Measuring concentrations of a dye in the hemolymph of a marine amphipod: Development of a protocol for exposure assessment.

The increasing pollution of aquatic environments due to old and emerging contaminants requires the development of integrative methods for exposure assessment. Internal concentrations are a reliable way to estimate total exposure of contaminants originated from different routes (water, sediment, and food). We developed a protocol to evaluate the concentration of a dye, C.I. Disperse Red 1, in the hemolymph of Parhyale hawaiensis, a marine amphipod. LOD and LOQ were satisfactory to detect the dye in all hemolymph samples. The concentration detected in the hemolymph varied related to exposure time and dye concentration (0.003 to 0.086 µg mL-1). Polynomial regression model was the best fit. The protocol was reliable to detect and quantify dye exposure in marine amphipods and can be considered for future assessments of estuarine and marine regions under the influence of dye processing plants. The method possibly can be easily adapted to other amphipods and other azo dyes.

Assessment of the compounds formed by oxidative reaction between p-toluenediamine and p-aminophenol in hair dyeing processes: Detection, mutagenic and toxicological properties.

Previous studies have demonstrated the presence of precursors and coupling agents in wastewater from hair dyeing processes. The complex reaction involved in the oxidation of these compounds can generate extremely hazardous sub-products, leading to an increase in the mutagenicity and toxicity of wastewater. Without proper treatment, this highly toxic wastewater may find its way into the drinking water treatment plant. The present work aimed to investigate the main products generated after the oxidation reaction involving p-toluenediamine (PTD) and p-aminophenol (PAP) - precursors that widely used in the composition of commercial permanent hair dyes, under experimental conditions close to the routine hair dyeing process (in the presence and absence of hydrogen peroxide in ammoniacal medium), using spectroscopic techniques. The study also investigated the mutagenicity and toxicity of the products formed in the hairdressing wash water and conducted detection analysis to determine the presence of the precursors and Bandrowski's Base Derivative (BBD) in samples of wastewater, surface and drinking water using HPLC-DAD and linear voltammetry techniques. Based on this investigation, we identified several PTD and PAP self-oxidation products and eleven sub-products derived from the reaction between PTD and PAP. Assays conducted using Salmonella typhimurium YG1041, with and without activation-induced rat liver metabolism (S9), indicated mutagenicity of the reaction products in concentrations above 10.0 µg µL-1. The concentrations of PTD, PAP, and several reactions and oxidation products of these precursors were detected in wastewater and water samples.

Occurrence and risk assessment of organophosphate esters in urban rivers from Piracicaba watershed (Brazil).

Organophosphate esters (OPEs) are substances globally used as flame retardants and plasticizers that have been detected in all environmental compartments. This study aimed to evaluate the occurrence and sources of ten OPEs in the Piracicaba River Basin (Brazil). Twelve sampling sites were selected in five rivers with different pollution sources; six sampling campaigns were performed encompassing dry and wet seasons. ΣOPEs ranged from 0.12 to 6.2 µg L-1; the levels in urban areas were higher than in rural and non-urban areas, but no overall tendency concerning the seasonal effect on OPEs concentrations was observed. Tris(2-butoxyethyl) phosphate (TBOEP), tris(2-chloroisopropyl) phosphate (TCIPP), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were the most abundant and frequently detected compounds. Nine OPEs were detected at higher concentrations in a site affected by effluents from textile industries. An acute toxicity test using Daphnia similis was performed for tris(2-ethylhexyl) phosphate (TEHP) for the calculation of a preliminary predicted no effect concentration (PNEC). The risk quotient (RQ) approach was applied and risk to aquatic environment related to TEHP levels was observed in areas adjacent to textile industries, but more toxicity studies are required for the determination of a more reliable PNEC.

New benzotriazoles generated during textile dyeing process: Synthesis, hazard, water occurrence and aquatic risk assessment.

Phenylbenzotriazoles (PBTA) can be generated unintentionally during textile dyeing factories by reduction of dinitrophenylazo dyes and their subsequent chlorination in disinfection process. Eight non-chlorinated PBTAs (non-Cl PBTA) and their related chlorinated PBTAs have been found in rivers and presented mutagenic activity. No data on their aquatic toxicity are available. In this work, two new phenylbenzotriazoles, non-Cl PBTA-9 and PBTA-9, derived from the dye C.I. Disperse Violet 93 (DV93) were synthesized and chemically/toxicologically characterized. Both compounds were more mutagenic than the parental dye in the Salmonella/microsome assay in the presence of metabolic activation (S9). Mutagenicity studies in vivo with mammals would confirm their potential hazard to humans. The two compounds were acutely toxic to Daphnia similis. We developed an analytical method to simultaneously quantify non-Cl PBTA-9, PBTA-9 and DV93 in river waters. Non-Cl PBTA-9 was found in sites under influence of textile effluents but at concentrations that do not pose risk to the aquatic life according to the P-PNEC calculated based on the acute toxicity tests. PBTA-9 was not detected in any samples analyzed. More studies on the aquatic toxicity and water occurrence of PBTAs should be conducted to verify the relevance of this class of compounds as aquatic contaminants.

