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The combination of chemical analyses and bioassays allows the identification of potentially mutagenic compounds in different types of samples. Dyes can be considered as emergent contaminants and were detected in waters, under the influence of textile activities. The objective of this study was to evaluate the contribution of 9 azo dyes to the mutagenicity of representative environmental samples. Samples were collected along one year in the largest conglomerate of textile industries of Brazil. We analyzed water samples from an important water body, Piracicaba River, upstream and downstream two main discharges, the effluent of a wastewater treatment plant (WWTP) and the tributary Quilombo River, which receives untreated effluent from local industries. Samples were analyzed using a LC-MS/MS and tested for mutagenicity in the Salmonella/microsome microsuspension assay with TA98 and YG1041. Six dyes were detected in the collected samples, Disperse Blue 291, Disperse Blue 373, Disperse Orange 30, Disperse Red 1, Disperse Violet 93, and Disperse Yellow 3. The most sensitive condition for the detection of the mutagenicity was the strain YG1041 with S9. The concentration of dyes and mutagenicity levels varied along time and the dry season represented the worst condition. Disperse Blue 373 and Disperse Violet 93 were the major contributors to the mutagenicity. We conclude that dyes are contributing for the mutagenicity of Piracicaba River water; and both discharges, WWTP effluent and Quilombo River, increase the mutagenicity of Piracicaba River waters in about 10-fold. The combination of chemical analysis and bioassays were key in the identification the main drivers of the water mutagenicity and allows the selection of priority compounds to be included in monitoring programs as well for the enforcing actions required to protect the water quality for multiple uses.

h i g h l i g h t s g r a p h i c a l a b s t r a c t Disperse Red 1 dye was found in river waters in concentrations above the PNEC.The PNEC was based on toxicity endpoints for a commercial dye and its purified form. The CRED method was used to evaluate the quality of endpoints used in PNEC derivation. a b s t r a c tWater quality criteria to protect aquatic life are not available for most disperse dyes which are often used as commercial mixtures in textile coloration. In this study, the acute and chronic toxicity of the commercial dye Disperse Red 1 (DR1) to eight aquatic organisms from four trophic levels was evaluated. A safety threshold, i.e. Predicted No-Effect Concentration (PNEC), was derived based on the toxicity information of the commercial product and the purified dye. This approach was possible because the toxicity of DR1 was accounting for most of the toxicity of the commercial mixture. A long-term PNEC of 60 ng L À1 was proposed, based on the most sensitive chronic endpoint for Daphnia similis. A short-term PNEC of 1800 ng L À1 was proposed based on the most sensitive acute endpoint also for Daphnia similis.Both key studies have been evaluated with the new "Criteria for Reporting and Evaluating ecotoxicity Data" (CRED) methodology, applying more objective criteria to assess the quality of toxicity tests, resulting in two reliable and relevant endpoints with only minor restrictions. HPLC-MS/MS was used to quantify the occurrence of DR1 in river waters of three sites, influenced by textile industry discharges, resulting in a concentration range of 50e500 ng L À1 . The risk quotients for DR1 obtained in this work Chemosphere 156 (2016) 95e100 Mixture PNEC suggest that this dye can pose a potential risk to freshwater biota. To reduce uncertainty of the derived PNEC, a fish partial or full lifecycle study should be performed.

We have optimized an SPE-LC-ESI-MS/MS method and used it to monitor disperse azo dyes in environmental aquatic samples. Calibration curves constructed for nine disperse dyes-Red 1, Violet 93, Blue 373, Orange 1, Orange 3, Orange 25, Yellow 3, Yellow 7 and Red 13-in aqueous solution presented good linearity between 2.0 and 100.0 ng mL(-1). The method provided limits of detection and quantification around 2.0 and 8.0 ng L(-1), respectively. For dyes at concentrations of 25.0 ng mL(-1), the intra- and interday analyses afforded relative standard deviation lower than 6 and 13%, respectively. The recovery values obtained for each target analyte in Milli-Q water, receiving waters and treated water samples spiked with the nine studied dyes at concentrations of 8.0, 25.0 and 50.0 ng L(-1) (n = 3) gave average recoveries greater than 70%, with RSD <20%. Statistical evaluation aided method validation. The validated method proved to be useful for analysis of organic extracts from effluents and receiving water samples after an SPE extraction step. More specifically, the method enabled detection of the dyes Disperse Red 1, Disperse Blue 373 and Disperse Violet 93 at concentrations ranging from 84 to 3452 ng L(-1) in the treated effluent (TE), affluent and points collected upstream and downstream of the drinking water treatment plant of a textile dye industry in Brazil.

