Chemically and thermally activated persulfate for theophylline degradation and application to pharmaceutical factory effluent.

Degradation of PPCPs by AOPs has gained major interest in the past decade. In this work, theophylline (TP) oxidation was studied in thermally (TAP) and chemically (CAP) activated persulfate systems, separately and in combination (TCAP). For [TP]0 = 10 mg L-1, (i) TAP resulted in 60% TP degradation at [PS]0 = 5 mM and T = 60 °C after 60 min of reaction and (ii) CAP showed slight degradation at room temperature; however, (iii) TCAP resulted in complete TP degradation for [PS]0 = [Fe2+]0 = 2 mM at T = 60 °C following a pseudo-first order reaction rate with calculated k obs = 5.6 (±0.4) × 10-2 min-1. In the TCAP system, the [PS]0 : [Fe2+]0 ratio of 1 : 1 presented the best results. A positive correlation was obtained between the TP degradation rate and increasing temperature and [PS]0, and a negative correlation was obtained with increasing pH. Both chloride and humic acid inhibited the degradation process, while nitrates enhanced it. TP dissolved in spring, sea and waste water simulating real effluents showed lower degradation rates than in DI water. Waste water caused the highest inhibition (k obs = 2.6 (±0.6) × 10-4 min-1). Finally, the TCAP system was tested on a real factory effluent highly charged with TP, e.g. [TP]0 = 160 mg L-1, with successful degradation under the conditions of 60 °C and [PS]0 = [Fe2+]0 = 50 mM.

A rapid and economical method for the quantification of hydrogen peroxide (H2O2) using a modified HPLC apparatus.

H2O2 is one of the most commonly used oxidants for the degradation of recalcitrant organic contaminants in advanced oxidation processes (AOPs). However, most research aiming to optimize AOPs is missing the monitoring of the remaining H2O2, an important parameter to assess the efficiency of the process. In this work, a novel method for [H2O2] quantification was developed using simple modifications of an HPLC-DAD setup that is available in most analytical chemistry laboratories. The modifications include the use of acidified potassium iodide solution as mobile phase and replacing the reverse phase column with a series of capillary columns. This instrument configuration allowed also the quantification of organic contaminants using the same H2O2 containing sample. The method's LOD and LOQ were calculated to be as low as 8.29 × 10-4 mM and 2.76 × 10-3 mM, respectively with an LDR range of 0.01-150 mM. The cost per analysis ranged between 0.8 and 1.8 USD cents depending on the concentration tested. This analytical method was validated by a statistical comparison to a well-known titrimetric method that is commonly used for H2O2 quantification. It was also tested using standards prepared in natural matrices such as spring and seawater, and in media containing high concentration of several spectator species such as chlorides, bicarbonates, humic acids, fumaric acids and micro pollutants. The method showed excellent robustness by maintaining high regression coefficient and excellent sensitivity in all calibration curves regardless of the matrix content.

Data for persulfate activation by UV light to degrade theophylline in a water effluent.

The aim of this study was to degrade theophylline (TP) drug in a pharmaceutical effluent solution utilizing persulfate (PS). A simulated and a real effluent solution were used, with different conditions tested to optimize the degradation process. HPLC analyses and a modified-HPLC method were used to track concentrations of TP and PS respectively in the treatment process. Experiments were done in triplicates and treated data is presented as graphs. A detailed analyses of this study can be found in the article "Degradation of theophylline in a UV254/PS system: matrix effect and application to a factory effluent" [1] published in Chemical Engineering Journal.

Rapid removal of flutriafol in water by zero-valent iron powder.

