Mussel-Inspired Immobilization of Photocatalysts with Synergistic Photocatalytic-Photothermal Performance for Water Remediation.

The serious problem of pharmaceutical and personal care product pollution places great pressure on aquatic environments and human health. Herein, a novel coating photocatalyst was synthesized by adhering Ag-AgCl/WO3/g-C3N4 (AWC) nanoparticles on a polydopamine (PDA)-modified melamine sponge (MS) through a facile layer-by-layer assembly method to degrade trimethoprim (TMP). The formed PDA coating was used for the anchoring of nanoparticles, photothermal conversion, and hydrophilic modification. TMP (99.9%; 4 mg/L) was removed in 90 min by the photocatalyst coating (AWC/PDA/MS) under visible light via a synergistic photocatalytic-photothermal performance route. The stability and reusability of the AWC/PDA/MS have been proved by cyclic experiments, in which the removal efficiency of TMP was still more than 90% after five consecutive cycles with a very little mass loss. Quantitative structure-activity relationship analysis revealed that the ecotoxicities of the generated intermediates were lower than those of TMP. Furthermore, the solution matrix effects on the photocatalytic removal efficiency were investigated, and the results revealed that the AWC/PDA/MS still maintained excellent photocatalytic degradation efficiency in several actual water and simulated water matrices. This work develops recyclable photocatalysts for the potential application in the field of water remediation.

Metal-free 2D/2D heterojunction of covalent triazine-based frameworks/graphitic carbon nitride with enhanced interfacial charge separation for highly efficient photocatalytic elimination of antibiotic pollutants.

A novel polymer-based 2D/2D heterojunction photocatalysts of covalent triazine-based frameworks/graphitic carbon nitride nanosheets (CTFNS/CNNS) heterojunction are successfully obtained by an electrostatic self-assembly method using amine-functionalized CNNS and carboxyl-rich CTFNS. Such large contact surface and appropriate interfacial contact between CNNS and CTFNS plays a critical role in transfer and separation of charge-carriers. The resulting CTFNS/CNNS heterojunction showed significantly enhanced photocatalytic activity under the irradiation of simulated solar light, which could decompose 10 ppm sulfamethazine (SMT) within 180 min with a high degradation efficiency of 95.8 %. Chloride ions can greatly promote the photocatalytic degradation of SMT due to the production of more radical species. O2- is the dominant active species for SMT decomposition over CTFNS/CNNS heterojunction. Moreover, the degradation intermediates of SMT were identified using high performance liquid chromatography-mass spectrometer and the degradation pathway was proposed. This study provides a new insight into the design of 2D/2D heterojunctions using carbon-based nanomaterials, which exhibits great potential in the degradation of sulfonamide antibiotics in wastewaters.

UV-FIA: UV-induced fluoro-immunochemical assay for ultra-trace detection of PETN, RDX, and TNT.

Fluorescence quenching based immunoassay format for the detection of a trace amount of some nitro-explosives with a high degree of selectivity is reported in this study. The immunoassay comprises anti-explosive antibodies functionalized microtitre strips specific to the targeted explosives, pentaerythritol tetranitrate (PETN), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), and 2,4,6-trinitrotoluene (TNT). UV induced photolysis of nitro-explosive bound to targeted antibodies generates primarily nitrite ions which after the quick reaction with the detector molecule, 2,3-diaminonaphthalene (DAN), a fluorophore, quenches its fluorescence intensity, however, proportionately undergo cyclization to produce a highly fluorescent product, 2,3-naphthotriazole (NAT). The synthesized product, NAT, was verified using various chromatographic and spectrophotometric techniques. This newly developed antibody-based detection method, utilizing DAN dye, demonstrated a high selectivity towards PETN, RDX, and TNT. This method can be used as an economical testing kit for direct quantification of explosives, implying the great potential for quick, low-cost trace detection of explosives.

Integrated photocatalytic-biological treatment of triazine-containing pollutants.

