Daniele Maia Bila

Degradation and estrogenic activity removal of 17β-estradiol and 17α-ethinylestradiol by ozonation and O3/H2O2

This work investigated the degradation of a natural (17beta-estradiol) and a synthetic (17alpha-ethinylestradiol) estrogens (pure or in the mixture) and the removal of estrogenic activity by the ozonation and O3/H2O2 process in three different pHs (3, 7 and 11). The effect of oxidation via OH radical was evaluated adding a radical scavenger (t-butanol) in the medium. Estrogenic activity was performed using the YES assay. 17beta-estradiol and 17alpha-ethinylestradiol presented similar estrogenic potential and the association of these estrogens resulted in an addictive effect for estrogenic activity. Ozonation and O3/H2O2 processes were effective in removing the estrogens in aqueous solution. In the mixture at pH 11, removals were higher than 98% and 96% for 17beta-estradiol and 17alpha-ethinylestradiol, respectively. In pH 3, 17beta-estradiol and 17alpha-ethinylestradiol removals were 100% and 99.7%, respectively. When estrogens were treated separately, the removals in pH 11 were superior to 99.7 and 98.8%, while in pH 3 were 100% and 99.5% for 17beta-estradiol and 17alpha-ethinylestradiol, respectively. 17alpha-ethinylestradiol has been always removed at lower rates (pure or in the mixture) for all applied conditions. Estrogenic activity was completely removed in pH 3 for ozonation or O3/H2O2. The samples oxidized in pH 11 presented higher estrogenic activity than those in pH 7. Estrogens removal was lower at pHs 7 and 11, when the scavenger was added to the media. The higher estrogen residual concentrations found in ozonation in presence of tert-butanol are contributing for higher estrogenic activity observed in pHs 7 and 11. By-products with estrogenic activity were formed by oxidation via OH radical. Only a few compounds could be identified in pHs 7 and 11 and they have a phenolic ring, which, probably is contributing to the estrogenic activity observed.

Analysis of estrogenic activity in environmental waters in Rio de Janeiro state (Brazil) using the yeast estrogen screen

The estrogenicity of waters collected from an important hydrological system in Brazil (Paraiba do Sul and Guandu Rivers) was assessed using the yeast estrogen screen (YES) assay. Sampling was performed in rivers and at the outlets of conventional water treatment plants (WTP). The removal of estrogenic activity by ozonation and chlorination after conventional water treatment (clarification and sand filtration) was investigated employing samples of the Guandu River spiked with estrogens and bisphenol A (BPA). The results revealed a preoccupying incidence of estrogenic activity at levels higher than 1ngL(-1) along some points of the rivers. Another matter of concern was the number of samples from WTPs presenting estrogenicity surpassing 1ngL(-1). The oxidation techniques (ozonation and chlorination) were effective for the removal of estrogenic activity and the combination of both techniques led to good results using less amounts of oxidants.

Determination of water quality, toxicity and estrogenic activity in a nearshore marine environment in Rio de Janeiro, Southeastern Brazil

Endocrine disrupting compounds (EDCs) can be found in domestic sewage, wastewater treatment plant effluents, natural water, rivers, lakes and in the marine environment. Jurujuba Sound, located in the state of Rio de Janeiro, Southeastern Brazil, receives untreated sewage into its waters, one the main sources of aquatic contamination in this area. In this context, the aim of the present study was to evaluate the estrogenic potential of water sampled from different depths and from areas with differential contamination levels throughout Jurujuba Sound. Water quality was evaluated and acute toxicity assays using Allviibrio fischeri were conducted, while estrogenic activity of the water samples was determined by a Yeast Estrogen Screening assay (YES). Water quality was mostly within the limits established for marine waters by the Brazilian legislation, with only DOC and ammoniacal nitrogen levels above the maximum permissible limits. No acute toxicity effects were observed in the Allivibrio fisheri assay. The YES assay detected moderate estrogenic activity in bottom water samples from 3 sampling stations, ranging from 0.5 to 3.2ngL-1, as well as in one surface water sample. Estrogenic activity was most frequently observed in samples from the bottom of the water column, indicating adsorption of estrogenic compounds to the sediment.

