Photoelectrocatalytic oxidation of hair dye basic red 51 at W/WO 3/TiO2 bicomposite photoanode activated by ultraviolet and visible radiation

We prepared a W/WO3/TiO2 bicomposite photoanode by simple electrochemical anodization of W foil, followed by cathodic electrodeposition of TiO2 and annealing at 450 C for 30 min. This photoanode shows good photoactivity under irradiation with UV and visible light. In optimized conditions, it promotes complete photoelectrocatalytic oxidation of 3.33 × 10-5 mol L-1 basic red 51 solution (which is used in hair dye) at 0.1 mol L-1 Na2SO4, pH 2.0, under a current density of 1.25 mA cm-2 and ultraviolet and visible radiation-total organic carbon removal is 94 and 88%, respectively. This effect paves the way for the sustainable solar-assisted remediation of water bodies contaminated with organic components of hair dyes. © 2013 Elsevier Ltd. All rights reserved.

A química e toxicidade dos corantes de cabelo

The market for hair dye involves a growing range of products, which requires greater understanding of hair properties, mechanisms of action and color development. In this work, we present a critical analysis of the classification, physical and chemical characteristics, chemical analysis and toxicological/mutagenic potential of dyes used in the hair dyeing process. A compilation of some studies was carried out, focusing on the available knowledge about these dyes and their effects on the environment and human health.

A química e toxicidade dos corantes de cabelo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aquatic Toxicity Of Dyes Before And After Photo-fenton Treatment.

This study evaluated the ecotoxicity of five dyes to freshwater organisms before and during their photo-Fenton degradation. EC50 (48h) of the five tested dyes ranged from of 6.9 to >1000mgL(-1) for Daphnia similis. In the chronic tests IC50 (72h) varied from 65 to >100mgL(-1) for Pseudokirchneriella subcapitata and IC50 (8 days) from 0.5 to 410mgL(-1) for Ceriodaphnia dubia. Toxicity tests revealed that although the applied treatment was effective for decolorization of the dye, the partial mineralization may be responsible for the presence of degradation products which can be either more toxic than the original dye, as is the case of Vat Green 3 and Reactive Black 5, lead to initially toxic products which may be further degraded to non toxic products (acid Orange 7 and Food Red 17), or generate non toxic products as in the case of Food Yellow 3. The results highlighted the importance of assessing both acute and chronic toxicity tests of treated sample before effluent discharge.

Heterogeneous photocatalytic degradation of acid dyes in aqueous TiO2 suspensions: Kinetics and toxicity

This work assesses the photocatalytic (TiO2/UV) degradation of a simulated acid dye bath (Yellow 3, Red 51, Blue 74, and auxiliary chemicals). Color and phytotoxicity removal were monitored by spectrophotometry and lettuce (Lactuca sativa) seeds as the test organism, respectively. Mineralization was determined by DOC analyses. Photocatalytic, photolytic, and adsorption experiments were performed, showing that adsorption was negligible. After 240 minutes of irradiation, it was achieved 96% and 78% of color removal with photocatalysis and photolysis, respectively. 37% of mineralization occurred with photocatalysis only. The dye bath was rendered completely non-toxic after 60 minutes of photocatalytic treatment; the same result was only achieved with photolysis after 90 minutes. A kinetic model composed of two first-order in series reactions was used. The first photocatalytic decolorization rate constant was k(1) = 0.062 min(-1) and the second k(2) = 0.0043 min(-1), approximately two times greater than the photolytic ones.

Effect of Ionic Liquid on the Determination of Aromatic Amines as Contaminants in Hair Dyes by Liquid Chromatography Coupled to Electrochemical Detection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aquatic toxicity of dyes before and after photo-Fenton treatment

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cytotoxic and genotoxic effects of two hair dyes used in the formulation of black color

According to the International Agency for Research on Cancer (IARC), some hair dyes are considered mutagenic and carcinogenic in in vitro assays and exposed human populations. Epidemiological studies indicate that hairdressers occupationally exposed to hair dyes have a higher risk of developing bladder cancer. In Brazil, 26% of the adults use hair dye. In this study, we investigated the toxic effects of two hair dyes, Basic Red 51 (BR51) and Basic Brown 17 (BB17), which are temporary dyes of the azo group (R-N=N-R'), used in the composition of the black hair dye. To this end, MTT and trypan blue assays (cytotoxicity), comet and micronucleus assay (genotoxicity) were applied, with HepG2 cells. For cytotoxic assessment, dyes were tested in serial dilutions, being the highest concentrations those used in the commercial formula for hair dyes. For genotoxic assessment concentrations were selected according to cell viability. Results showed that both dyes induced significant cytotoxic and genotoxic effects in the cells, in concentrations much lower than those used in the commercial formula. Genotoxic effects could be related to the azo structure present in the composition of the dyes, which is known as mutagenic and carcinogenic. These results point to the hazard of the hair dye exposure to human health.

