Chlorine disinfection of dye wastewater: Implications for a commercial azo dye mixture

Azo dyes, the most widely used family of synthetic dyes, are often employed as colorants in areas such as textiles, plastics, foods/drugs/cosmetics, and electronics. Following their use in industrial applications, azo dyes have been found in effluents and various receiving waters. Chemical treatment of effluents containing azo dyes includes disinfection using chlorine, which can generate compounds of varying eco/genotoxicity. Among the widely known commercial azo dyes for synthetic fibers is C.I. Disperse Red 1. While this dye is known to exist as a complex mixture, reports of eco/genotoxicity involve the purified form. Bearing in mind the potential for adverse synergistic effects arising from exposures to chemical mixtures, the aim of the present study was to characterize the components of commercial Disperse Red 1 and its chlorine-mediated decoloration products and to evaluate their ecotoxicity and mutagenicity. In conducting the present study, Disperse Red 1 was treated with chlorine gas, and the solution obtained was analyzed with the aid of LC-ESI-MS/MS to identify the components present, and then evaluated for ecotoxicity and mutagenicity, using Daphnia similis and Salmonella/microsome assays, respectively. The results of this study indicated that chlorination of Disperse Red 1 produced four chlorinated aromatic compounds as the main products and that the degradation products were more ecotoxic than the parent dye. These results suggest that a disinfection process using chlorine should be avoided for effluents containing hydrophobic azo dyes such commercial Disperse Red 1. © 2012 Elsevier B.V..

Assessment of the breakdown products of solar/UV induced photolytic degradation of food dye tartrazine

The food dye tartrazine (CI 19140) was exposed to UV irradiation from an artificial source, a mercury vapor lamp, and a natural one, sunlight. It was observed that conditions such as energy dose, irradiation time, pH and initial dye concentration affected its discoloration. There was 100% of color removal, after 30 min of irradiation, when a dye solution 1 x 10(-5) mol L-1 was submitted to an energy dose of 37.8 J cm(-2). Liquid Chromatography coupled to Diode Array Detection and Mass Spectrometry confirmed the cleavage of the chromophore group and the formation of five by-products at low concentration. Although by-products were formed, the Salmonella/microsome mutagenicity assay performed for both, the dye solution at a dose of 5.34 mg/plate and the solutions obtained after exposure to UV irradiation, did not present mutagenic activity for TA98 and TA100 with and without S9. (C) 2014 Elsevier Ltd. All rights reserved.

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

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

Potential of a bacterial consortium to degrade azo dye Disperse Red 1 in a pilot scale anaerobic-aerobic reactor

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

Using SPE-LC-ESI-MS/MS analysis to assess disperse dyes in environmental water samples

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.

Mutagenicity profile of atmospheric particulate matter in a small urban center subjected to airborne emission from vehicle traffic and sugar cane burning

Atmospheric particulate matter (PM) is genotoxic and recently was classified as carcinogenic to humans by the International Agency for Research on Cancer. PM chemical composition varies depending on source and atmospheric conditions. The Salmonella/microsome assay is the most used mutagenicity test and can identify the major chemical classes responsible for observed mutagenicity. The objective of this work was to characterize the mutagenicity of PM samples from a countryside city, Limeira, Brazil, which is influenced by heavy traffic and sugar cane biomass burning. Six samples of total PM were collected. Air mass backward trajectories were calculated. Organic extracts were assayed using the Salmonella/microsome microsuspension mutagenicity assay using TA98, YG1041, and TA1538, with and without metabolic activation (S9). YG1041 was the most sensitive strain and mutagenicity reached 9,700 revertants per m(3) without metabolic activation. Potency for TA1538 was higher than TA98, indicating that this strain should be considered in air mutagenicity studies. The increased response to YG1041 relative to TA98, and the decreased response with S9, suggests that nitroaromatics are the major contributors. Limeira is among the most mutagenic cities in the world. High mutagenicity in Limeira seems to occur when the air mass from the area of sugarcane production is mixed with air from the region impacted by anthropogenic activities such as traffic. An increase in the formation of nitro-polycyclic aromatic hydrocarbons may result from longer contact time between the aromatic compounds and the atmosphere with high NOx and ozone concentration, although more studies are required to confirm this hypothesis. Environ. Mol. Mutagen., 2015. © 2015 Wiley Periodicals, Inc.

