Ricardo A. Torres-Palma

Ultrasonic treatment of water contaminated with ibuprofen

The application of ultrasound (US) waves for remediation of wastewater is an area of increasing interest and promising results. The aim of this paper is to evaluate the influence of several parameters of the US process on the degradation of ibuprofen (IBP), a widely used non-steroidal anti-inflammatory recalcitrant drug found in water. Applied US power, dissolved gas, pH and initial concentration of IBP were the parameters investigated under sonication (300 kHz). Ultrasound increased the degradation of IBP from 30 to 98% in 30 min. Initial rate of IBP degradation was evaluated in the range of 1.35 and 6.1 micromolL(-1)min(-1) for initial concentrations of 2 to 21 mgL(-1) or 9.7 micromolL(-1) to 101 micromolL(-1), respectively. Under air and oxygen the degradation rate of IBP was 4 micromolL(-1)min(-1) being higher than that when argon was used. The most favorable degradation pH was acidic media. Complete removal of IBP was achieved but some dissolved organic carbon (DOC) remained in solution showing that long-lived intermediates were recalcitrant to the US irradiation. However, chemical and biological oxygen demands (COD and BOD(5)) indicated that the process oxidize the ibuprofen compound to biodegradable substances removable in a subsequent biological step.

Degradation of the antibiotic oxolinic acid by photocatalysis with TiO2 in suspension

In the work presented here, a photocatalytic system using titanium Degussa P-25 in suspension was used to evaluate the degradation of 20mg L(-1) of antibiotic oxolinic acid (OA). The effects of catalyst load (0.2-1.5 g L(-1)) and pH (7.5-11) were evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, low pH values and 1.0 g L(-1) of TiO(2) favoured the efficiency of the process. Under optimal conditions the evolution of the substrate, chemical oxygen demand, dissolved organic carbon, toxicity and antimicrobial activity on Escherichia coli cultures were evaluated. The results indicate that, under optimal conditions, after 30 min, the TiO(2) photocatalytic system is able to eliminate both the substrate and the antimicrobial activity, and to reduce the toxicity of the solution by 60%. However, at the same time, ∼53% of both initial DOC and COD remain in solution. Thus, the photocatalytical system is able to transform the target compound into more oxidized by-products without antimicrobial activity and with a low toxicity. The study of OA by-products using liquid chromatography coupled with mass spectrometry, as well as the evaluation of OA degradation in acetonitrile media as solvent or in the presence of isopropanol and iodide suggest that the reaction is initiated by the photo-Kolbe reaction. Adsorption isotherm experiments in the dark indicated that under pH 7.5, adsorption corresponded to the Langmuir adsorption model, indicating the dependence of the reaction on an initial adsorption step.

Removal of polycyclic aromatic hydrocarbons in aqueous environment by chemical treatments: A review

Due to their carcinogenic, mutagenic and teratogenic potential, the removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous environment using physical, biological and chemical processes has been studied by several researchers. This paper reviews the current state of knowledge concerning PAHs including their physico-chemical properties, input sources, occurrence, adverse effects and conventional and alternative chemical processes applied for their removal from water. The mechanisms and reactions involved in each treatment method are reported, and the effects of various variables on the PAH degradation rate as well as the extent of degradation are also discussed. Extensive literature analysis has shown that an effective way to perform the conversion and mineralization of this type of substances is the application of advanced oxidation processes (AOPs). Furthermore, combined processes, particularly AOPs coupled with biological treatments, seem to be one of the best solutions for the treatment of effluents containing PAHs.

Enhanced sonochemical degradation of bisphenol-A by bicarbonate ions

Sonochemical elimination of organic pollutants can take place through two degradation pathways. Molecules with relatively large Henrys law constants will be incinerated inside the cavitation bubble, while nonvolatile molecules with low Henrys law constants will be oxidised by the OH(*) ejected from the bubble of cavitation. Taking bisphenol-A as a model pollutant, this study points out an alternate degradation route, mediated by bicarbonate ions, which is significant for the elimination of micro-pollutants at concentrations present in natural waters. In this process, OH(*) radicals react with bicarbonate ions to produce the carbonate radical, which, unlike the OH(*) radical, can migrate towards the bulk of the solution and therefore induce the degradation of the micro-pollutants present in the bulk solution. As a consequence, initial degradation rate is increased by a factor 3.2 at low concentration of bisphenol-A (0.022 micromol l(-1)) in presence of bicarbonate in water.