Assessment of p-aminophenol oxidation by simulating the process of hair dyeing and occurrence in hair salon wastewater and drinking water from treatment plant.

This work reports the study of oxidation reaction of p-aminophenol (PAP) in ammoniacal medium in dissolved atmospheric oxygen and hydrogen peroxide, simulating the process of hair dyeing with permanent dyes. The products formed, which included semi-quinoneimine radical, quinoneimine, dimers, trimers and tetramers, were identified by mass spectrometry, infrared spectroscopy, UV-vis spectrophotometry, and nuclear magnetic resonance of hydrogen. The process was found to involve an autoxidation mechanism. The mutagenicity of the products was carried out by Salmonella Typhimurium YG1041 assay, and the results indicated no mutagenic properties. The presence of PAP and its oxidative products in samples of wastewater collected from hairdressing salon effluent (WW), raw river water (RRW), and water inlet and outlet of drinking water treatment plant (DWTP) was analyzed by HPLC-DAD. PAP was detected in the collected samples of WW, water samples from DWTP (before and after treatment), at concentrations of 2.1 ± 0.5 mg L-1, 1.9 ± 0.3 × 10-3 mg L-1 and 1.3 ± 0.2 × 10-3 mg L-1, respectively. The reaction products, including dimers, trimers and tetramers were identified only in the WW sample; this shows that both the precursor in the sample and its derivatives were released into the wastewater.

Assessment of the autoxidation mechanism of p-toluenediamine by air and hydrogen peroxide and determination of mutagenic environmental contaminant in beauty salon effluent.

The present work investigated the autoxidation reaction of p-toluenediamine (PTD) - a precursor - widely used in permanent hair dyeing formulation, under experimental conditions close to the hair dyeing process (oxygen and/or peroxide in ammoniacal medium), by chromatographic and spectroscopic techniques. In additional, evaluated the mutagenicity of the PTD oxidation products and the presence of PTD and this products in wastewater from beauty salon, as well as in surface water and drinking water using HPLC coupled to a diode array detector and linear scan voltammetry. Through this study, it was possible the identification of semi-quinonediimine, quinonediimine, dimers (derived from toluenediamine), and trimer radical identified as Bandrowski's Base derivative (BBD) formed during autoxidation of PTD. Salmonella Typhimurium YG1041 assay with and without metabolic activation induced rat-liver (S9) indicated mutagenic activity for BBD. Levels of PTD were determined by the standard addition method in samples collected from the wastewater of a beauty salon, as well as from the water before and after treatment in a drinking water treatment plant (DWTP) reached concentrations of 2.08 ±â€¯0.21, 2.36 ±â€¯0.10 × 10-3, and 1.77 ±â€¯0.13 × 10-3 mg L-1, respectively. In addition, linear sweep voltammetry was used to monitor the BBD found at the concentration of 1.59 ±â€¯0.35 mg L-1 in wastewater collected from the beauty salon.

Nutrients, emerging pollutants and pesticides in a tropical urban reservoir: Spatial distributions and risk assessment.

Reservoirs located in urban areas suffer specific pressures related to human activities. Their monitoring, management, and protection requirements differ from reservoirs situated in non-urbanized areas. The objectives of this study were: (a) to determine the concentrations of select pesticides and emerging pollutants (EPs) present in an urban reservoir; (b) to describe their possible spatial distributions; and (c) to quantify the risks for aquatic life and safeguard drinking water supplies. For this purpose, the Guarapiranga reservoir was studied as an example of a multi-stressed urban reservoir in a tropical region. A total of 31 organic compounds (including pesticides, illicit drugs, pharmaceuticals, and endocrine disruptors) were analyzed twice over a period of one year, together with classical indicators of water quality. The physical and chemical data were treated using principal component analysis (PCA) to identify possible temporal or spatial patterns. Risk assessment was performed for biota and drinking water use, comparing maximum environmental concentrations (MECs) with the predicted no-effect concentrations (PNECs) or drinking water quality criteria (DWC), respectively. The results demonstrated the presence of pesticides and EPs, as well as pollution by high levels of nutrients and Chlorophyll a (Chl. a), during the study period. The nutrients and Trophic State Index (TSI) showed gradients in the reservoir and regional distributions, while the pesticides and EPs only clearly showed this pattern in the dry season. The concentrations and distributions of the pesticides and EPs therefore showed seasonality. These findings suggested that the two groups of pollutants (EPs+pesticides and nutrients) possessed different sources and behavior and were not always correlated in the reservoir studied. In the studied period, no risk was observed in raw water for drinking water use, but carbendazim, imidacloprid, and BPA showed risks for the biota in the reservoir.