The degradation of triazine-containing pollutants including simazine, Irgarol® 1051 and Reactive Brilliant Red K-2G (K-2G) by photocatalytic treatment was investigated. The effects of titanium dioxide (TiO2) concentration, initial pH of reaction mixture, irradiation time and ultraviolet (UV) intensity on photocatalytic treatment efficiency were examined. Complete decolorization of K-2G was observed at 60 min photodegradation while only 15 min were required to completely degrade simazine and Irgarol® 1051 under respective optimized conditions. High-performance liquid chromatography (HPLC), gas chromatography/mass spectrometry (GC/MS) and ion chromatography (IC) were employed to identify the photocatalytic degradation intermediates and products. Dealkylated intermediates of simazine, deisopropylatrazine and deethyldeisopropylatrazine, and Irgarol® 1051 were detected by GC/MS in the initial phase of degradation. Complete mineralization could not be achieved for all triazine-containing pollutants even after prolonged (>72 h) UV irradiation due to the presence of a photocatalysis-resistant end product, cyanuric acid (CA). The toxicities of different compounds before and after photocatalytic treatment were also monitored by three bioassays. To further treat the photocatalysis-resistant end product, a CA-degrading bacterium was isolated from polluted marine sediment and further identified as Klebsiella pneumoniae by comparing the substrate utilization pattern (Biolog™ microplate), fatty acid composition and 16S rRNA gene sequencing. K. pneumoniae efficiently utilized CA from 1 to 2000 mg/L as a good nitrogen source and complete mineralization of CA was observed within 24 h of incubation. This study demonstrates that the biodegradability of triazine-containing pollutants was significantly improved by the photocatalytic pre-treatment, and this proposed photocatalytic-biological integrated system can effectively treat various classes of triazine-containing pollutants.

Optimisation of radiolysis of Reactive Red 120 dye in aqueous solution using ionising (60)Co gamma radiation by response surface methodology.

In recent years, employing radiation technology is gaining great interest in degradation of industrial effluents. In this work the possibility of using gamma irradiation to degrade Reactive Red 120 (C.I.292775) was explored. The effects of pH, dose of gamma irradiation and concentration of dye were examined and their interaction were also established based on their response. For the analysis and optimisation of variables, three factor three level Box-Wilson face centred central composite design (CCF) was used. Analysis of variance with R(2) = 0.9988, adjusted R(2) = 0.9981 and the adequate precision value of 122.303 indicates that the CCF model can be used. The coefficient of variation (0.54%) indicates the reliability of the model. The dose of gamma irradiation (kGy) and the concentration of dye (mg/L) showed significant effects on the degradation of RR 120, while a difference of 6 to 10% degradation was observed in extending the pH towards the acid or alkali range from pH 7.00. The maximum concentration of dye degraded was observed as 347.509 mg/L at initial pH: 7.0, dose of gamma irradiation: 5.94 kGy and initial concentration of dye: 500 mg/L. This predicted value was found to be in agreement with the experimental value on the optimised conditions.

The novel isotopically coded short-range photo-reactive crosslinker 2,4,6-triazido-1,3,5-triazine (TATA) for studying protein structures.