An innovative ultrasound, Fe2+ and TiO2 photoassisted process for bisphenol a mineralization

This paper explores the degradation of a model pollutant, bisphenol A, by an advanced oxidation process that combines sonolysis, Fe(2+), and TiO(2) in a photoassisted process. Experiments were done under saturated oxygen conditions. The effect of different Fe(2+) (0.56 and 5.6 mg/L) and TiO(2) (10 and 50 mg/L) concentrations was investigated on both the elimination and mineralization of the pollutant. A pronounced synergistic effect that led to the complete and rapid elimination of dissolved organic carbon (DOC) was observed even at low catalyst loadings. In this system, almost a complete removal of DOC (93%) was observed after 4 h using 10 and 5.6 mg/L of TiO(2) and Fe(2+), respectively, whereas at the same time, only 5, 6, and 22% of DOC was removed by an individual process alone (TiO(2) photocatalysis, ultrasound, and photo-Fenton, respectively). In this system, ultrasound has the principal role of eliminating the initial substrate and providing hydrogen peroxide for the photocatalytic systems, while photo-Fenton and TiO(2) photocatalysis are mainly responsible for the transformation of the intermediates in CO(2) and H(2)O. The role of H(2)O(2) generated from the sonochemical process is also discussed.

Solar photocatalitycal treatment of carbofuran at lab and pilot scale: effect of classical parameters, evaluation of the toxicity and analysis of organic by-products.

In this work the TiO(2) solar-photocatalytical degradation of the pesticide carbofuran (CBF) in water, at lab and pilot scale, was studied. At lab scale the evaluation of CBF concentration (14-282 μmol L(-1)) showed that the system followed a Langmuir-Hinshelwood kinetics type. TiO(2) concentration (0.05-2 g L(-1)) and initial pH (3-9) were also evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, initial pH 7.60 and 1.43 g L(-1) of TiO(2) favoured the efficiency of the process. Under optimal conditions the evolution of substrate, chemical oxygen demand, dissolved organic carbon, toxicity and organics by-products were evaluated. In the pilot scale tests, using direct sunlight, 55 mg L(-1) of CBF in a commercial formulation was eliminated after 420 min; while after 900 min of treatment 80% of toxicity (1/E(50) on Vibrium Fischeri), 80% of chemical oxygen demand and 60% of dissolved organic carbon were removed. The analysis and evolution of five CBF by-products, as well the evaluation of the treatment in the presence of isopropanol or using acetonitrile as a solvent suggest that the degradation is mainly carried out by OH radical attack. Finally, a schema depicting the main degradation pathway is proposed.

Ultrasonic degradation of acetaminophen in water: Effect of sonochemical parameters and water matrix

This paper deals about the sonochemical water treatment of acetaminophen (ACP, N-acetyl-p-aminophenol or paracetamol), one of the most popular pharmaceutical compounds found in natural and drinking waters. Effect of ultrasonic power (20-60 W), initial ACP concentration (33-1323 μmol L(-1)) and pH (3-12) were evaluated. High ultrasonic powers and, low and natural acidic pH values favored the efficiency of the treatment. Effect of initial substrate concentration showed that the Langmuir-type kinetic model fit well the ACP sonochemical degradation. The influence of organic compounds in the water matrix, at concentrations 10-fold higher than ACP, was also evaluated. The results indicated that only organic compounds having a higher value of the Henrys law constant than the substrate decrease the efficiency of the treatment. On the other hand, ACP degradation in mineral natural water showed to be strongly dependent of the initial substrate concentration. A positive matrix effect was observed at low ACP concentrations (1.65 μmol L(-1)), which was attributed to the presence of bicarbonate ion in solution. However, at relative high ACP concentrations a detrimental effect of matrix components was noticed. Finally, the results indicated that ultrasonic action is able to transform ACP in aliphatic organic compounds that could be subsequently eliminated in a biological system.