Potential endocrinedisruptor activity of drinking water samples

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Optimization of in situ derivatization SPME by experimental design for GC-MS multi-residue analysis of pharmaceutical drugs in wastewater

This paper presents the development of a procedure, which enables the analysis of nine pharmaceutical drugs in wastewater using gas chromatography-mass spectrometry (GC-MS) associated with solid-phase microextraction (SPME) for the sample preparation. Experimental design was applied to optimize the in situ derivatization and the SPME extraction conditions. Ethyl chloroformate (ECF) was employed as derivatizing agent and polydimethylsiloxane-divinylbenzene (PDMS-DVB) as the SPME fiber coating. A fractional factorial design was used to evaluate the main factors for the in situ derivatization and SPME extraction. Thereafter, a Doehlert matrix design was applied to find out the best experimental conditions. The method presented a linear range from 0.5 to 10 mu g/L, and the intraday and interday precision were lower than 16%. Applicability of the method was verified from real influent and effluent samples of a wastewater treatment plant, as well as from samples of an industry wastewater and a river.

Mutagenicity of Blue Rayon Extracts of Fish Bile as a Biomarker in a Field Study

Blue rayon (BR) in combination with the Salmonella/microsome assay was used to evaluate the mutagenicity of fish bile samples. Specimens of Mugil curema from two sites were collected over a 1-year period. Piacaguera channel contains high concentrations of total polycyclic aromatic hydrocarbons (PAHs) and other contaminants, while Bertioga channel was considered the reference sites in this study. Bile was extracted with BR and tested with TA98, TA100, and YG1041 strains with and without S9 in dose response experiments. PAH metabolite equivalents were analyzed using reverse-phase high performance liquid chromatography /fluorescence. Higher mutagenic responses were observed for the contaminated site; YG1041 with S9 was the most sensitive strain/condition. Mutagenicity ranged from 3,900 to 14,000 rev./mg at the contaminated site and from 1,200 to 2,500 rev./mg of BR at the reference site. The responses of YG1041 were much higher in comparison with the TA98 indicating the presence of polycyclic compounds from the aromatic amine class that cause frameshift mutation. TA100 showed a positive mutagenic response that was enhanced following S9 treatment at both sites suggesting the presence of polycyclic compounds that require metabolic activation. benzo(a)pyrene, naphthalene, and phenanthrene metabolite equivalents were also higher in the bile of fish collected at the contaminated site. It was not possible to correlate the PAH metabolite quantities with the mutagenic potency. Thus, a combination of the Salmonella/microsome assay with YG1041 with S9 from BR bile extract seems to be an acceptable biomarker for monitoring the exposure of fish to mutagenic polycyclic compounds. Environ. Mal. Mutagen. 51:173-179, 2010. (C) 2009 Wiley-Liss, Inc.

An integrated approach to evaluate emerging contaminants in drinking water

The chemical stock of emerging contaminants in Brazilian drinking water is of great interest due to the poor water quality at surface water intakes. In addition, little is known about the effect of some contaminants, such as endocrine disrupting chemicals (EDCs), which may be present in both raw and treated water. The aim of this work was to evaluate selected emerging contaminants in Brazilian waters using both chemical and biological analyses. Sampling sites were established in different municipalities based upon raw water quality data. Estrone, 17 beta-estradiol, estriol, 17 alpha-ethinylestradiol, bisphenol A, 4-n-octylphenol and 4-n-nonylphenol were determined in the samples by liquid chromatography-tandem mass spectrometry. A yeast assay using a Saccharomyces cerevisiae bioluminescent bioreporter was used to evaluate the estrogenic activity of the water samples. The first integrated results revealed similarities between the two individual approaches, since higher values for the bioassay were accompanied by significant concentrations of some selected compounds in surface water samples. No estrogenicity was observed for drinking water samples. Our results also indicate that the usual paradigm of evaluating water quality by measuring selected EDCs in a given water sample via chemical analysis, needs to be reviewed since the observed estrogenicity of a water sample is now a better guiding parameter to the selection of samples and substances to be chemically investigated in further analysis. So far, the data bank produced in this work, i.e., the comparison between chemical burden and observed estrogenicity, is not yet sufficiently robust to fully guide this decision. (C) 2011 Elsevier B.V. All rights reserved.

Future water quality monitoring--adapting tools to deal with mixtures of pollutants in water resource management.

Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.

The SOLUTIONS project: challenges and responses for present and future emerging pollutants in land and water resources management.