Differential Toxicity of Disperse Red 1 and Disperse Red 13 in the Ames Test, HepG2 Cytotoxicity Assay, and Daphnia Acute Toxicity Test

Azo dyes are of environmental concern due to their degradation products, widespread use, and low-removal rate during conventional treatment. Their toxic properties are related to the nature and position of the substituents with respect to the aromatic rings and amino nitrogen atom. The dyes Disperse Red 1 and Disperse Red 13 were tested for Salmonella mutagenicity, cell viability by annexin V, and propidium iodide in HepG2 and by aquatic toxicity assays using daphnids. Both dyes tested positive in the Salmonella assay, and the suggestion was made that these compounds induce mainly frame-shift mutations and that the enzymes nitroreductase and O-acetyltransferase play an important role in the observed effect. In addition, it was shown that the presence of the chlorine substituent in Disperse Red 13 decreased the mutagenicity about 14 times when compared with Disperse Red 1, which shows the same structure as Disperse Red 13, but without the chlorine substituent. The presence of this substituent did not cause cytotoxicity in HepG2 cells, but toxicity to the water flea Daphnia similis increased in the presence of the chlorine substituent. These data suggest that the insertion of a chlorine substituent could be an alternative in the design of dyes with low-mutagenic potency, although the ecotoxicity should be carefully evaluated. (C) 2010 Wiley Periodicals, Inc. Environ Toxicol 26: 489-497, 2011.

Decolorization and toxicity of municipal waste by horseradish (Cochlearia armoracia)

The Municipal Station of Americana, SP, Brazil, treats a volume of 400 l s-1 of effluent, of domestic and textile origin, and produces about 20 t of sludge per day. The plant horseradish, which contains high amount of peroxidases, was able to decolorize this effluent in 2 h and the solid waste in 2 days, at concentrations of 10 and 50%, respectively. However, there was an increase in the toxicity for the bioassays with Hydra attenuatta, Selenastrum capricornutum and lettuce seeds, indicating formation of more toxic substances. Since horseradish showed the ability to decolorize these residues, it can be used as pre-treatment resulting in a sludge of less complex composition.

Differential Toxicity of Disperse Red 1 and Disperse Red 13 in the Ames Test, HepG2 Cytotoxicity Assay, and Daphnia Acute Toxicity Test

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Bioremediation of direct dyes in simulated textile effluents by a paramorphogenic form of Aspergillus oryzae

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Heterogeneous photocatalytic treatment of organic dyes in air and aqueous media

This review focuses on the heterogeneous photocatalytic treatment of organic dyes in air and water. Representative studies spanning approximately three decades are included in this review. These studies have mostly used titanium dioxide (TiO2) as the inorganic semiconductor photocatalyst of choice for decolorizing and decomposing the organic dye to mineralized products. Other semiconductors such as ZnO, CdS, WO3, and Fe2O3 have also been used, albeit to a much smaller extent. The topics covered include historical aspects, dark adsorption of the dye on the semiconductor surface and its role in the subsequent photoreaction, semiconductor preparation details, photoreactor configurations, photooxidation kinetics/mechanisms and comparison with other Advanced Oxidation Processes (e.g., UV/H2O2, ozonation, UV/O3, Fenton and photo-Fenton reactions), visible light-induced dye decomposition by sensitization mechanism, reaction intermediates and toxicity issues, and real-world process scenarios. © 2008 Elsevier B.V. All rights reserved.

Highly Ordered TiO2 Nanotubes for Electrochemical Sensing of Hair Dye Basic Brown 17

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Comparative study of toxicity of azo dye Procion Red MX-5B following biosorption and biodegradation treatments with the fungi Aspergillus niger and Aspergillus terreus

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)