Experimental design approach applied to the elimination of crystal violet in water by electrocoagulation with Fe or Al electrodes.

An experimental design methodology was applied to evaluate the decolourization of crystal violet (CV) dye by electrocoagulation using iron or aluminium electrodes. The effects and interactions of four parameters, initial pH (3-9), current density (6-28 A m(-2)), substrate concentration (50-200 mg L(-1)) and supporting electrolyte concentration (284-1420 mg L(-1) of Na(2)SO(4)), were optimized and evaluated. Although the results using iron anodes were better than for aluminium, the effects and interactions of the studied parameters were quite similar. With a confidence level of 95%, initial pH and supporting electrolyte concentration showed limited effects on the removal rate of CV, whereas current density, pollutant concentration and the interaction of both were significant. Reduced models taking into account significant variables and interactions between variables have shown good correlations with the experimental results. Under optimal conditions, almost complete removal of CV and chemical oxygen demand were obtained after electrocoagulation for 5 and 30 min, using iron and aluminium electrodes, respectively. These results indicate that electrocoagulation with iron anodes is a rapid, economical and effective alternative to the complete removal of CV in waters. Evolutions of pH and residual iron or aluminium concentrations in solution are also discussed.

Sonochemical degradation of the pharmaceutical fluoxetine: Effect of parameters, organic and inorganic additives and combination with a biological system

Fluoxetine (FLX), one of the most widely used antidepressants in the world, is an emergent pollutant found in natural waters that causes disrupting effects on the endocrine systems of some aquatic species. This work explores the total elimination of FLX by sonochemical treatment coupled to a biological system. The biological process acting alone was shown to be unable to remove the pollutant, even under favourable conditions of pH and temperature. However, sonochemical treatment (600 kHz) was shown to be able to remove the pharmaceutical. Several parameters were evaluated for the ultrasound application: the applied power (20-60 W), dissolved gas (air, Ar and He), pH (3-11) and initial concentration of fluoxetine (2.9-162.0 μmol L(-1)). Additionally, the presence of organic (1-hexanol and 2-propanol) and inorganic (Fe(2+)) compounds in the water matrix and the degradation of FLX in a natural mineral water were evaluated. The sonochemical treatment readily eliminates FLX following a kinetic Langmuir. After 360 min of ultrasonic irradiation, 15% mineralization was achieved. Analysis of the biodegradability provided evidence that the sonochemical process transforms the pollutant into biodegradable substances, which can then be mineralized in a subsequent biological treatment.

Enhancement and inhibition effects of water matrices during the sonochemical degradation of the antibiotic dicloxacillin

The sonochemical degradation of dicloxacillin (DXC) was studied in both synthetic and natural waters. Degradation routes and the effect of experimental conditions such as pH, initial DXC concentration and ultrasonic power were evaluated. Experiments were carried out with a fixed frequency (600kHz). The best performances were achieved using acidic media (pH=3) and high power (60W). The degradation process showed pseudo-first order kinetics as described by the Okitsu model. To evaluate water matrix effects, substrate degradation, in the presence of Fe(2+) and organic compounds such as glucose and 2-propanol, was studied. A significant improvement was achieved with Fe(2+) (1.0mM). Inhibition of the degradation process was observed at a relatively high concentration of 2-propanol (4.9mM), while glucose did not show any effect. Natural water showed an interesting effect: for a low concentration of DXC (6.4μM), an improvement in the degradation process was observed, while at a higher concentration of DXC (0.43mM), degradation was inhibited. Additionally, the extent of degradation of the process was evaluated through the analysis of chemical oxygen demand (COD), antimicrobial activity, total organic carbon (TOC) and biochemical oxygen demand (BOD5). A 30% removal of COD was achieved after the treatment and no change in the TOC was observed. Antimicrobial activity was eliminated after 360min of ultrasonic treatment. After 480min of treatment, a biodegradable solution was obtained.