Stephan Brosillon

Analysis and occurrence of odorous disinfection by-products from chlorination of amino acids in three different drinking water treatment plants and corresponding distribution networks.

Previous studies have established that odorous and stable chloraldimines are formed during amino acid chlorination in drinking water treatment. In order to identify at low level (10(-8) M) the presence of these odorous disinfection by-products in drinking water matrixes an analytical method was developed by using head space apparatus (HS) combined with a sorbent trap system linked to a GC with a mass spectrometer detector (HS/Trap/GC/MS). The analyses were carried out in three different drinking water supplies from the Paris area, during the four seasons. Free amino acids were monitored at the inlet of the plant. The odorous disinfection by-products were analyzed at the outlet of each drinking water treatment plant and the different distribution networks were connected to the corresponding plant. The results confirmed that the odorous chloraldimines are produced during chlorination of free amino acids in three different matrixes in different seasons throughout the year (N-chloroisobutaldimine; N-chloromethyl-2-butaldimine; N-chloromethyl-3-butaldimine (6-10 nM). The analytical method (HS/Trap/GC/MS) used to monitor odorous disinfection by-products appeared to be adapted for the detection of these by-products at nM level.

Integrated Process for Degradation of Amitrole in Wastewaters: Photocatalysis/Biodegradation

Preliminary studies highlight the positive effect of coupling photocatalysis and biological processes for the treatment of biorecalcitrant compounds. Before biological treatment, photocatalysis can be used as a pre-treatment process to increase pesticide biodegradability. Kinetics of amitrole biodegradation during cultures of Pseudomonas fluorescens was examined to ensure that the target compound was biorecalcitrant; its inhibitory effect justified a pre-oxidation. The biodegradation of cyanuric acid, one of the by-products resulting from photocatalyis of amitrole was confirmed. Pseudomonas fluorescens could metabolize this compound as a nitrogen source when a supplementary carbon source was added. The addition of supplementary carbon and nitrogen sources favoured growth and accordingly cyanuric acid degradation. Degradation yields (with TiO2 coated on cellulose fibers, 25 g.m-2) in the range 47% to 55% were obtained after 50h of irradiation for solutions of amitrole in the range concentrations between 70 to 6000 ppm. Between 10% and 34% of amitrole was mineralized to carbon dioxide. The production of ammonium and nitrate ions was negligible. An inhibition of TiO2 active sites was assumed to account for the weak mineralization. Identification of some of the intermediate by-products by LC-MS/MS shows negligible quantity of cyanuric acid. This work demonstrates that the hybrid process photocatalysis/bioremediation is a cost-effective promising solution for the treatment of wastewater containing biorecalcitrant compounds.

Study of photocatalytic degradation of tributyltin, dibutylin and monobutyltin in water and marine sediments

This study reports on the first assessment of the treatment of sediments contaminated by organotin compounds using heterogeneous photocatalysis. Photocatalysis of organotins in water was carried out under realistic concentration conditions (μgL(-1)). Degradation compounds were analyzed by GC-ICP-MS; a quasi-complete degradation of tributyltin (TBT) in water (99.8%) was achieved after 30min of photocatalytic treatment. The degradation by photolysis was about (10%) in the same conditions. For the first time decontamination of highly polluted marine sediments (certified reference material and harbor sediments) by photocatalysis proves that the use of UV and the production of hydroxyl radicals are an efficient way to treat organotins adsorbed onto marine sediment despite the complexity of the matrix. In sediment, TBT degradation yield ranged from 32% to 37% after only 2h of irradiation (TiO2-UV) and the by-products: dibutyltin (DBT) and monobutyltin (MBT) were degraded very rapidly in comparison with TBT. It was shown that during photocatalysis of organotins in sediments, the hydroxyl radical attack and photolysis are the two ways for the degradation of adsorbed TBT.

Integration of photocatalysis and biological treatment for azo dye removal--application to AR183.