A study of the effect of zero-valent iron (ZVI) powder is carried out for the first time on the degradation of flutriafol ((RS)-2,4'-difluoro-alpha-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, C(16)H(13)F(2)N(3)O), a bifluorinated soil and water persistent triazole pesticide using a laboratory scale device consisting of a 20 ml pyrex serum vials fixed to a Vortex agitator. Different amounts of ZVI powder (10-50 g l(-1)) at pH 6.6 and room temperature were investigated. Experiments showed an observed degradation rate k(obs) directly proportional to the surface of contact of flutriafol with ZVI. Flutriafol degradation reactions demonstrated first order kinetic with a half-live of about 10.8+/-0.5 min and 3.6+/-0.2 min when experiments were conducted at [ZVI]=10 g l(-1) into oxygenated and anoxic solutions, respectively. Three analytical techniques were employed to monitor flutriafol degradation and to understand solution and by-products behaviors: (1) A UV-Vis spectrophotometer; (2) a high performance liquid chromatography (HPLC) coupled with a photo diode array (PDA) and fluorescence detectors; (3) a similar HPLC coupled with a PDA and a mass spectrometer detectors equipped with an atmospheric pressure photoionization source. Results showed a complete disappearance of flutriafol after 20 min of contact with ZVI, the loss of fluorescence properties of the final by-products, the defluorination of the triazole pesticide via hydroxylation reaction and finally the hydrogenation of the triazole ring.

Catalytic degradation of chlorothalonil in water using bimetallic iron-based systems.

Modified zero valent iron (MZVI) was used to study the transformation of a chlorothalonil (CLT) solution and the variation of the observed degradation rate of the reduction reactions. This was carried out when transition metals e.g. Pd, Cu and Co plated on the surface of micrometric iron particles (< 150 microm) were used as reducing catalytic agents for pesticide removal. Reactions were undertaken under both oxic and anoxic conditions in the presence and the absence of a phosphate buffer solution (PBS). Results of batch studies in nitrogen sparged solutions revealed that incomplete slow dechlorination merely occurred with zero valent iron (ZVI), however, complete rapid dechlorination reactions took place with MZVI especially Fe/Pd. Dechlorination was depicted by studying UV absorbance and MS spectra of CLT and all corresponding by-products. Typical blue shifts (deltalambda = 4-6 nm/chlorine atom) were observed at the same time as chlorine cluster isotopes disappeared. After the plating process, metal loading was controlled by analyzing the remaining metal in the solution by atomic absorption spectroscopy. Experiments showed that CLT degradation mechanism is faster in nitrogen sparged solutions in the absence of PBS. Time needed for complete removal of 2.08 +/- 0.19 microM CLT solution was about 2 h when experiments were conducted with ZVI (t1/2 = 15.0 min) and about 10 min when the reaction was carried out under the same conditions with Fe/Pd 1% (t1/2 = 1.0 min). Degradation rates for all bimetallic systems were determined showing that Pd is the more exciting catalytic transition metal followed by Cu and Co. Furthermore, MZVI method showed obvious advantage to traditional CLT treatment methods.

Rapid quantification of persulfate in aqueous systems using a modified HPLC unit.

Existing analytical techniques used for the quantification of persulfate (PS) in water mostly rely on polarography, reductometry or spectrophotometry. Although acceptable to a certain extent, these methods did not satisfy environmental chemists seeking rapid, reproducible and accurate quantification of PS upon the application of ISCO and AOPs technologies. Accordingly, a novel flow injection/spectroscopy analytical technique is developed via the use of an HPLC coupled to bypass capillary columns and a DAD detector. Special HPLC configuration uses concentrated KI solution as mobile phase to readily reduce PS present in the sample. The reaction takes place inside the capillary columns, under moderate pressure facilitating the production of Iodine suspension (I2), to yield finally the formation of the Triiodide anion (I3-) in the presence of an excess of I-. Triiodide absorbs at 352nm which minimizes interferences from other organic contaminants (OCs). The method was validated by comparison to traditional PS quantification methods and tested on several environmental samples. The new method proved its superiority in terms of time requirement, labor need, material consumption, sample volume and simplicity. It eliminates the inconsistency present in other idiometric methods which is caused by the delay between the PS/I- reaction and I3- measurement. The obtained LDR extends from 0.075 to 300mmolL-1 with a LOD of 6.6 × 10-3mmol L-1 and a LOQ of 2.20 × 10-2mmolL-1. The method is successfully implemented in our laboratory to rapidly and automatically monitor the variation in the concentration of PS used in different projects, which facilitates the rapid determination of the reaction stoichiometric efficiency (RSE) of the oxidation reaction, a key factor toward the optimization of the mineralization process and its sustainability.