Short-distance molecular-modeling constraints are advantageous for elucidating the structures of individual proteins and protein conformational changes. Commonly used amine-reactive crosslinks are relatively long (14Å), partly due to the length of the lysine side-chain, and are sparsely distributed throughout a protein. Short-distance non-specific crosslinkers can provide a larger number of tighter molecular-modeling constraints. Here we describe the use of a short-range homo-trifunctional isotopically-coded non-specific photo-reactive crosslinking reagent, 2,4,6-triazido-1,3,5-triazine (TATA)-12C3/13C3, for MS-based protein crosslinking studies. Upon activation by 254nm UV light, TATA-12C3/13C3 generates up to three nitrene radicals capable of non-selective crosslinking at ~5Å. This reagent was validated using cyclohexane, several test peptides, and myoglobin, and was found to react with a large number of amino acids, forming multiple crosslinked products. The myoglobin crosslinks detected by MS agreed with the known structure of myoglobin; arranging the protein's secondary-structure motifs into their correct fold was possible based solely on the constraints imposed by the crosslinks. Finally, TATA was used to crosslink the α-synuclein monomer. The 10 short-distance constraints provided by TATA crosslinking led to an initial model of the molten-globule form of the native α-synuclein monomer; this provides a suggested structure for the precursor of the misfolded α-synuclein proteoforms involved in synucleopathies. BIOLOGICAL SIGNIFICANCE: The isotopically labeled short-range non-specific crosslinker TATA-12C3/13C3 was characterized for use in crosslinking-based protein structural studies. The crosslinking products of TATA can provide a distance constraint of merely 5Ǻ between crosslinked residues. TATA-12C3/13C3 had broad reactivity, crosslinking a wide variety of amino acids, including lysine, glutamic and aspartic acid, asparagine, glutamine, glycine, alanine, valine, proline, methionine, serine, cysteine, tyrosine, and the N-terminus. The short-distance crosslinking constraints provided by TATA allowed us to predict the fold of myoglobin using a combination of these distance constraints with a prediction of myoglobin's secondary structure motifs. TATA was also used to crosslink α-synuclein in its native, molten globule form, which has not been characterized using other structural biology techniques. The distance constraints provided by the crosslinks allowed for the manual modeling of a rudimentary structure for the α-synuclein monomer.

Photolytic degradation of tris-(2,3-dibromopropyl) isocyanurate (TBC) in aqueous systems.

Tris-(2,3-dibromopropyl) isocyanurate (TBC) is a brominated flame retardant, which has been found in several environmental and biological matrices in recent years. TBC has aroused high environmental concerns because of its bioaccumulation and biological toxicity. This work studied photodegradation of TBC for the first time. The optimal degradation conditions have been found that 95% of 10 µmol/LTBC was effectively decomposed after 120 min of UV radiation. UV lamp was found to be more effective than Xe lamp on the photodegradation. The degradation rate of TBC increased with increasing light intensity. Under UV illumination, the effect of pH on the photodegradation of TBC could be ignored and degradation reactions followed the pseudo-first-order kinetics. The addition of [Formula: see text] could not accelerate the degradation of TBC. The quenching experiments showed that TBC was directly photodegraded by UV illumination. These findings suggest that UV photodegradation is a potential method for the removal of TBC in aqueous solutions.

Photostability evaluation of five UV-filters, trans-resveratrol and beta-carotene in sunscreens.

Trans-resveratrol (RES) is used in cosmetic formulations and beta-carotene (BTC) is a classical sunscreen antioxidant, but their photostability in sunscreens, a property directly correlated to performance and safety has not been addressed in the literature. This paper reports the assessment of RES and/or BTC influence on the photostability of five UV-filters (octyl methoxycinnamate - OMC, avobenzone -AVO, octocrylene - OCT, bemotrizinole - BMZ, octyltriazone - OTZ) in three different combinations after UVA exposure followed by the identification of degradation products and the assessment of photoreactivity. The evaluation of sunscreen photostability was performed by HPLC and spectrophotometric analysis, and degradation products were identified by GC-MS analysis. Components RES, BTC, OMC and AVO were significantly degraded after UV exposure (reduction of around 16% in recovery). According to HPLC analysis, all formulations presented similar photostability profiles. Eleven degradation products were identified in GC-MS analysis, among them products of RES, BTC, OMC and AVO photodegradation. All evaluated formulations were considered photoreactive, as well as the isolated compounds RES and AVO. Considering HPLC, spectrophotometric and GC-MS results, it is suggested that formulations containing BMZ were considered the most photostable. The combination RES+BTC in a sunscreen improved the photostability of AVO. The benefits of using a combination of antioxidants in sunscreens was demonstrated by showing that using RES+BTC+studied UV-filters led to more photostable formulations, which in turn implies in better safety and efficacy.

Tris-biphenyl triazine, a new ultraviolet filter studied in terms of photoprotective efficacy.

