Emerging pollutants in textile wastewater: an ecotoxicological assessment focusing on surfactants.

Water and several chemicals, including dyestuffs, surfactants, acids, and salts, are required during textile dyeing processes. Surfactants are harmful to the aquatic environment and induce several negative biological effects in exposed biota. In this context, the present study aimed to assess acute effects of five surfactants, comprising anionic and nonionic classes, and other auxiliary products used in fiber dyeing processes to aquatic organisms Vibrio fischeri (bacteria) and Daphnia similis (cladocerans). The toxicities of binary surfactant mixtures containing the anionic surfactant dodecylbenzene sulfonate + nonionic fatty alcohol ethoxylate and dodecylbenzene sulfonate + nonionic alkylene oxide were also evaluated. Nonionic surfactants were more toxic than anionic compounds for both organisms. Acute nonionic toxicity ranged from 1.3 mg/L (fatty alcohol ethoxylate surfactant) to 2.6 mg/L (ethoxylate surfactant) for V. fischeri and from 1.9 mg/L (alkylene oxide surfactant) to 12.5 mg/L (alkyl aryl ethoxylated and aromatic sulfonate surfactant) for D. similis, while the anionic dodecylbenzene sulfonate EC50s were determined as 66.2 mg/L and 19.7 mg/L, respectively. Both mixtures were very toxic for the exposed organisms: the EC50 average in the anionic + fatty alcohol ethoxylate mixture was of 1.0 mg/L ± 0.11 for V. fischeri and 4.09 mg/L ± 0.69 for D. similis. While the anionic + alkylene oxide mixture, EC50 of 3.34 mg/L for D. similis and 3.60 mg/L for V. fischeri. These toxicity data suggested that the concentration addition was the best model to explain the action that is more likely to occur for mixture for the dodecylbenzene sulfonate and alkylene oxide mixtures in both organisms. Our findings also suggest that textile wastewater surfactants may interact and produce different responses in aquatic organisms, such as synergism and antagonism. Ecotoxicological assays provide relevant information concerning hazardous pollutants, which may then be adequately treated and suitably managed to reduce toxic loads, associated to suitable management plans.

Acute and chronic ecotoxicological effects of pharmaceuticals and their mixtures in Daphnia similis.

Pharmaceuticals have increasingly received attention from the scientific community due to their growing intake, improved detection and potential ecological risks. Several pharmaceuticals, including antidepressants, anti-inflammatory and antidiabetic compounds and antibiotics, have been described as contaminants in different water matrices. In this context, the aim of the present study was to assess the acute and chronic effects of four classes of pharmaceuticals (acetylsalicylic acid, fluoxetine, metformin and ciprofloxacin) individually and in binary and quartenary mixture. Furthermore, the toxicity of binary mixtures containing the antidepressant fluoxetine was also evaluated. The results of the single acute and chronic toxicity assays indicate lower acetylsalicylic acid and higher fluoxetine toxicity towards Daphnia similis. Regarding the evaluated mixture toxicity, the nature of potential toxicological interactions was predicted by applying mathematical concentration addition and independent action models. The findings revealed both antagonistic and synergistic features, depending on the applied amounts and doses. Finally, the chronic assays performed with the quaternary mixture indicated the presence of a hormetic effect at low concentrations. In sum, the present study demonstrated that the effects of individual pharmaceuticals can underestimate the risk level of these contaminants in the environment.

Multiple adverse effects of textile effluents and reactive Red 239 dye to aquatic organisms.

Textile dyeing consumes high volumes of water, generating proportional number of colored effluents which contain several hazardous chemical. These contaminants can implicate in significant changes in aquatic environmental, including several adverse effects to organisms in different trophic levels. The present study was developed to assess the ecotoxicological effects of textile effluent samples and reactive Red 239 dye (used in cotton dyeing) to aquatic organisms Vibrio fischeri bacteria, Daphnia similis crustacean, and Biomphalaria glabrata snail (adults and embryos). Chronic assays with lethal and sublethal effects for Daphnia similis were included and performed only for textile effluents samples. The mutagenicity was also evaluated with Salmonella/microsome assay (TA98, TA100, and YG1041 strains). V. fischeri bacteria was the most sensitive to reactive Red 239 dye (EC50 = 10.14 mg L-1) followed by mollusk embryos at all stages (EC50 = 116.41 to 124.14 mg L-1), D. similis (EC50= 389.42 mg L-1), and less sensitive to adult snails (LC50= 517.19 mg L-1). The textile effluent was toxic for all exposed organisms [E(L)C50 < 15%] and B. glabrata embryos showed different responses in the early stages of blastulae and gastrulae (EC50 = 7.60 and 7.08%) compared to advanced development stages trochophore and veliger (EC50 = 21.56 and 29.32%). Developmental and sublethal effects in B. glabrata embryos and D. similis were evidenced. In the chronic assay with effluent, the EC10/NOEC = 3% was obtained. Mutagenic effects were not detected for dye aqueous solutions neither for effluents samples. These data confirmed the importance of evaluating the effects in aquatic organisms from different trophic levels and reinforce the need for environmental aquatic protection.