The fate of selected pharmaceuticals in solar stills: Transfer, thermal degradation or photolysis?

The increase in demand for, and disposal of, pharmaceuticals, positively correlated with the growing human population, has led to the emergence of contaminants with high environmental and health impacts. Several developing countries that endure problems related to water sufficiency and/or quality resort to the use solar stills as an affordable water treatment method. This research is aimed at investigating the fate of five chemically distinct pharmaceuticals that might pervade solar stills; ibuprofen (IBU), diclofenac (DCF), carbamazepine (CBZ), ampicillin (AMP) and naproxen (NPX). The experiments were conducted under three conditions. The first condition studied the combined effect of temperature and light in simulated field-test-scale solar stills. The effect of temperature as a sole variable was investigated in the second while the third condition studied the effect of light only via concentrated solar power (CSP). Results show that distillates from solar stills did not contain the parent compounds for four out of the five pharmaceuticals. IBU was the only pharmaceutical that showed a transfer via vapor into the distillate with the highest recorded transfer percentage of 2.1% at 50°C when subjected to temperature alone and 0.6% under the combined effect of temperature and light. In the case of NPX and DCF, the parent compounds did not undergo transfer into the distillate phase; however their degradation by-products did. In addition, the results also showed that in the case of NPX, IBU and CBZ both high temperatures and sunlight combined were required to attain noticeable degradation. CSP accelerated the degradation of DCF, NPX and IBU with a three-minutes-degradation percentage of 44%, 13% and 2% respectively.

Aqueous removal of diclofenac by plated elemental iron: bimetallic systems.

The aqueous removal of diclofenac (DF) by micrometric iron particles (Fe(0)) and amended Fe(0) (Me(0)(Fe(0))) under oxic and anoxic conditions was investigated. Bimetallic systems were obtained by plating the surface of Fe with Co, Cu, Ir, Ni, Pd and Sn. Experimental results confirmed the superiority of (Me(0)(Fe(0))) for DF removal except for IrFe (oxic) and SnFe (anoxic). Under anoxic conditions, Pd was by far the most efficient plating element followed by Ir, Ni, Cu, Co and Sn. However, under oxic conditions, Pd and Cu showed almost the same efficiency in removing DF followed by Ni, Co, Sn and Ir. Oxidative and reductive DF transformation products were identified under oxic and anoxic conditions respectively. In some systems (e.g. CoFe and SnFe oxic/anoxic; PdFe oxic; NiFe anoxic), no transformation products could be detected. This was ascribed to the nature of the plating element and its impact on the process of the formation of metal corrosion products (MCPs). MCPs are known for their high potential to strongly adsorb, bond, sequestrate and enmesh both the original contaminant and its reaction products. Obtained results corroborate the universal validity of the view, that aqueous contaminants are basically removed by adsorption and co-precipitation.

Investigating the mechanism of clofibric acid removal in Fe(0)/H2O systems.

Since the introduction of iron wall technology, the inherent relationship between contaminant removal and iron corrosion has been mostly attributed to electron transfer from the metal body (direct reduction). This thermodynamically founded premise has failed to explain several experimental facts. Recently, a new concept considering adsorption and co-precipitation as fundamental contaminant removal mechanisms was introduced. This consistent concept has faced very skeptic views and necessarily needs experimental validation. The present work was the first independent attempt to validate the new concept using clofibric acid (CLO) as model compound. For this purpose, a powdered Fe(0) material (Fe(0)) was used in CLO removal experiments under various experimental conditions. Additional experiments were performed with plated Fe(0) (mFe(0): Fe(0)/Pd(0), Fe(0)/Ni(0)) to support the discussion of removal mechanism. Main investigated experimental variables included: abundance of O(2), abundance of iron corrosion products (ICPs) and shaking operations. Results corroborated the concept that quantitative contaminant removal in Fe(0)/H(2)O systems occurs within the oxide-film in the vicinity of Fe(0). Additionally, mixing type and shaking intensity significantly influenced the extent of CLO removal. More importantly, HPLC/MS revealed that the identity of reaction products depends on the extent of iron corrosion or the abundance of ICPs. The investigation of the CLO/Fe(0)/H(2)O system disproved the popular view that direct reduction mediates contaminant removal in the presence of Fe(0).