The feasibility of coupling photocatalysis with biological treatment to treat effluents containing azo dyes was examined in this work. With this aim, the degradation of Acid Red 183 was investigated. The very low biodegradability of AR183 was confirmed beforehand by measuring the biological oxygen demand (BOD5). Photocatalysis experiments were carried out in a closed‐loop step photoreactor. The reactor walls were covered by TiO2 catalyst coated on non‐woven paper, and the effluent flowed over the photocatalyst as a thin falling film. The removal of the dye was 82.7% after 4 h, and a quasi‐complete decolorization (98.5%) was obtained for 10 h of irradiation (initial concentration 100 mg L−1). The decrease in concentration followed pseudo‐first‐order kinetics, with a constant k of 0.47 h−1. Mineralization and oxidation yields were 80% and 75%, respectively, after 10 h of pretreatment. Therefore, even if target compound oxidation occurs (COD removal), indicating a modification to the chemical structure, the concomitant high mineralization was not in favour of subsequent microbial growth. The BOD5 measurement confirmed the non‐biodegradability of the irradiated solution, which remained toxic since the EC50 decreased from 35 to 3 mg L−1. The proposed integrated process appeared, therefore, to be not relevant for the treatment of AR183. However, this result should be confirmed for other azo dyes.

Evidence of solute-solute interactions and cake enhanced concentration polarization during removal of pharmaceuticals from urban wastewater by nanofiltration.

The objective of this paper is to help understanding the distinctive influence of the matrix and of the flux decline (e.g. through the cake enhanced concentration polarization (CECP) phenomenon) on the removal mechanisms of four pharmaceutically active compounds (PhACs) from wastewater treatment plant (WWTP) effluent by nanofiltration (NF). PhACs which are commonly encountered in secondary treated effluent were spiked in various matrix (real and synthetic) to investigate the separate and synergetic effects of the organic and ionic environment on PhACs rejection by two commercial membranes (NF-90 and NF-270). With pure water, rejection of NF membranes is dependent on the type of PhACs and of the permeate flux variations. Then, it appeared that the rejection of PhACs by NF-90 was poorly influenced by the type of compounds, because of the prevalence of steric mechanisms, but rather influenced by permeate flux variations and thus to fouling. For this tight NF membrane, CECP impacts PhACs rejection at the start of filtration while after a dense cake is formed, it became enhanced. On the contrary, rejections of PhACs by the NF-270 were enhanced during the filtration of the real wastewater in comparison with spiked pure water. It appeared that for loose-NF membranes, PhACs rejection is mainly governed by solute-solute interactions (EfOM-compound association) or electrostatic membrane-solute interactions. Finally, it seems that calcium concentration of the effluent is a critical parameter for the rejection of PhACs as it alters both the availability of sites for PhACs association and the fouling layer density. Rejections of the NF-270 were negatively impacted in the presence of Ca2+. Such a study has practical implications for further understanding of the fate of trace organic compounds during nanofiltration of wastewater for reuse applications.

Oxidative photodegradation of herbicide fenuron in aqueous solution by natural iron oxide α-Fe2O3, influence of polycarboxylic acids

The photodegradation of the herbicide fenuron (1,1-dimethyl-3-phenylurea) by using a natural iron oxide (NIO), α-Fe2O3, in aqueous solution at acidic pH has been undertaken. The NIO was characterized by the Raman spectroscopy method. The degradation pathways and the formation of degradation products were studied. A high-pressure mercury lamp and sunlight were employed as light source. Fenuron photodegradation using NIO with oxalic acid followed the pseudo-first-order kinetics, the optimal experimental conditions were [oxalic acid]0 = 10−3 M and [NIO] = 0.1 g L−1 at pH 3. A UVA/NIO/oxalic acid system led to a low fenuron half-life (60 min). The results were even better when solar light is used (30 min). The variables studied were the doses of iron oxide, of carboxylic acids, the solution pH and the effect of sunlight irradiation. The effects of four carboxylic acids, oxalic, citric, tartaric and malic acids, on the fenuron photodegradation with NIO have been investigated, oxalic acid was the most effective carboxylic acid used at pH 3. A similar trend was observed for the removal of total organic carbon (TOC), 75% of TOC was removed. The analytical study showed many aromatic intermediates, short-chain carboxylic acids and inorganic ion.

