José Antonio Perdigón-Melón

Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation

This work reports a systematic survey of over seventy individual pollutants in a Sewage Treatment Plant (STP) receiving urban wastewater. The compounds include mainly pharmaceuticals and personal care products, as well as some metabolites. The quantification in the ng/L range was performed by Liquid Chromatography-QTRAP-Mass Spectrometry and Gas Chromatography coupled to Mass Spectrometry. The results showed that paraxanthine, caffeine and acetaminophen were the main individual pollutants usually found in concentrations over 20 ppb. N-formyl-4-amino-antipiryne and galaxolide were also detected in the ppb level. A group of compounds including the beta-blockers atenolol, metoprolol and propanolol; the lipid regulators bezafibrate and fenofibric acid; the antibiotics erythromycin, sulfamethoxazole and trimethoprim, the antiinflammatories diclofenac, indomethacin, ketoprofen and mefenamic acid, the antiepileptic carbamazepine and the antiacid omeprazole exhibited removal efficiencies below 20% in the STP treatment. Ozonation with doses lower than 90 microM allowed the removal of many individual pollutants including some of those more refractory to biological treatment. A kinetic model allowed the determination of second order kinetic constants for the ozonation of bezafibrate, cotinine, diuron and metronidazole. The results show that the hydroxyl radical reaction was the major pathway for the oxidative transformation of these compounds.

Removal of pharmaceuticals and kinetics of mineralization by O3/H2O2 in a biotreated municipal wastewater

The ozonation of an effluent from the secondary clarifier of two Municipal Wastewater Treatment Plants was performed by using alkaline ozone and a combination of ozone and hydrogen peroxide. Alkaline ozonation achieved only a moderate degree of mineralization, essentially concentrated during the first few minutes; but the addition of hydrogen peroxide eventually led to a complete mineralization. The evolution of total organic carbon (TOC) as a measure of the extent of mineralization and the concentration of dissolved ozone were analyzed and linked in a kinetic model whose parameter represented the product of the exposure to hydroxyl radicals and the kinetic constant of indirect ozonation. This rate parameter yielded the highest values during the first part of O(3)/H(2)O(2) runs. The kinetic constant for the decomposition of ozone at the end of the run was also measured and computed for the non-oxidizable water matrix and yielded essentially the same values regardless of whether or not hydrogen peroxide was used. A group of 33 organic compounds, mainly pharmaceuticals and some relevant metabolites present in the wastewater effluents, were evaluated before and after the ozonation process using a liquid chromatography-hybrid triple-quadrupole linear ion trap system (LC-QqLIT-MS). The results demonstrate that the ozonation degrades these compounds with efficiencies of over 99% in most cases, even under low mineralization conditions in alkaline ozonation.

Application of the combination index (CI)-isobologram equation to study the toxicological interactions of lipid regulators in two aquatic bioluminescent organisms.

Pharmaceuticals in the aquatic environment do not appear singly and usually occur as complex mixtures, whose combined effect may exhibit toxicity to the aquatic biota. We report an environmental application of the combination index (CI)-isobologram equation, a method widely used in pharmacology to study drug interactions, to determine the nature of toxicological interactions of three fibrates toward two aquatic bioluminescent organisms, Vibrio fischeri and the self-luminescent cyanobacterial recombinant strain Anabaena CPB4337. The combination index-isobologram equation method allows computerized quantitation of synergism, additive effect and antagonism. In the Vibrio test, the fibrate combinations showed antagonism at low effect levels that turned into an additive effect or synergism at higher effect levels; by contrast, in the Anabaena test, the fibrate combinations showed a strong synergism at the lowest effect levels and a very strong antagonism at high effect levels. We also evaluated the nature of the interactions of the three fibrates with a real wastewater sample in the cyanobacterial test. We propose that the combination index-isobologram equation method can serve as a useful tool in ecotoxicological assessment.

