Antipyrine removal by TiO2 photocatalysis based on spinning disc reactor technology.

The photo-degradation of the emerging contaminant antipyrine (AP) was studied and optimized in a novel photocatalytic spinning disc reactor (SDR). A heterogeneous process (UV/H2O2/TiO2) was used. TiO2 was immobilized on the surface of a glass disc using a sol-gel method. A factorial design of experiments followed by a Neural Networks fitting allowed the optimal conditions to be determined for treating 50 mg/L of AP. Under these conditions (pH = 4; [H2O2]0 = 1500 mg/L; disc speed = 500 rpm; flowrate = 25 mL/s), AP was completely degraded in 120 min and regeneration of the disc allowed 10 cycles with no loss in efficiency. The value of the apparent volumetric rate constant was found to be 6.9·10-4 s-1 with no apparent mass transfer limitation. Based on the main intermediates identified, a mechanism is proposed for antipyrine photodegradation: Firstly, cleavage of the NN bond of penta-heterocycle leads to the formation of two aromatic acids and N-phenylpropanamide. An attack to the CN bond in the latter compound produces benzenamine. Finally, the phenyl ring of the aromatic intermediates are opened and molecular organic acids are formed.

Study of the intensification of solar photo-Fenton degradation of carbamazepine with ferrioxalate complexes and ultrasound.

The intensification of the solar photo-Fenton system with ferrioxalate photoactive complexes and ultrasound applied to the mineralization of 15mg/L carbamazepine aqueous solution (CBZ) was evaluated. The experiments were carried out in a solar compound parabolic collector (CPC) pilot plant reactor coupled to an ultrasonic processor. The dynamic behavior of hydroxyl radicals generated under the different studied reaction systems was discussed. The initial concentrations of hydrogen peroxide and ferrous/oxalic acid and pH were found to be the most significant variables (32.79%, 25.98% and 26.04%, respectively). Under the selected optimal conditions ([H2O2]0=150mg/L; [Fe2+]0=2.5mg/L/[(COOH)2]0=12.1mg/L; pH=5) CBZ was fully degraded after 5min and 80% of TOC was removed using a solar photo-Fenton system intensified with ferrioxalate (SPFF). However, no improvement in the mineralization using SPFF process combined with ultrasound was observed. More mild pH conditions could be used in the SPFF system if compared to the traditional photo-Fenton (pH 3) acidic systems. Finally, a possible reaction pathway for the mineralization of CBZ by the SPFF system was proposed and therein discussed.

Dynamic behavior of hydroxyl radical in sono-photo-Fenton mineralization of synthetic municipal wastewater effluent containing antipyrine.

The aim of this study was to examine the kinetics of the different mechanisms (radical pathway, photolysis, molecular reaction with H2O2 and reaction with ultrasonically generated oxidative species) involved in the homogeneous sono-photoFenton (US/UV/H2O2/Fe) mineralization of antipyrine present in a synthetic municipal wastewater effluent (ASMWE). The dynamic behavior of hydroxyl (HO) radical generation and consumption in mineralization reaction under different systems was investigated by measuring hydroxyl radical concentration during the reaction. The overall mineralization process was optimized using a Central-Composite Experimental Design (CCED) with four variables (initial concentrations of H2O2 and Fe(II), amplitude and pulse length). The response functions (pseudo-first order mineralization kinetic rate constants) were fitted using neural networks (NNs). Under the optimal conditions ([H2O2]o=500mgL-1, [Fe(II)]o=27mgL-1, Amplitude (%)=20andPulse length=1), the TOC removal was 79% in 50min. The radical reaction in the bulk solution was found be the primary mineralization pathway (94.8%), followed by photolysis (3.65%), direct reaction with H2O2 (0.86%), and reaction by ultrasonically generated oxidative species (0.64%). The role of the Fe catalyst on the radical reaction and the presence of refractory intermediates towards hydroxyl radical were also studied.

Sono-photo-degradation of carbamazepine in a thin falling film reactor: Operation costs in pilot plant.

The photo-Fenton degradation of carbamazepine (CBZ) assisted with ultrasound radiation (US/UV/H2O2/Fe) was tested in a lab thin film reactor allowing high TOC removals (89% in 35min). The synergism between the UV process and the sonolytic one was quantified as 55.2%. To test the applicability of this reactor for industrial purposes, the sono-photo-degradation of CBZ was also tested in a thin film pilot plant reactor and compared with a 28L UV-C conventional pilot plant and with a solar Collector Parabolic Compound (CPC). At a pilot plant scale, a US/UV/H2O2/Fe process reaching 60% of mineralization would cost 2.1 and 3.8€/m3 for the conventional and thin film plant respectively. The use of ultrasound (US) produces an extra generation of hydroxyl radicals, thus increasing the mineralization rate. In the solar process, electric consumption accounts for a maximum of 33% of total costs. Thus, for a TOC removal of 80%, the cost of this treatment is about 1.36€/m3. However, the efficiency of the solar installation decreases in cloudy days and cannot be used during night, so that a limited flow rate can be treated.