Is ionizing radiation effective in removing pharmaceuticals from wastewater?

Wastewater and effluent discharges are the main causes of receiving water body pollution and important challenges in water quality management. Among the emerging contaminants, pharmaceuticals have increasingly drawn attention due to their incomplete removal during conventional biological treatment, inducing potential and actual risks to living organisms following residue discharges in river effluent. Electron beam irradiation (EBI) is a clean process technology for organic compound degradation and mineralization, as well as persistent pollutant detoxification. This study aimed to evaluate EBI effects on the degradation and toxicity removal of anti-inflammatory aspirin (ASA) in a single solution and in a fluoxetine (FLX) mixture. Results indicate that 98% of the single aspirin was degraded at 5.0 kGy. Aspirin toxicity to Daphnia similis, however, increased with increasing absorbed dose (1.0 to 5.0 kGy), possibly as a result of the presence of H2O2 and other byproducts formed during the oxidation process. Regarding the irradiated mixture, complete degradation was achieved for both pharmaceuticals. Toxicity removals for the mixture were of 56.2 ± 0.9% and 58.8 ± 5.4% for 1.0 and 2.5 kGy, respectively. These findings demonstrate that EBI can be an interesting alternative process to be applied as a pre-treatment followed by biological treatment.

Multiple adverse effects of textile effluents and reactive Red 239 dye to aquatic organisms

Textile dyeing consumes high volumes of water, generating proportional number of colored effluents which contain several hazardous chemical. These contaminants can implicate in significant changes in aquatic environmental, including several adverse effects to organisms in different trophic levels. The present study was developed to assess the ecotoxicological effects of textile effluent samples and reactive Red 239 dye (used in cotton dyeing) to aquatic organisms Vibrio fischeri bacteria, Daphnia similis crustacean, and Biomphalaria glabrata snail (adults and embryos). Chronic assays with lethal and sublethal effects for Daphnia similis were included and performed only for textile effluents samples. The mutagenicity was also evaluated with Salmonella/microsome assay (TA98, TA100, and YG1041 strains). V. fischeri bacteria was the most sensitive to reactive Red 239 dye (EC50 = 10.14 mg L−1) followed by mollusk embryos at all stages (EC50 = 116.41 to 124.14 mg L−1), D. similis (EC50= 389.42 mg L−1), and less sensitive to adult snails (LC50= 517.19 mg L−1). The textile effluent was toxic for all exposed organisms [E(L)C50 < 15%] and B. glabrata embryos showed different responses in the early stages of blastulae and gastrulae (EC50 = 7.60 and 7.08%) compared to advanced development stages trochophore and veliger (EC50 = 21.56 and 29.32%). Developmental and sublethal effects in B. glabrata embryos and D. similis were evidenced. In the chronic assay with effluent, the EC10/NOEC = 3% was obtained. Mutagenic effects were not detected for dye aqueous solutions neither for effluents samples. These data confirmed the importance of evaluating the effects in aquatic organisms from different trophic levels and reinforce the need for environmental aquatic protection.

HSP70 expression in Biomphalaria glabrata snails exposed to cadmium.

In this study, the effects of the heavy metal cadmium on the stress protein HSP70 are investigated in freshwater mollusks Biomphalaria glabrata. Adult snails were exposed for 96h to CdCl2 at concentrations ranging from 0.09 to 0.7mgL-1 (LC50/96h=0.34 (0.30-0.37). Time and concentration-dependent increases in the expression of HSP70 were observed at sub-lethal levels in the immunoblotting assay. Further, an increased survival to a lethal heat shock was observed in animals pre-exposed to a nonlethal concentration of cadmium, evidencing the induction of acquired tolerance. The present study demonstrated the inducibility of B. glabrata HSP70 by cadmium, a relevant environmental contaminant, at non-lethal levels, providing evidences that the assessment of HSP70 in B. glabrata can be regarded as a suitable biomarker for ecotoxicological studies.

HSP70 expression in Biomphalaria glabrata snails exposed to cadmium

In this study, the effects of the heavy metal cadmium on the stress protein HSP70 are investigated in freshwater mollusks Biomphalaria glabrata. Adult snails were exposed for 96 h to CdCl2 at concentrations ranging from 0.09 to 0.7 mg L-1 (LC50/96 (h) = 0.34 (0.30-0.37). Time and concentration-dependent increases in the expression of HSP70 were observed at sub-lethal levels in the immunoblotting assay. Further, an increased survival to a lethal heat shock was observed in animals pre-exposed to a nonlethal concentration of cadmium, evidencing the induction of acquired tolerance. The present study demonstrated the inducibility of B. glabrata HSP70 by cadmium, a relevant environmental contaminant, at non-lethal levels, providing evidences that the assessment of HSP70 in B. glabrata can be regarded as a suitable biomarker for ecotoxicological studies.