Waters receiving textile discharges can exhibit genotoxic and mutagenic activity, which has been related to the presence of dyes and aromatic amines as synthesis precursors or byproducts. The aim of this study was to identify dyes and aromatic amines in water samples impacted by textile discharges, and to evaluate the genotoxic responses of these samples using the Salmonella/microsome assay in strains TA98 and YG1041, and the Fpg-modified comet assay in the RTL-W1 fish cell line. The genotoxicity of river samples downstream of the discharge was greater than the upstream samples in both of the Ames tests. The Fpg-modified comet assay detected similar levels of DNA damage in the upstream and downstream samples. Mutagenicity was not detected with TA98, except for the Quilombo River samples, but when YG1041 was used as the tester strain mutagenicity was detected for all sites with a very different profile in upstream sites relative to the other sites. The mutagenic response strongly indicated that aromatic amines or dyes were contributing to the mutagenic activity downstream. The impact of textile discharges was also confirmed by chemical analysis, because the highest concentrations of azo dyes and aromatic amines were detected in the river downstream. This study shows the value of combining assays measuring complementary endpoints to better characterize the mutagenicity of environmental samples, with the advantage that this approach provides an indication of what classes of compounds are responsible for the effect. Environ. Mol. Mutagen. 57:559-571, 2016. © 2016 Wiley Periodicals, Inc.

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The international textile wet processing industry produces large amounts of wastewater, which if discharged into the environment could have adverse effects on aquatic life and drinking water. Efforts to reduce wastewater production include the development of chemical finishing technology that employs atmospheric plasma to apply repellent finishes to textile fibers. With this in mind, the use of atmospheric plasma technology to apply dyes to textile fibers was examined in the present study, as no water is needed for the dyeing process. Our work involved the design and synthesis of suitable dyes for waterless technology and examination of their utility for dyeing cotton, nylon, and polyester (PET). Results indicated that the obtained azo dyes having one or two acrylate groups gave good bonding to and good technical properties on cotton, nylon, or PET following spray application and plasma treatment. Dyes that worked best were also nonmutagenic in the Ames test.

Background: The Max Weaver Dye Library (MWDL) from North Carolina State University is a repository of around 98,000 synthetic dyes. Historically, the uses for these dyes included the coloration of textiles, paper, packaging, cosmetic and household products. However, little is reported about their ecotoxicological properties. It is anticipated that prediction models could be used to help provide this type information. Thus, the purpose of this work was to determine whether a recently developed QSAR (quantitative structure-activity relationships) model, based on ACO-SVM techniques, would be suitable for this purpose. Results: We selected a representative subset of the MWDL, composed of 15 dyes, for testing under controlled conditions. First, the molecular structure and purity of each dye was confirmed, followed by predictions of their solubility and pKa to set up the appropriate test conditions. Only ten of the 15 dyes showed acute toxicity in Daphnia, with EC 50 values ranging from 0.35 to 2.95 mg L −1. These values were then used to determine the ability of the ACO-SVM model to predict the aquatic toxicity. In this regard, we observed a good prediction capacity for the 10 dyes, with 90% of deviations within one order of magnitude. The reasons for this outcome were probably the high quality of the experimental data, the consideration of solubility limitations, as well as the high purity and confirmed chemical structures of the tested dyes. We were not able to verify the ability of the model to predict the toxicity of the remaining 5 dyes, because it was not possible to determine their EC 50. Conclusions: We observed a good prediction capacity for the 10 of the 15 tested dyes of the MWDL, but more dyes should be tested to extend the existing training set with similar dyes, to obtain a reliable prediction model that is applicable to the full MWDL.