SOLUTIONS (2013 to 2018) is a European Union Seventh Framework Programme Project (EU-FP7). The project aims to deliver a conceptual framework to support the evidence-based development of environmental policies with regard to water quality. SOLUTIONS will develop the tools for the identification, prioritisation and assessment of those water contaminants that may pose a risk to ecosystems and human health. To this end, a new generation of chemical and effect-based monitoring tools is developed and integrated with a full set of exposure, effect and risk assessment models. SOLUTIONS attempts to address legacy, present and future contamination by integrating monitoring and modelling based approaches with scenarios on future developments in society, economy and technology and thus in contamination. The project follows a solutions-oriented approach by addressing major problems of water and chemicals management and by assessing abatement options. SOLUTIONS takes advantage of the access to the infrastructure necessary to investigate the large basins of the Danube and Rhine as well as relevant Mediterranean basins as case studies, and puts major efforts on stakeholder dialogue and support. Particularly, the EU Water Framework Directive (WFD) Common Implementation Strategy (CIS) working groups, International River Commissions, and water works associations are directly supported with consistent guidance for the early detection, identification, prioritisation, and abatement of chemicals in the water cycle. SOLUTIONS will give a specific emphasis on concepts and tools for the impact and risk assessment of complex mixtures of emerging pollutants, their metabolites and transformation products. Analytical and effect-based screening tools will be applied together with ecological assessment tools for the identification of toxicants and their impacts. The SOLUTIONS approach is expected to provide transparent and evidence-based candidates or River Basin Specific Pollutants in the case study basins and to assist future review of priority pollutants under the WFD as well as potential abatement options.

Os efeitos das queimadas na Amazônia em nível celular e molecular

The Amazon holds over half of the planet's remaining tropical forests and comprises the largest biodiversity in the world, accounting for approximately 60 % of the Brazilian territory. However, deforestation fires in the region causes serious problems to exposed human. The aim of this study was to evaluate the chemical compounds as well as the cellular and molecular effects after exposure to organic material extracted from particulate matter less than 10 µm (PM10) in the Amazon region. As for the chemical composition, n-alkanes analysis showed a prevalence of anthropogenic influence during the fires in the region. In addition, there was a predominance of monosaccharides from biomass burning markers. Also, the Polycyclic Aromatic Hydrocarbons (PAH) and their derivatives have also been identified in samples collected in the Amazon. By using the PAH concentrations was possible to calculate the BaP-equivalent and it was found that the dibenz(a) anthracene contributes with 83% to potential carcinogenic risk. As for the potential mutagenic risk, the benzo (a) pyrene is the HPA that has a major contribution in this analysis. It may be noted that the retene was the most abundant PAH. This compound was genotoxic and cause death by necrosis in the human lung cells. In biological tests, the data showed that organic PM10 is capable of causing genetic damage in both plant cells and in human lung cells. This damage cause an arrest in the G1 phase of the cell cycle exposed, increasing the expression of p53 and p21. Additionally, the PM10 caused cell death by apoptosis, increasing the foci of histone - H2AX. Given these results, it is important to emphasize the reduction and better control of biomass burning in the Amazon region thus improving the quality of health of the population being exposed. As clearly stated recently by the World Health Organization, the reduction of air pollution could save millions of lives annually.

Spondias tuberosa Arr. (UMBU): estudo fitoquímico e avaliação do potencial anti-inflamatório

Spondias tuberosa Arruda (Anacardiaceae) is a fruitful tree popularly known as umbuzeiro, tapereba or umbu. It is a native and endemic species from Brazil, widespread in Brazilian Northeast. The species is important in folk medicine of the semi-arid Northeast, where it is mainly used to treat various inflammatory conditions, digestive problems as well as viral and bacterial infections. However, despite the common use in folk medicine, there are scarce pharmacological and phytochemicals studies that afford scientific evidence to its popular use. Therefore, this study aimed to characterize the chemical markers in S. tuberosa leaves extract, obtained by maceration ethanol:water (70:30, [v/v]), and evaluate its anti-inflammatory potential in vivo. The phytochemical profile in TLC analysis suggested the occurence of the flavonoids rutin and isoquercitrin. HPLC analysis enabled us to confirm the presence of flavonoids and also, were detected the phenolic acids, chlorogenic acid and caffeic acid. In addition was developed and validated a HPLC method to evaluate the content of the identified compounds in S. tuberosa leaves extract according to RDC 899/2003 of ANVISA and ICH Guidelines 2005. In order to evaluate the anti-inflammatory potential of S. tuberosa leaves extract, the peritonitis and paw edema models induced by carrageenan were used, administration i.p. in mice. The results highlighted the anti-inflammatory property in vivo at 125, 250 and 500 mg/kg since a decrease in leukocyte influx to the site of inflammation, diameter of the edema and the level of myeloperoxidase were observed when compared to the drug control dexamethasone (2 mg/kg, i.p. route). Taken together, the results pointed out S. tuberosa as a potential species for developing phytotherapic derivatives in according to its popular use. With regard to the characterization markers, chlorogenic acid, caffeic acid, rutin and isoquercitrin were identified and quantified in Spondias tuberosa leaves extract so they could be used in quality control analyses of the raw material and extracts of this species.