Occurrence and risk assessment of an azo dye - The case of Disperse Red 1.

Water 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(-1) was proposed, based on the most sensitive chronic endpoint for Daphnia similis. A short-term PNEC of 1800 ng L(-1) 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 50-500 ng L(-1). The risk quotients for DR1 obtained in this work 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.

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.

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 30min of irradiation, when a dye solution 1×10(-5)molL(-1) was submitted to an energy dose of 37.8Jcm(-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 µg/plate [DOSAGE ERROR CORRECTED] and the solutions obtained after exposure to UV irradiation, did not present mutagenic activity for TA98 and TA100 with and without S9.

Assessment of by-products of chlorination and photoelectrocatalytic chlorination of an azo dye.

The present work describes a more efficient methodology for the chlorination of water containing disperse dyes, where the chlorinated byproducts identified by mass spectra are compared. For this investigation, we tested the degradation of CI Disperse Blue 291 dye, 2-[(2-Bromo-4,6-dinitrophenyl)azo]-5-(diethylamino)-4-methoxyacetanilide) a commercial azo dye with mutagenic properties. The present work evaluates the photoelectrocatalytic efficiency of removing the CI Disperse Blue 291 dye from a wastewater of the textile industry. We employed NaCl as a supporting electrolyte. It should be noted that photoelectrocatalytic techniques are non-conventional method of generating chlorine radicals. The by-products formed in this process were analyzed using spectrophotometry, liquid chromatography, dissolved organic carbon, mass spectral analysis and mutagenicity assays. The process efficiency was compared with the conventional chlorination process adopted during sewage and effluents treatment processes. This conventional chlorination process is less efficient in removing color, total organic carbon than the photoelectrochemistry technique. Furthermore, we shall demonstrate that the mutagenicity of the generated by-products obtained using photoelectrocatalysis is completely different from that obtained by the conventional oxidation of chloride ions in the drinking water treatment process.

Assessment of water contamination caused by a mutagenic textile effluent/dyehouse effluent bearing disperse dyes.

High performance liquid chromatography coupled to a diode array detector method was developed to detect disperse dyes in water samples over the range 0.50-35 ng, with detection limits of 0.09 ng, 0.84 ng and 0.08 ng, respectively, with good repeatability and accuracy. This study identifies the disperse azo dyes C.I. Disperse Blue 373, C.I. Disperse Orange 37 and Disperse Violet 93 as components of a commercial dye formulation assigned as Dispersol Black Dye (CVS) used in the textile industry for dyeing synthetic fibers that are contributing to the mutagenicity found in the Cristais River, São Paulo, Brazil. High performance liquid chromatography coupled to a diode array detector was applied to monitor the occurrence of these dyes in: (1) the treated industrial effluent, (2) raw river water, (3) treated river water, and (4) the sludge produced by a Drinking Water Treatment Plant (DWTP) which is located 6 km downstream from the textile industrial discharge, where dyes' concentrations changed from 1.65 ng L(-1) to 316 microL(-1).

Photoelectrocatalytic oxidation of remazol turquoise blue and toxicological assessment of its oxidation products.

The ability of photoelectrocatalytic oxidation to degrade the commercially important copper-phtalocyanine dye, remazol turquoise blue 15 (RTB) was investigated. The best experimental condition was optimized, evaluating the performance of Ti/TiO2 thin-film electrodes prepared by sol-gel method in the decolourization of 32 mg L(-1) RTB dye in 0.5 mol L(-1) Na2SO4 pH 8 and applied potential of +1.5 V versus SCE under UV irradiation. Spectrophotometric measurements, high performance liquid chromatography, dissolved organic carbon (TOC) evaluation and stripping analysis of yielding solution obtained after 3 h of photoelectrolysis leads to 100% of absorbance removal from wavelength of 250-800 nm, 79.6% of TOC reduction and the releasing of up to 54.6% dye-bound copper (0.85 mg L(-1)) into the solution. Both, original and oxidized dye solution did not presented mutagenic activity with the strains TA98 and TA100 of Salmonella in the presence and absence of S9 mix at the tested doses. Nevertheless, the yielding photoelectrocatalytic oxidized solution showed an increase in the acute toxicity for Vibrio fischeri bacteria, explained by copper liberation during treatment.