Reductive destruction and decontamination of aqueous solutions of chlorinated antimicrobial agent using bimetallic systems.

Palladium, ruthenium and silver were investigated as catalysts for the dechlorination of dichlorophen (DCP, 2,2'-methylenebis(4-chlorophenol)), an antimicrobial and anthelmintic agent largely used as algicide, fungicide and bactericide. Experiments were undertaken under oxic and anoxic conditions for experimental durations up to 180 min (3h). The anoxic conditions were achieved by purging the solutions with nitrogen gas. Reactions were performed in a 12+/-0.5 mg L(-1) DCP solution (V=20 mL) using 0.8 g of Fe(0) (40 g L(-1)). Along with micrometric Fe(0), five Fe(0)-plated systems were investigated: Pd (1%), Ru (0.01%), Ru (0.1%), Ru (1%) and Ag (1%). Metal plating was controlled by atomic absorption spectroscopy. DCP degradation was monitored using: (i) two HPLC devices, (ii) ion chromatography, (iii) UV and fluorescence spectrophotometry. Results indicated: (i) total dechlorination with Fe/Pd, (ii) partial dechlorination (40%) with Fe/Ru, and no reaction with Fe/Ag. DCP is vanished completely after 90 min of contact with Fe/Pd following a first order kinetic. The observed degradation rate k(obs) was about (3.98+/-0.10)x10(-2)min(-1), the calculated half-life t(1/2) about 17.4+/-0.9 min and a t(50) about 10.1+/-0.5 min. A DCP degradation pathway map was also proposed.

Antibiotic removal from water: elimination of amoxicillin and ampicillin by microscale and nanoscale iron particles.

Zerovalent iron powder (ZVI or Fe(0)) and nanoparticulate ZVI (nZVI or nFe(0)) are proposed as cost-effective materials for the removal of aqueous antibiotics. Results showed complete removal of Amoxicillin (AMX) and Ampicillin (AMP) upon contact with Fe(0) and nFe(0). Antibiotics removal was attributed to three different mechanisms: (i) a rapid rupture of the beta-lactam ring (reduction), (ii) an adsorption of AMX and AMP onto iron corrosion products and (iii) sequestration of AMX and AMP in the matrix of precipitating iron hydroxides (co-precipitation with iron corrosion products). Kinetic studies demonstrated that AMP and AMX (20 mg L(-1)) undergo first-order decay with half-lives of about 60.3+/-3.1 and 43.5+/-2.1 min respectively after contact with ZVI under oxic conditions. In contrast, reactions under anoxic conditions demonstrated better degradation with t(1/2) of about 11.5+/-0.6 and 11.2+/-0.6 min for AMP and AMX respectively. NaCl additions accelerated Fe(0) consumption, shortening the service life of Fe(0) treatment systems.

Use of FTIR spectroscopy coupled with ATR for the determination of atmospheric compounds.

Attenuated total reflection Fourier transformed infrared spectroscopy (ATR-FTIR) can be successfully used for the quantitative determination of small amounts of pollutants like the organic fraction of aerosols. The relation between sample concentration and reflectance is described by the Kubelka-Munk equation and was found to be linearly proportional to the absorption band of some functional group. Several parameters like the matter of solid matrix, the cleaning of the sampling support, the treatment of reflectance spectra and the base line correction considerably influenced the reflectance spectra and facilitated data interpretations. The feasibility of the ATR-FTIR was evaluated by the monitoring of specific organic group bands on filters collected in the French cities of Grenoble and Clermont-Ferrand. We have obtained for hydroxyl group a calibration curve by plotting the relative intensity of reflectance versus the concentration. The linearity was obtained for OH from 1x10(-1) to 1x10(0)molL(-1) with r(2)=0.9959. We can consider that for a direct measurement of the intensity of reflectance, it is possible to perform quantitative ATR-FTIR organic group analysis.