Ozone Quantification by Selected Ion Flow Tube Mass Spectrometry: Influence of Humidity and Manufacturing Gas of Ozone Generator.

The quantification of ozone by SIFT-MS was investigated in conditions suitable with an industrial emission context (high ozone demand, dry air/oxygen as the manufacturing gas of the ozone generator, and high humidity levels beyond saturation at room conditions). Ozone reacts with four negative precursor ions available in the SIFT-MS device (NO2-, O2-, HO-, and O-), each precursor ion having its specific domain of linearity. For a high ozone concentration range, only NO2- and O2- have resulted in a linear behavior (between 1 and 100 ppmv of O3 for NO2-, between 1 and 50 ppmv of O3 for O2-). No water interference was identified during ozone measurements by SIFT-MS using NO2- and O2- precursor ions, even with extreme humidity levels. The presence of nitrogen oxide contaminants (due to the use of dry air as the manufacturing gas of the ozone generator) affected the ozone quantification by SIFT-MS. It is critical for NO2- precursor ions, whose rate constant varied as a function of NO2 concentrations. With O2- precursor ion, ozone was successfully measured in the presence of nitrogen oxides; however, the secondary chemistry must be taken into account.

Aldehydes gas ozonation monitoring: Interest of SIFT/MS versus GC/FID.

Two analytical techniques - online Gas Chromatography coupled with Flame Ionization Detector (often used method for VOCs monitoring) versus Selected Ion Flow Tube coupled with Mass Spectrometry (a more recent technique based on direct mass spectrometry) - were compared in association to an ozone-based gas treatment. Selecting aldehydes as the representative VOCs, their concentrations were monitored during ozonation experiments by both techniques in parallel. Contradictory results were obtained in the presence of ozone. Aldehydes were up to 90% removed due to a reaction with ozone according to GC/FID analysis, whereas with SIFT/MS, aldehydes concentration remained at the same level during the experiments regardless of the ozone presence. In addition, it was demonstrated that the apparent aldehydes removal was affected by GC injector temperature, varying from 90% (when it was at 250 °C) to 60% (at 100 °C). Meanwhile, even when the ozonation reactor was heated to 100 °C, no aldehydes conversion was evidenced by SIFT/MS, suggesting that the GC injector temperature was not the only interference-causing parameter. The ozone-aldehyde reaction is probably catalyzed by some material of GC injector and/or column. An ozone-GC interference was therefore confirmed, making unsuitable the use of GC/FID with silicone stationary phase to monitor aldehydes in presence of high concentrations of ozone (at least 50 ppmv). On the other hand, SIFT/MS was validated as a reliable technique, which can be employed in order to measure VOCs concentrations in ozonation processes.

Fixed-bed adsorption of toluene on high silica zeolites: experiments and mathematical modelling using LDF approximation and a multisite model.

The adsorption of toluene (TOL) as a target volatile organic compound has been studied experimentally and modelled on various hydrophobic zeolites: Faujasite (FAU), ZSM-5 (Z) and Mordenite (MOR). The influence of the nature of the compensating cation (H+ or Na+) has also been investigated for ZSM-5 zeolite, which is known to possess three kinds of adsorption sites (sinusoidal channels, straight channels and intersections). Type I isotherms observed on FAU, Na-Z and MOR fitted well with the Langmuir model. A deviation from a type I isotherm was observed for H-Z, because of the structure of this zeolite. The Successive Langmuir Model was more successful to fit the 'bump' of the experimental curve than the Double Langmuir. Classical shapes were found for MOR, FAU and Na-Z breakthrough curves that were fitted with good accuracy using the Linear Driving Force (LDF) approximation. In the case of H-Z, a change of profile was observed during the dynamic adsorption and the differences seen between the Na-Z and H-Z behaviours were explained by the strong interactions between Na+ and adsorbed TOL at the intersection sites. The Na+ cations prevented reorientation of TOL molecules at the intersection and thereby avoided the filling of the sinusoidal channel segments. Thus, a specific model was developed for fitting the breakthrough curve of H-Z. The model developed took into account these two types of adsorption sites with the overall uptake for each site being given by an LDF approximation.

Transformation characteristics of organic pollutants in Fered-Fenton process for dry-spun acrylic fiber wastewater treatment.

The Fered-Fenton process using Ti sheet as cathode and RuO2/Ti as anode was employed for the pretreatment of dry-spun acrylic fiber manufacturing wastewater. The effects of feeding mode and concentration of H2O2 on chemical oxygen demand (COD) removal efficiency as well as the biodegradability variation during the Fered-Fenton process were investigated. The feeding mode of H2O2 had significant influence on COD removal efficiency: the removal efficiency was 44.8% if all the 60.0 mM H2O2 was fed at once, while it could reach 54.1% if the total H2O2 was divided into six portions and fed six times. The biochemical oxygen demand/COD ratio increased from 0.29 to above 0.68 after 180 min treatment. The transformation characteristics of organic pollutants during the Fered-Fenton process were evaluated by using gas chromatography-mass spectrometry (GC-MS), Fourier transform infrared spectroscopy (FTIR) and fluorescence excitation-emission matrix (EEM) spectroscopy. Most of the refractory organic pollutants with aromatic structure or large molecular weight were decomposed during the Fered-Fenton process.