Degradation and acute toxicity removal of the antidepressant Fluoxetine (Prozac(®)) in aqueous systems by electron beam irradiation.

Electron beam irradiation (EBI) has been considered an advanced technology for the treatment of water and wastewater, whereas very few previous investigations reported its use for removing pharmaceutical pollutants. In this study, the degradation of fluoxetine (FLX), an antidepressant marketed as Prozac(®), was investigated by using EBI at FLX initial concentration of 19.4 ± 0.2 mg L(-1). More than 90 % FLX degradation was achieved at 0.5 kGy, with FLX below the detection limit (0.012 mg L(-1)) at doses higher than 2.5 kGy. The elucidation of organic byproducts performed using direct injection mass spectrometry, along with the results of ion chromatography, indicated hydroxylation of FLX molecules with release of fluoride and nitrate anions. Nevertheless, about 80 % of the total organic carbon concentration remained even for 7.5 kGy or higher doses. The decreases in acute toxicity achieved 86.8 and 9.6 % for Daphnia similis and Vibrio fischeri after EBI exposure at 5 kGy, respectively. These results suggest that EBI could be an alternative to eliminate FLX and to decrease residual toxicity from wastewater generated in pharmaceutical formulation facilities, although further investigation is needed for correlating the FLX degradation mechanism with the toxicity results.

Developmental toxicity, acute toxicity and mutagenicity testing in freshwater snails Biomphalaria glabrata (Mollusca: Gastropoda) exposed to chromium and water samples.

A protocol combining acute toxicity, developmental toxicity and mutagenicity analysis in freshwater snail Biomphalaria glabrata for application in ecotoxicological studies is described. For acute toxicity testing, LC50 and EC50 values were determined; dominant lethal mutations induction was the endpoint for mutagenicity analysis. Reference toxicant potassium dichromate (K2Cr2O7) was used to characterize B. glabrata sensitivity for toxicity and cyclophosphamide to mutagenicity testing purposes. Compared to other relevant freshwater species, B. glabrata showed high sensitivity: the lowest EC50 value was obtained with embryos at veliger stage (5.76mg/L). To assess the model applicability for environmental studies, influent and effluent water samples from a wastewater treatment plant were evaluated. Gastropod sensitivity was assessed in comparison to the standardized bioassay with Daphnia similis exposed to the same water samples. Sampling sites identified as toxic to daphnids were also detected by snails, showing a qualitatively similar sensitivity suggesting that B. glabrata is a suitable test species for freshwater monitoring. Holding procedures and protocols implemented for toxicity and developmental bioassays showed to be in compliance with international standards for intra-laboratory precision. Thereby, we are proposing this system for application in ecotoxicological studies.

Photolysis of atrazine in aqueous solution: role of process variables and reactive oxygen species.

Photochemical advanced oxidation processes have been considered for the treatment of water and wastewater containing the herbicide atrazine (ATZ), a possible human carcinogen and endocrine disruptor. In this study, we investigated the effects of the photon emission rate and initial concentration on ATZ photolysis at 254 nm, an issue not usually detailed in literature. Moreover, the role of reactive oxygen species (ROS) is discussed. Photon emission rates in the range 0.87 × 10(18)-3.6 × 10(18) photons L(-1) s(-1) and [ATZ]0 = 5 and 20 mg L(-1) were used. The results showed more than 65 % of ATZ removal after 30 min. ATZ photolysis followed apparent first-order kinetics with k values and percent removals decreasing with increasing herbicide initial concentration. A fivefold linear increase in specific degradation rate constants with photon emission rate was observed. Also, regardless the presence of persistent degradation products, toxicity was efficiently removed after 60-min exposure to UV radiation. Experiments confirmed a noticeable contribution of singlet oxygen and radical species to atrazine degradation during photolysis. These results may help understand the behavior of atrazine in different UV-driven photochemical degradation treatment processes.