Influence of volumetric reduction factor during ozonation of nanofiltration concentrates for wastewater reuse

Global population growth induces increased threat on drinking water resources. One way to address this environmental issue is to reuse water from wastewater treatment plant. The presence of pathogenic microorganisms and potentially toxic organic micropollutants does not allow a direct reuse of urban effluents. Membrane processes such reverse osmosis (RO) or nanofiltration (NF) can be considered to effectively eliminate these pollutants. The integration of membrane processes involves the production of concentrated retentates which require being disposed. To date, no treatment is set up to manage safely this pollution. This work focuses on the application of ozonation for the treatment of NF retentates in the framework of the wastewater reuse. Ozonation is a powerful oxidation process able to react and degrade a wide range of organic pollutants. Four pharmaceutical micropollutants were selected as target molecules: acetaminophen, carbamazepine, atenolol and diatrozic acid. This study highlighted that NF represents a viable alternative to the commonly used RO process ensuring high retention at much lower operating costs. Ozonation appears to be effective to degrade the most reactive pollutants toward molecular ozone but is limited for the reduction of refractory ozone pollutants due to the inhibition of the radical chain by the high content of organic matter in the retentates. The ozonation process appears to be a promising NF retentate treatment, but additional treatments after ozonation are required to lead to a zero liquid discharge treatment scheme.

The Reductive Dehydration of Cellulose by Solid/Gas Reaction with TiCl4 at Low Temperature: A Cheap, Simple, and Green Process for Preparing Anatase Nanoplates and TiO2/C Composites

Metal oxides and metal oxide/carbon composites are entering the development of new technologies and should therefore to be prepared by sustainable chemistry processes. Therefore, a new aspect of the reactivity of cellulose is presented through its solid/gas reaction with vapour of titanium(IV) chloride in anhydrous conditions at low temperature (80 °C). This reaction leads to two transformations both for cellulose and titanium(IV) chloride. A reductive dehydration of cellulose is seen at the lowest temperature ever reported and results in the formation of a carbonaceous fibrous solid as the only carbon-containing product. Simultaneously, the in situ generation of water leads to the formation of titanium dioxide with an unexpected nanoplate morphology (ca. 50 nm thickness) and a high photocatalytic activity. We present the evidence showing the evolution of the cellulose and the TiO2 nanostructure formation, along with its photocatalytic activity. This low-temperature process avoids any other reagents and is among the greenest processes for the preparation of anatase and also for TiO2 /carbon composites. The anisotropic morphology of TiO2 questions the role of the cellulose on the growing process of these nanoparticles.

Ozonation as a pretreatment process for nanofiltration brines: Monitoring of transformation products and toxicity evaluation

Considerable interest has been given to using nanofiltration (NF) in lieu of reverse osmosis for water reclamation schemes due to lower energy consumption, higher flux rates while ensuring good micropollutants rejection. The application NF results in the generation of a large concentrated waste stream. Treatment of the concentrate is a major hurdle for the implementation of membrane technologies since the concentrate is usually unusable due to a large pollutants content. This work focuses on the application of ozonation as pretreatment of urban NF concentrates, the generation of transformation products and their relative toxicity. Three pharmaceutical micropollutants largely encountered in water cycle were selected as target molecules: acetaminophen, carbamazepine and atenolol. Through accurate-mass Q-TOF LC-MS/MS analyses, more than twenty ozonation products were detected, structure proposals and formation pathways were elaborated. Attempts were made to understand the correlation between the transformation products and acute toxicity on Vibrio fischeri strain. It is the first time that an integrated study reported on the ozonation of pharmaceuticals in urban membrane concentrates, in terms of transformation products, kinetics, degradation mechanisms, as well as toxicity assessment.

Photo-oxidation of Tributyltin, Dibutyltin and Monobutyltin in Water and Marine Sediments

Abstract This study reports on the first assessment of the treatment of sediment contaminated by organotin compounds using homogenous and heterogeneous photocatalysis. Photo-Fenton and photocatalysis of low level (µg/L) organotins in water were carried out. A quasi-complete degradation of tributyltin (TBT) in water (99.8%) was reached after 30 and 7 min for photocatalytic and photo-Fenton treatment, respectively. For the first time decontamination of highly polluted marine sediments by photo-oxidation proves that the use of UV and the production of hydroxyl radicals are an efficient way to treat organotins adsorbed onto marine sediment despite the complexity of the matrix.