products produced, with higher endocrine disrupting activity than the parent compounds, were effectively retained by the membrane. The combination of direct LP/UV photolysis with nanofiltration is promising for a drinking water utility that needs to cope with sudden punctual discharges or deterioration of the water quality and wants to decrease the levels of chemicals in the nanofiltration retentate.

Drinking water treatment of priority pesticides using low pressure UV photolysis and advanced oxidation processes.

This study reports the efficiency of low pressure UV photolysis for the degradation of pesticides identified as priority pollutants by the European Water Framework Directive 2000/60/EC. Direct low pressure UV photolysis and advanced oxidation processes (using hydrogen peroxide and titanium dioxide) experiments were conducted in laboratory grade water, surface water, and groundwater. LP direct photolysis using a high UV fluence (1500 mJ/cm(2)) was found to be extremely efficient to accomplish the degradation of all pesticides except isoproturon, whereas photolysis using hydrogen peroxide and titanium dioxide did not significantly enhance their removal. In all matrices tested the experimental photolysis of the pesticides followed the same trend: isoproturon degradation was negligible, alachlor, pentachlorophenol, and atrazine showed similar degradation rate constants, whereas diuron and chlorfenvinphos were highly removed. The degradation trend observed for the selected compounds followed the decadic molar absorption coefficients order with exception of isoproturon probably due to its extremely low quantum yield. Similar direct photolysis rate constants were obtained for each pesticide in the different matrices tested, showing that the water components did not significantly impact degradation. Extremely similar photolysis rate constants were also obtained in surface water for individual compounds when compared to mixtures. The model fluence and time-based rate constants reported were very similar to the direct photolysis experimental results obtained, while overestimating the advanced oxidation results. This model was used to predict how degradation of isoproturon, the most resilient compound, could be improved.

Evaluation of UV irradiation for photolytic and oxidative degradation of pharmaceutical compounds in water.

A medium-pressure (MP) ultraviolet (UV) system was used to investigate the UV photolysis and UV/H(2)O(2) oxidation of pharmaceutically active compounds (PhACs) that belong to different therapeutic classes and were found to occur in the aquatic environment. The results obtained in laboratory-grade water (LGW) and surface water (SW) were compared with low-pressure (LP) results reported previously. Overall, MP lamps proved to be more efficient to maximize the bench-scale degradation of the selected group of compounds (ketoprofen, naproxen, carbamazepine, ciprofloxacin, clofibric acid, and iohexol) by both UV photolysis and UV/H(2)O(2) oxidation. Fundamental direct and indirect photolysis parameters obtained in LGW are reported and used to model the MP-UV photolysis and MP-UV/H(2)O(2) oxidation of the pharmaceuticals in SW, predicting the experimental results very well.

UV degradation kinetics and modeling of pharmaceutical compounds in laboratory grade and surface water via direct and indirect photolysis at 254 nm.

Direct and indirect photolysis of pharmaceutically active compounds (PhACs) was investigated in laboratory-grade water (LGW) and a local surface water using a low-pressure ultraviolet batch reactor. The PhACs selected in this study belong to different therapeutic classes and are known to occur in environmental samples. Fundamental photolysis and advanced oxidation process parameters obtained in LGW (such as the decadic molar absorption coefficient, quantum yield, and degradation rate constants) are reported and discussed. These parameters, together with the incident photon irradiance, solution depth, and solution absorbance were used to develop UV and UV/ H202 photolysis models that were compared with experimental results obtained in the surface water. The model predicted the experimental UV photolysis removals well but underestimated the UV/H2O2 photolysis results. These models were used to discuss the effects of optical path length and H2O2 concentration on the UV-based rate constant predictions.