There are relatively few authorized ultraviolet filters in Europe and this presents a certain number of problems when we want to formulate a sun protection product which both ensures a high level of protection and respects the recommendations in force in terms of broad-spectrum efficacy, with, in particular, a critical wavelength (λc) greater than or equal to 370 nm. A new ultraviolet filter has just been launched on the market. Known as tris-biphenyl triazine, it is the first filter to be registered on Annexe VI of "Cosmetics Regulation" (EC) No. 1223/2009 of the European Parliament and of the Council, which gives a list of the ultraviolet filters allowed in cosmetic products, since the regulation came into force in July 2013. This filter is both very effective (as it enables 2 SPF units and 1 UVA-PF units to be obtained respectively, by percentage of use) and very photostable (since the SPF and UVA-PF do not vary after 2h of irradiation in a solar simulator). Its broad spectrum associated with its qualities in terms of efficacy and photostability make it a choice ingredient for the formulation of sun protection products.

Combination of retinyl palmitate and UV-filters: phototoxic risk assessment based on photostability and in vitro and in vivo phototoxicity assays.

This study aimed to assess the phototoxic potential of combined UV-filters and retinyl palmitate (RP) in the presence or not of bemotrizinol (BMTZ), employing photostability and in vitro and in vivo phototoxicity assays. The formulations tested contained octocrylene (OCT), octyl methoxycinnamate (OMC), benzophenone-3 (BZP-3) and RP (photostable) or octocrylene (OCT), octyl methoxycinnamate (OMC), avobenzone (AVO) and RP (less photostable). Both formulations were supplemented with bemotrizinol. Photostability was evaluated by exposing, or not, formulations spread on a glass plate to UVA/UVB irradiation. The resulting products were quantified by HPLC analysis. In vitro phototoxicity of UV-filters and combinations were evaluated using 3T3 viable monolayer fibroblast cultures submitted, or not, to irradiation according to OECD TG 432. In vivo photoallergy and photoxicity were assessed by clinical studies (photopatch test). Photostability assays showed that UV-filter bemotrizinol was a better photostabilizer for RP/benzophenone-3 than for RP/avobenzone. The in vitro phototoxicity of the combination RP/avobenzone was reduced by bemotrizinol. Clinical studies did not indicate phototoxic or photoallergenic potentials in all formulations tested. It is concluded that the 3T3 NRU phototoxicity test may be considered a supplementary assay in formulation developments, since it can detect chemically unstable and potentially phototoxic combinations. However, extrapolation of in vitro positive results to human photopatch tests may be performed only to a limited extent.

Photodegradation of the benzotriazine 1,4-Di-N-oxide hypoxia-activated prodrug SN30000 in aqueous solution.

SN30000 is a benzotriazine di-N-oxide which is selectively toxic to radio-resistant hypoxic cells in tumours. Given the complex photochemistry of some aromatic N-oxides, we evaluated the potential for photodegradation of SN30000 solutions. Initial studies demonstrated significant oxygen-insensitive degradation under normal laboratory lighting conditions. The kinetics of photodegradation showed marked concentration dependence of the form predicted by Beer's law, with a quantum yield of 0.016. The photoproducts could be rationalised as arising from an oxaziridine intermediate. The major stable product (cmpd 6; yield ∼50% of SN30000 loss under either UV or visible light) was characterised as resulting from intra-molecular oxygen transfer to the morpholine side chain of SN30000. This mechanism is consistent with lack of formation of the corresponding morpholine N-oxide from an analogue (SN29751) in which the proposed six-membered-ring transition state cannot form. Cmpd 6 was less cytotoxic than SN30000 to human tumour cells in culture, under either hypoxic or aerobic conditions, and was not toxic when administered intra-peritoneally to NIH-III nude mice at a dose (750 µmol/kg) above the maximal tolerated dose of SN30000 itself. In conclusion, SN30000 solutions are significantly photosensitive at low concentration, requiring protection from light, but the major photoproduct is less toxic than the parent.