Ion chromatography as highly suitable method for rapid and accurate determination of antibiotic fosfomycin in pharmaceutical wastewater.

A rapid and accurate ion chromatography (IC) method (limit of detection as low as 0.06 mg L(-1)) for fosfomycin concentration determination in pharmaceutical industrial wastewater was developed. This method was compared with the performance of high performance liquid chromatography determination (with a high detection limit of 96.0 mg L(-1)) and ultraviolet spectrometry after reacting with alizarin (difficult to perform in colored solutions). The accuracy of the IC method was established in the linear range of 1.0-15.0 mg L(-1) and a linear correlation was found with a correlation coefficient of 0.9998. The recoveries of fosfomycin from industrial pharmaceutical wastewater at spiking concentrations of 2.0, 5.0 and 8.0 mg L(-1) ranged from 81.91 to 94.74%, with a relative standard deviation (RSD) from 1 to 4%. The recoveries of effluent from a sequencing batch reactor treated fosfomycin with activated sludge at spiking concentrations of 5.0, 8.0, 10.0 mg L(-1) ranging from 98.25 to 99.91%, with a RSD from 1 to 2%. The developed IC procedure provided a rapid, reliable and sensitive method for the determination of fosfomycin concentration in industrial pharmaceutical wastewater and samples containing complex components.

Determination of struvite crystallization mechanisms in urine using turbidity measurement.

Sanitation improvement in developing countries could be achieved through wastewater treatment processes. Nowadays alternative concepts such as urine separate collection are being developed. These processes would be an efficient way to reduce pollution of wastewater while recovering nutrients, especially phosphorus, which are lost in current wastewater treatment methods. The precipitation of struvite (MgNH(4)PO(4)∙6H(2)O) from urine is an efficient process yielding more than 98% phosphorus recovery with very high reaction rates. The work presented here aims to determine the kinetics and mechanisms of struvite precipitation in order to supply data for the design of efficient urine treatment processes. A methodology coupling the resolution of the population balance equation to turbidity measurement was developed, and batch experiments with synthetic and real urine were performed. The main mechanisms of struvite crystallization were identified as crystal growth and nucleation. A satisfactory approximation of the volumetric crystal size distribution was obtained. The study has shown the low influence on the crystallization process of natural organic matter contained in real urine. It has also highlighted the impact of operational parameters. Mixing conditions can create segregation and attrition which influence the nucleation rate, resulting in a change in crystals number, size, and thus final crystal size distribution (CSD). Moreover urine storage conditions can impact urea hydrolysis and lead to spontaneous struvite precipitation in the stock solution also influencing the final CSD. A few limits of the applied methodology and of the proposed modelling, due to these phenomena and to the turbidity measurement, are also discussed.

Removal of volatile organic compounds by heterogeneous ozonation on microporous synthetic alumina silicate.

A hybrid process combining adsorption and ozonation was examined as an alternative treatment for odorous volatile organic compounds (VOCs). Methyl ethyl ketone (MEK) was chosen to study the influence of operating parameters. Two synthetic aluminosilicates (faujasite-Y and ZSM-5) were tested for adsorption and reactivity with ozone. The adsorption equilibrium measurement on both adsorbents showed that adsorption performance depends on temperature but is not sensitive to relative humidity, due to the hydrophobic properties of the materials. Adsorbed VOCs were oxidized at low temperature when ozonated flow was sent to the reactor. Regeneration of the fixed bed was achieved at the same time, releasing mainly CO(2) and H(2)O. Intermediates of oxidation, such as 2,3-butanedione and acetic acid, were identified, leading to incomplete mineralization. The influence of concentration and humidity are discussed. Four successive cycles were tested: after the first adsorption/ozonation cycle, the adsorption efficiency was not affected during subsequent cycles. These results show that the same sample of adsorbent can be used in the treatment process for a long time. Ozonation regeneration is a promising process for VOC removal.

Ozonation of azo dyes (Orange II and Acid Red 27) in saline media.

Ozonation of two azo dyes was investigated in a monitored bench scale bubble column reactor (8.5-L), varying liquid media salt content (0, 1, 40 and 100 g L(-1), NaCl). In experiments with Orange II pH was varied (5, 7.5 and 9) but ozonation of Acid Red 27 was performed at pH 7.5. Ozone self-decomposition rate-constant increased with salt concentration. Color removal was very effective and fast achieved under all experimental conditions. For the two azo dyes tested, more than 98% of color intensity was removed in 30-min ozonation assays. However, only partial mineralization of azo dyes (45%-Orange II; 20%-Acid Red 27) was attained in such experiments. The degree of mineralization (TOC removal) was negatively affected by salt concentration. Biodegradation assays conducted by respirometry revealed the inhibitory effect of dye degradation products formed during ozonation.