Degradation of caffeine and identification of the transformation products generated by ozonation

The ozonation of caffeine in water was performed at different pH values, including acidic conditions. Kinetic experiments were conducted by adding pulses of a concentrated caffeine solution to ozone saturated water. The results showed a rapid decrease of ozone concentration during the first 15s after injection, followed by a gradual decline at a much slower rate. The data were fitted to a second order kinetic model with rate constants increasing from 0.25 to 1.05 M(-1)s(-1) for pH in the 3-10 range. The initial ozone consumption per mol of ozonated caffeine was greater at high pH values, reflecting a higher ozone decomposition rate. The decomposition of ozone was positively affected by the concentration of caffeine, an effect that could be attributed to the presence of a reaction intermediate from the ozonation of caffeine that behaved as a strong promoter of ozone decomposition. A study of the transformation products identified by liquid chromatography in combination with time-of-flight mass spectrometry was carried out, which permitted a tentative degradation pathway to be proposed and several persistent by-products to be identified at both pH 3 and 8. Most transformation products were the result of the opening of the imidazole ring after breaking caffeines N9C8 double bond.

Coagulation-fenton coupled treatment for ecotoxicity reduction in highly polluted industrial wastewater.

A coupled coagulation-Fenton process was applied for the treatment of cosmetic industry effluents. In a first step, FeSO(4) was used as coagulant and the non-precipitated Fe(2+) remaining in dissolution was used as catalyst in the further Fenton process. In the coagulation process a huge decrease in total organic carbon (TOC) was achieved, but the high concentration of phenol derivatives was not diminished. The decrease in TOC in the coagulation step significantly reduces the amount of H(2)O(2) required in the Fenton process for phenol depletion. The coupled process, using a H(2)O(2) dose of only 2 g l(-1), reduced TOC and total phenol to values lower than 40 and 0.10 mg l(-1), respectively. The short reaction period (less than 15 min) in TOC and phenol degradation bodes well for improving treatment in a continuous regime. The combination of both processes significantly reduced the ecotoxicity of raw effluent and markedly increased its biodegradability, thus allowing easier treatment by the conventional biological units in conventional sewage treatment plants (STPs).

Ozone-Based Technologies in Water and Wastewater Treatment

Ozone is a strong oxidant that can be used in the potabilization of surface or ground water as well as in wastewater treatment to remove microorganisms, inorganic ions and organic pollutants. The oldest use of ozone is as a biocide in drinking water potabilization. The integral ozone exposure required for a given degree of disinfection can be calculated from the deactivation kinetic constant of the microorganism. Ozone removes iron, manganese and arsenic from water by oxidation to an insoluble form that is further separated by filtration. Both processes require ozone in molecular form, but the removal of organic pollutants that are refractory to other treatments can be possible only by exploiting the indirect radical reactions that take place during ozonation. Ozone decomposes in water, especially when hydrogen peroxide is present, to yield the hydroxyl radical, the strongest oxidizer available in water treatment. Models for the ozonation process are required to adjust the ozone dosing to the desired degree of removal of a given pollutant or an aggregate measure of pollution. Mineralization, defined as the removal of organic carbon, has been accomplished in wastewaters from urban and domestic treatment plants. The results show that the logarithmic decrease of TOC as a function of the integral ozone exposure usually presents two zones with different kinetic parameters. Among advanced oxidation processes, a promising alternative currently under development is the use of ozone in combination with solid catalysts. The mechanism of catalytic ozonation is not clear, but in the case of metal oxides, the adsorption of ozone or organic compounds on Lewis acid sites is only possible near the point of zero charge of the surface. Activated carbon seems to behave as an initiator of ozone decomposition, a role that may also occur with other types of catalysts. Some results on the mineralization of water with the drugs naproxen (non-steroidal anti-inflammatory) and carbamazepine (anticonvulsant) are presented using titanium dioxide as catalyst.

Continuous ozonation treatment of ofloxacin: transformation products, water matrix effect and aquatic toxicity.

The continuous ozonation of the antibiotic ofloxacin (OFX) has been performed using a synthetic water matrix and in a sewage treatment plant (STP) effluent. The aim was to study the effect of the water matrix on the ozonation with particular emphasis on the aquatic toxicity of treated water. OFX was completely removed in both water matrices, although the amount of ozone consumed for its depletion was strongly matrix-dependent. The extent of mineralization was limited and a number of intermediate transformation products (TPs) appeared, twelve of which could be identified. OFX reaction pathway includes the degradation of piperazinyl and quinolone moieties. The further oxidation of TPs gave rise to the formation and accumulation of carboxylic acids, aldehydes, nitrogen-containing organic compounds and inorganic ions. Aquatic toxicity of treated mixtures was assessed using four standard species: the bacteria Vibrio fischeri and Pseudomonas putida as target organisms and the algae Pseudokirchneriella subcapitata and the protozoan Tetrahymena thermophila as non-target organisms. OFX was toxic for the bacteria and the microalgae at the spiked concentration in untreated water. However, the continuous ozonation at the upper operational limit removed its toxic effects. T. thermophila was not affected by OFX, but was sensitive to STP effluent.