Preparation and photocatalytical performance of TiO2:SiO2 nanocomposites produced by the polymeric precursors method.

Anatase TiO2 is a promising photocatalyst due to its chemical stability, non-toxic characteristics, notable UV light absorption as well as photo-corrosion resistance and oxidative properties. Surface area and TiO2 dispersion quality are important factors that affect photoactivity of TiO2:SiO2 nanocomposites. In order to improve these factors, TiO2 nanoparticles were immobilized on mesoporous silica substrate through the polymeric precursors method, obtaining the nanocomposites in a simple routine. The TiO2 resin was synthesized by the polymeric precursors method and different resin thickness (0.5; 1.0; 2.0; 3.5; 5.0 nm) on silica were synthesized by calcination during 4 hours at 450 degrees C in pH 1.5. The selected pH for immobilization ensured adhesion of TiO2 nanoparticles onto the silica substrate surface. X-Ray Diffraction patterns indicate that all samples were predominantly anatase phase and immobilization improved surface area. Ametryn kinetic evaluation presents better results for SAM 3.5 and SAM 0.5. The results show that difference in TiO2 loading, surface area and crystallinity of samples are factors that influence photocatalytic efficiency.

Comparing atrazine and cyanuric acid electro-oxidation on mixed oxide and boron-doped diamond electrodes.

The breakdown of pesticides has been promoted by many methods for clean up of contaminated soil and wastewaters. The main goal is to decrease the toxicity of the parent compound to achieve non-toxic compounds or even, when complete mineralization occurs, carbon dioxide and water. Therefore, electrochemical degradation (potentiostatic and galvanostatic) of both the pesticide atrazine and cyanuric acid (CA) at boron-doped diamond (BDD) and Ti/Ru0.3Ti0.7O2 dimensionally stable anode (DSA) electrodes, in different supporting electrolytes (NaCl and Na2SO4), is presented with the aim of establishing the influence of the operational parameters on the process efficiency. The results demonstrate that both the electrode material and the supporting electrolyte have a strong influence on the rate of atrazine removal. In the chloride medium, the rate of atrazine removal is always greater than in sulfate under all conditions employed. Furthermore, in the sulfate medium, atrazine degradation was significant only at the BDD electrode. The total organic carbon (TOC) load decreased by 79% and 56% at the BDD and DSA electrodes, respectively, in the chloride medium. This trend was maintained in the sulfate medium but the TOC removal was lower (i.e. 33% and 13% at BDD and DSA electrodes, respectively). CA, a stable atrazine degradation intermediate, was also studied and it is efficiently removed using the BDD electrode in both media, mainly when high current densities are employed. The use of the BDD electrode in the chloride medium not only degrades atrazine but also mineralized cyanuric acid leading to the higher TOC removal.

Solar active photocatalyst for effective degradation of RR 120 with dye sensitized mechanism.

Solar active WO3 loaded Ag-ZnO (WO3-Ag-ZnO) was successfully synthesized by precipitation-decomposition method. XPS reveals that the presence of metallic silver in the catalyst. The photocatalytic activity of WO3-Ag-ZnO was investigated for the degradation of Reactive Red 120 (RR 120) in aqueous solution using solar light. WO3-Ag-ZnO is found to be more efficient than Ag-ZnO, WO3-ZnO, Ag-WO3, commercial ZnO, prepared ZnO, Degussa TiO2-P25, pure WO3 and TiO2 (Merck) at pH 7 for the mineralization of RR 120. The effects of operational parameters such as the amount of photocatalyst, dye concentration, initial pH on photo mineralization of RR 120 have been analyzed. The mineralization of RR 120 has been confirmed by COD measurements. A dual mechanism has been proposed for efficient degradation of RR 120 dye with WO3-Ag-ZnO under solar light at neutral pH. This catalyst is found to be reusable.

An insight into the influence of low dose irradiation pretreatment on the microbial decolouration and degradation of Reactive Red-120 dye.