Avaliação da toxicidade em sedimento do rioCubatão-SP / Toxicity assessment into sediments from Cubatão River-SP

O presente trabalho visou avaliar efeitos agudos e crônicos em amostras de sedimento do rio Cubatão e dois de seusafluentes (Perequê e Pilões), por meio de ensaios ecotoxicológicos. Os organismos-teste foram a Hyalella azteca para avaliaçãode sedimento integral. A análise de crescimento corpóreo do organismo também foi realizada. As amostras foramcoletadas entre 2010 e 2011 (quatro campanhas), em nove pontos da Bacia do rio Cubatão. Os ensaios de toxicidade paraefeitos agudos do sedimento integral em H. azteca resultaram em toxicidade para as amostras de P2 e P5 (2ª e 4ª campanhas),com mortalidade superior a 50% dos organismos expostos. A análise de crescimento corpóreo identificou menorcrescimento nos organismos expostos ao sedimento proveniente dos locais P4 e P5, onde ocorreu a industrialização naregião estudada.

The present paper assessed acute and chronic biological effects at sediment samples from Cubatão River and two othercontributors (Perequê and Pilões Rivers), by using ecotoxicity assays. Hyalella azteca were exposed to integral sediments.Body growing size was also determined. The samples were collected in 2010 and 2011 (four data) and nine different siteswere included, representing the Cubatão River Basin. The acute effects for Hyalella azteca were obtained at P2 and P5 (2ªand 4ª samplings), with mortality higher than 50% of the total number of exposed organisms. Organisms body size analysisdetected lower growing rates at sites P4 and P5, places identified as pertaining to the mainly industrialized sites.

Schistosomiasis control using piplartine against Biomphalaria glabrata at different developmental stages.

BACKGROUND: Schistosomiasis is one of the most significant diseases in tropical countries and affects almost 200 million people worldwide. The application of molluscicides to eliminate the parasite's intermediate host, Biomphalaria glabrata, from infected water supplies is one strategy currently being used to control the disease. Previous studies have shown a potent molluscicidal activity of crude extracts from Piper species, with extracts from Piper tuberculatum being among the most active. METHODS AND FINDINGS: The molluscicidal activity of P. tuberculatum was monitored on methanolic extracts from different organs (roots, leaves, fruit and stems). The compounds responsible for the molluscicidal activity were identified using (1)H NMR and ESIMS data and multivariate analyses, including principal component analysis and partial least squares. These results indicated that the high molluscicidal activity displayed by root extracts (LC50 20.28 µg/ml) was due to the presence of piplartine, a well-known biologically-active amide. Piplartine was isolated from P. tuberculatum root extracts, and the molluscicidal activity of this compound on adults and embryos of B. glabrata was determined. The compound displayed potent activity against all developmental stages of B. glabrata. Next, the environmental toxicity of piplartine was evaluated using the microcrustacean Daphnia similis (LC50 7.32 µg/ml) and the fish Danio rerio (1.69 µg/ml). The toxicity to these organisms was less compared with the toxicity of niclosamide, a commercial molluscicide. CONCLUSIONS: The development of a new, natural molluscicide is highly desirable, particularly because the commercially available molluscicide niclosamide is highly toxic to some organisms in the environment (LC50 0.25 µg/ml to D. similis and 0.12 µg/ml to D. rerio). Thus, piplartine is a potential candidate for a natural molluscicide that has been extracted from a tropical plant species and showed less toxic to environment.

Contaminação das águas por resíduos de medicamentos: ênfase ao cloridrato de fluoxetina / Water contamination by drugs residues, with an emphasis influoxetine chloridrate

Este trabalho teve como objetivo fazer um levantamento sucinto da presença de resíduos de medicamentos no ambiente aquático e em estações de tratamento de esgotos, bem como discutir a necessidade iminente de ações que possam auxiliar nesse tipo de contaminação ao reduzir as emissões, orientar o gerenciamento adequado de resíduos de farmácia e de descarte em domicílios. Além disso, foram apresentados resultados de ensaios ecotoxicológicos empregados na avaliação de efeitos da fluoxetina em Vibrio fischeri e em H. azteca, organismos aquáticos frequentemente expostos a contaminantes ambientais. Dos resultados obtidos, observou-se que a partir de 0,3 mg.l-1 de cloridrato de fluoxetina ocorreu mortalidade em H. azteca, enquanto que a inibição de fotoluminescência em Vibrio fischeri foi obtida a partir de 30 mg.l-1. Nesse último caso, os menores valores de CE50 demonstraram toxicidade mais elevada nos ensaios com o produto genérico.

The objective of this paper was to review data on residues of medical products in aquatic environments and at waste water treatment plants. Secondarily the paper presents a discussion about the need for a good management of drugs residues and effluents generated by this sector. Bringing the evidences of environmental possible damages reported by ecotoxicity data on the effects of fluoxetine to Vibrio fischeri and H. azteca, aquatic organisms daily exposed to environmental contaminants. From the results we observed that 0.3 mg.l-1 of fluoxetine hidrochloride induced lethality to H. azteca and 30 mg.l-1 reduced the luminescence of Vibrio fischeri. This assay evidenced higher toxicity when we used the “generic” product.