Environmental optimization of continuous flow ozonation for urban wastewater reclamation

Wastewater samples from the secondary clarifier of two treatment plants were spiked in the microgram-to-tens-of-microgram per liter range with diuron (herbicide), ibuprofen and diclofenac (anti-inflammatory drugs), sulfamethoxazole and erythromycin (antibiotics), bezafibrate and gemfibrozil (lipid regulators), atenolol (β-blocker), carbamazepine (anti-epileptic), hydrochlorothiazide (diuretic), caffeine (stimulant) and N-acetyl-4-amino-antipiryne, a metabolite of the antipyretic drug dypirone. They were subsequently ozonated in continuous flow using 1.2L lab-scale bubble columns. The concentration of all spiking compounds was monitored in the outlet stream. The effects of varying ozone input, expressed as energy per unit volume, and water flow rate, and of using single or double column were studied in relation to the efficiency of ozone usage and the ratio of pollutant depletion. The ozone dosage required to treat both wastewaters with pollutant depletion of >90% was in the 5.5-8.5 mg/L range with ozone efficiencies greater than 80% depending on the type of wastewater and the operating conditions. This represented 100-200 mol of ozone transferred per mole of pollutant removed. Direct and indirect environmental impacts of ozonation were assessed according to Life Cycle Assessment, a technique that helped identify the most effective treatments in terms of potential toxicity reduction, as well as of toxicity reduction per unit mass of greenhouse-gas emissions, which were used as an indicator of environmental efficiency. A trade-off between environmental effectiveness (toxicity reduction) and greenhouse-gas emissions was observed since maximizing toxicity removal led to higher greenhouse-gas emissions, due to the latters relatively high ozone requirements. Also, there is an environmental trade-off between effectiveness and efficiency. Our results indicate that an efficient use of ozone was not compatible with a full pollutant removal.

Electrospun cellulose acetate composites containing supported metal nanoparticles for antifungal membranes

Electrospun cellulose acetate composites containing silver and copper nanoparticles supported in sepiolite and mesoporous silica were prepared and tested as fungistatic membranes against the fungus Aspergillus niger. The nanoparticles were in the 3-50nm range for sepiolite supported materials and limited by the size of mesopores (5-8nm) in the case of mesoporous silica. Sepiolite and silica were well dispersed within the fibers, with larger aggregates in the micrometer range, and allowed a controlled release of metals to create a fungistatic environment. The effect was assessed using digital image analysis to evaluate fungal growth rate and fluorescence readings using a viability stain. The results showed that silver and copper nanomaterials significantly impaired the growth of fungi when the spores were incubated either in direct contact with particles or included in cellulose acetate composite membranes. The fungistatic effect took place on germinating spores before hyphae growth conidiophore formation. After 24h the cultures were separated from fungistatic materials and showed growth impairment only due to the prior exposure. Growth reduction was important for all the particles and membranes with respect to non-exposed controls. The effect of copper and silver loaded materials was not significantly different from each other with average reductions around 70% for bare particles and 50% for membranes. Copper on sepiolite was particularly efficient with a decrease of metabolic activity of up to 80% with respect to controls. Copper materials induced rapid maturation and conidiation with fungi splitting in sets of subcolonies. Metal-loaded nanomaterials acted as reservoirs for the controlled release of metals. The amount of silver or copper released daily by composite membranes represented roughly 1% of their total load of metals. Supported nanomaterials encapsulated in nanofibers allow formulating active membranes with high antifungal performance at the same time minimizing the risk of nanoparticle release into the environment.

Kinetics and Mechanism of Catalytic Ozonation of Aqueous Pollutants on Metal Oxide Catalysts

The catalytic ozonation of fenofibric and clofibric acids and the herbicides atrazine and linuron was studied using titanium dioxide, alumina, and manganese oxide supported on activated alumina and on silica SBA-15. The organics studied did not adsorb significantly either in wastewater or in phosphate-buffered water. The catalysts did not modify the rate of the hydroxyl-mediated ozonation with respect to the homogeneous value. The mode of action of metal oxide catalysts would be an enhanced generation of oxidant species from the catalytic decomposition of ozone. All catalysts increased the efficiency in the production of hydroxyl radicals from ozone.