The influence of low dose irradiation pretreatment on the microbial decolouration and degradation of Reactive Red-120 (RR-120) dye was investigated in detail by using Pseudomonas sp. SUK1. About 27%, 56% and 66% decolouration of 150 ppm RR-120 dye solution was observed by applying 0, 0.5 and 1 kGy doses, respectively, in the first step followed by microbial treatment for 24 h under static condition. Similarly, about 70%, 88% and 90% TOC removal was observed by applying 0, 0.5 and 1 kGy doses, respectively, in the first step followed by the microbial treatment for 96 h under static condition. The radiation induced fragmented products of RR-120 at doses of 0.5 and 1 kGy were investigated by FTIR and electrospray ionization-MS analysis. The induction of the enzymes viz. laccase, tyrosinase, azoreductase and NADH-2,6-dichlorophenol indophenol reductase was studied in the decolourised solution obtained after irradiating 150 ppm RR-120 dye solution with 0 and 1 kGy doses followed by the microbial treatment for 96 h under static condition. The enzymatic degradation products were studied by FTIR, HPLC and GC-MS. The toxicity study of the treated dye solution on plants revealed the degradation of RR-120 into non-toxic products by combined radiation-microbial treatment. This study explores a reliable and promising way to use industrially viable dose (≤1 kGy) and microbial strain viz. Pseudomonas sp. SUK1 for permissible safe disposal of dye solutions from textile industries.

Degradation of reactive dyes in a photocatalytic circulating-bed biofilm reactor.

Decolorization and mineralization of reactive dyes by intimately coupled TiO2-photocatalysis and biodegradation (ICPB) on a novel TiO2-coated biofilm carrier were investigated in a photocatalytic circulating-bed biofilm reactor (PCBBR). Two typical reactive dyes--Reactive Black 5 (RB5) and Reactive Yellow 86 (RY86)--showed similar first-order kinetics when being photocatalytically decolorized at low pH (~4-5) in batch experiments. Photocatalytic decolorization was inhibited at neutral pH in the presence of phosphate or carbonate buffer, presumably due to electrostatic repulsion from negatively charged surface sites on TiO2, radical scavenging by phosphate or carbonate, or both. Therefore, continuous PCBBR experiments were carried out at a low pH (~4.5) to maintain high photocatalytic efficiency. In the PCBBR, photocatalysis alone with TiO2-coated carriers could remove target compound RB5 and COD by 97% and 47%, respectively. Addition of biofilm inside macroporous carriers maintained a similar RB5 removal efficiency, but COD removal increased to 65%, which is evidence of ICPB despite the low pH. ICPB was further proven by finding microorganisms inside carriers at the end of the PCBBR experiments. A proposed ICPB pathway for RB5 suggests that a major intermediate, a naphthol derivative, was responsible for most of the residual COD, while most of the nitrogen in the azo-bonds (-N=N-) was oxidized to N2.

Thin wetted film cylindrical flow photo reactor for the degradation of Procion blue H-B dye over TiO2 and ZnO.

A thin wetted film cylindrical flow reactor was fabricated for photocatalytic oxidation of Procion blue H-B dye in textile washwater with the suspensions of TiO2 and ZnO. The disappearance of colour and organic reduction were studied in terms of the removal of colour and chemical oxygen demand (COD). Operating parameters such as effect of pH, UV irradiation with and without catalyst, initial concentration of dye and effect of flow rate were studied and kinetics of Procion blue H-B dye has been studied over TiO2 and ZnO surfaces. Since adsorption is the prerequisite condition for decolorization/degradation of dye molecules in the presence of heterogeneous catalysis, the Langmuir and Freundlich isotherms were examined to verify the adsorption intensity. The results clearly demonstrated that, the optimum loading of the photocatalyst was found to be 300 and 400 mg/L of TiO2 and ZnO, respectively. The maximum COD reduction efficiency was 68% for TiO2 and 58% for ZnO. On the other hand, the colour removal efficiency was found to be 74% and 69%, respectively for TiO2- and ZnO-assisted systems under optimum conditions. Conclusively, these two semiconductors could degrade Procion blue H-B dye at different time intervals and both isotherms fit well.