Application of activated persulfate for removal of intermediates from antipyrine wastewater degradation refractory towards hydroxyl radical.

Complete mineralisation of reaction intermediates refractory towards hydroxyl radical, generated from a previous ineffective degradation of urban wastewater containing antipyrine by HO-mediated sono-photo-Fenton reaction, has been attained using persulfate anions simultaneously activated by heat energy (thermally, ultrasound) and UV-C light. The SO4(-)-based mineralisation process enables another reaction pathway generating more easy degradable derivatives. The influences of the initial concentration of persulfate, ultrasound amplitude, temperature and the reaction time in the previous HO-based previous oxidation on the mineralisation degree were studied by using a Central-Composite Experimental Design. Under optimal conditions ([S2O8(2-)]o=1200mgL(-1), temperature=50°C, amplitude=10%, pH 2.8, HO-based reaction time=25min) practically complete degradation was achieved in approximately 120min. The contribution of HO and SO4(-) radicals in this system was also evaluated. The presence of chloride ion in urban wastewater can benefit the oxidation of acetate by sulfate radical. Results demonstrated that this activated persulfate-based oxidation system is a potential alternative to degrade intermediate compounds, which are refractory against hydroxyl radicals, generated in Advanced Oxidation Processes used to treat wastewater containing emerging contaminants such as antipyrine.

Effects of clenbuterol hydrochloride on pulmonary gas exchange and hemodynamics in anesthetized horses.

We evaluated the effects of clenbuterol HCl (0.8 micrograms/kg, of body weight, IV), a beta 2 agonist, on ventilation-perfusion matching and hemodynamic variables in anesthetized (by IV route), laterally recumbent horses. The multiple inert gas elimination technique was used to assess pulmonary gas exchange. Clenbuterol HCl induced a decrease in arterial oxygen tension (from 57.0 +/- 1.8 to 49.3 +/- 1.2 mm of Hg; mean +/- SEM) as a result of increased shunt fraction (from 6.6 +/- 2.1 to 14.4 +/- 3.1%) and ventilation to regions with high ventilation-perfusion ratios. In contrast, no changes in these variables were found in horses given sterile water. In horses given clenbuterol HCl, O2 consumption increased from 2.23 +/- 0.18 to 2.70 +/- 0.14 ml.min-1.kg-1, and respiratory exchange ratio decreased from 0.80 +/- 0.02 to 0.72 +/- 0.01. Respiratory exchange ratio and O2 consumption were not significantly modified in sterile water-treated (control) horses. Clenbuterol HCl administration was associated with increased cardiac index (from 57.4 +/- 4.0 to 84.2 +/- 6.3 ml.min-1.kg-1), decreased total peripheral vascular resistance (from 108.3 +/- 9.3 to 47.6 +/- 2.8 mm of Hg.s.kg.ml-1), and decreased pulmonary vascular resistance (from 31.3 +/- 3.8 to 13.6 +/- 0.7 mm of Hg.s.kg.ml-1). Our findings indicated that clenbuterol HCl may potentiate hypoxemia as a result of increased shunt fraction in horses anesthetized by the IV route, and caused changes in hemodynamic variables that were consistent with its ability to stimulate beta 2-adrenergic receptors.

Platelet count in deep saturation diving.

Platelet counts were measured in 10 divers during the course of 4 experimental deep dives (450 and 600 m) and different anticoagulants were tested. The use of sodium citrate as an anticoagulant was associated with artifactual thrombocytopenia, whereas ethylenediaminetetraacetic acid proved to be satisfactory. During one of the dives (450 m) the use of fluorocarbon to remove excess dissolved inert gas before decompression of the samples was systematically tested. Mean platelet count decreased from 272,600 +/- 29,400 mm-3 (mean +/- SD) on Day 7 (450 m) to 177,700 +/- 26,400 mm-3 on Day 12 (360 m). Platelet count had recovered to 209,900 +/- 20,700 mm-3 at the time of surfacing. Mean hematocrit (expressed in percent) increased from 44.7 +/- 2.2 predive to 59.4 +/- 2.0 on Day 7 (450 m) to 40.9 +/- 2.8 at the time of surfacing. These changes were statistically significant (P less than 0.05). Platelet counts on samples that had been degassed with fluorocarbon were not different from samples that had been decompressed without degassing.