Effects of TiO2 dosage, pH and temperature on decolorization of C.I. Reactive Red 2 in a UV/US/TiO2 system.

This study elucidates the decolorization of C.I. Reactive Red 2 (RR2) in ultrasound (US), US/TiO(2), ultraviolet (UV)/TiO(2) and UV/US/TiO(2) systems. The effects of TiO(2) dosage, pH and temperature on RR2 decolorization were determined in a UV/US/TiO(2) system. The pseudo-first-order decolorization rate constants of 0.5, 1 and 2g/l TiO(2) in the UV/US/TiO(2) system were 0.45, 0.57 and 0.94 h(-1), respectively. In the UV/US/TiO(2) system, the decolorization rate of RR2 declines as pH increases, and increases as temperature increasing. At pH 7, the decolorization rates followed the order of UV/US/TiO(2) (0.94 h(-1))>UV/TiO(2) (0.85h(-1))>US/TiO(2) (0.25 h(-1))>US. The activation energy of the UV/US/TiO(2) system at pHs of 4, 7 and 10 was 6.58, 11.62 and 21.32kJ/mol, respectively. Experimental results suggest that the RR2 decolorization in the UV/US/TiO(2) system was a diffusion-controlled reaction.

Photodegradation of C.I. Reactive Red 2 in UV/TiO2-based systems: effects of ultrasound irradiation.

This investigation elucidated the decolorization of C.I. Reactive Red 2 (RR2) in US/TiO(2), UV/TiO(2) and UV/US/TiO(2) systems and evaluated the effect of ultrasound (US) irradiation in photocatalysis. The effects of RR2 concentration, temperature and the addition of NaCl, Na(2)S(2)O(8) and radical scavenger were determined. The decolorization reactions obeyed the pseudo-first-order kinetics in all tested systems. In US-related systems, the decolorization rate of RR2 declines as RR2 concentration increases. At pH 7, the decolorization rates followed the order UV/US/TiO(2) (0.94 h(-1))>UV/TiO(2) (0.85 h(-1))>US/TiO(2) (0.25 h(-1)). The promotion efficiencies of adding NaCl in US/TiO(2), UV/TiO(2) and UV/US/TiO(2) systems were 16%, 18% and 29%, respectively. The decolorization rate increased with the temperature; additionally, the decolorization rate in UV/US/TiO(2)/Na(2)S(2)O(8) exceeded that in UV/US/TiO(2). The inhibition of RR2 decolorization by adding 1-butanol reveals that the primary decolorization pathway involves hydroxyl radicals, and that direct oxidation by photogenerated holes is probably important in the UV/TiO(2)-based system. After 120 min of the reaction, the TOC degradation efficiencies of UV/TiO(2) and UV/US/TiO(2) systems were 47% and 63%, respectively.

Evaluation of a TiO2 photocatalysis treatment on nitrophenols and nitramines contaminated plant wastewaters by solid-phase extraction coupled with ESI HPLC-MS.

Nitration reactions of aromatic compounds are commonly involved in different industrial processes for pharmaceutical, pesticide or military uses. For many years, most of the manufacturing sites used lagooning systems to treat their process effluents. In view of a photocatalytic degradation assay, the wastewater of a lagoon was investigated by using HPLC coupled with mass spectrometry. The wastewater was highly concentrated in RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and two herbicides Dinoterb (2-tert-butyl-4,6-dinitrophenol) and Dinoseb (2-sec-butyl-4,6-dinitrophenol). First of all, an analytical method using solid-phase extraction (SPE) combined with HPLC ESI MS/MS was put in work for identification and titration of RDX, HMX and the two dinitrophenols in a complex natural matrix. Then, the UV/TiO2 treatment was investigated for pollutants removal. Dinitrophenolic compounds were significantly degraded after a 8-h-exposition of the wastewater/TiO2 suspension, whereas RDX and HMX were poorly affected.