Regulation of the synthetic estrogen 17α-ethinylestradiol in water bodies in Europe, the United States, and Brazil

O estrogenio sintetico 17α-etinilestradiol, principal componente utilizado em formulacoes de contraceptivos orais, tem sido apontado como um dos principais compostos responsaveis por provocar efeitos adversos no sistema endocrino de varias especies. O objetivo deste estudo foi analisar o estado da arte dos dispositivos legais e normativos referentes ao controle desse estrogenio sintetico nas aguas da Europa e dos Estados Unidos, e tracar um paralelo com a realidade brasileira. No geral, os paises tem buscado ampliar a regulamentacao e monitoramento de alguns micropoluentes emergentes que antes nao eram objeto de atencao por parte dos dispositivos legais. A Europa esta mais avancada no que tange a qualidade dos corpos hidricos, enquanto que nos Estados Unidos esta substância e alvo de regulamentacao apenas para a agua destinada ao consumo humano. No Brasil, ainda nao ha nenhum dispositivo legal ou normativo que aborde esse estrogenio, o que pode ser associado a uma baixa maturidade do sistema brasileiro quanto ao controle de poluentes hidricos.The synthetic estrogen 17α-ethinylestradiol, the principal component of oral contraceptives, has been identified as one of the main compounds accounting for adverse effects on the endocrine system in various species. This study aimed to analyze the state-of-the-art in legislation and guidelines for the control of this synthetic estrogen in water bodies in Europe and the United States and to draw a parallel with the Brazilian reality. Countries have generally attempted to expand the regulation and monitoring of certain emerging micropollutants not previously covered by legislation. Europe is more advanced in terms of water quality, while in the United States this estrogen is only regulated in water for human consumption. Brazil still lacks legal provisions or standards for this estrogen, which can be explained by the relatively limited maturity of the countrys system for controlling water pollutants.

Sequential treatment of an old-landfill leachate

This work investigates the performance of combined techniques applied to the treatment of an old-landfill leachate, which presents high salinity, low biodegradability (BOD5/COD around 0.05) and high ammonia concentration. Three sequences of processes were employed, including coagulation/flocculation, chemical oxidation, biological treatment and ammonia stripping. The association of coagulation/flocculation with ozonation promoted an increase on landfill leachate biodegradability (BOD5/COD raised to 0.20). Ammonia stripping was an essential procedure for reducing toxic effects on the biological treatment step. The treatment sequence combining coagulation/flocculation, ammonia stripping, ozonation and biological treatment led to high global removals of COD (92%) and DOC (95%).

Evaluation of the biodegradability and toxicity of landfill leachates after pretreatment using advanced oxidative processes

Leachate from urban solid waste landfills is a complex mixture of organic and inorganic substances that cause damage to the environment, due to the high concentration of recalcitrant organic matter and toxicity. The objective of this study was to apply advanced oxidation processes (AOP), namely the dark Fenton and solar photo-Fenton processes, to young and old landfill leachates prior to biological treatment. The leachates were obtained from the Seropedica and Gramacho landfill sites, respectively, located in Rio de Janeiro State, Brazil. For the two Fenton processes, different conditions of pH (1.5, 3.0 and 5.0) and Fe2+: H2O2 ratio (1:2, 1:5 and 1:10) were evaluated. Biodegradability was evaluated using the Zahn-Wellens methodology and Aliivibrio fischeri acute toxicity tests were conducted in order to predict the toxicity in the activated sludge. The best conditions for both Fenton processes were pH of 3.0 and Fe2+: H2O2 and CODRAW:H2O2 mass ratios of 1:5 and 1:1, respectively. The solar photo-Fenton process was more effective at improving the quality for both leachates, reaching COD, TOC and abs 254 nm reductions of 82%, 85% and 96.3%, respectively, for the Seropedica landfill leachate. In the case of the Gramacho landfill leachate, the corresponding reductions were 78.2, 80.7% and 91.1%, respectively. The biodegradability results for the untreated leachates from the Seropedica and Gramacho sites were 65% and 30% respectively. The biodegradability of both leachates was improved by the Fenton processes, especially the solar photo-Fenton process, which increased the leachate biodegradability to 89% (Seropedica) and 69% (Gramacho). For both leachates, a greater reduction in the acute toxicity was achieved with the solar photo-Fenton compared to the dark-Fenton process. The Seropedica landfill leachate showed high toxicity (EC50 = 33%, 15 min), after the dark Fenton and solar photo Fenton processes, with EC50 values of 81 and 91%, respectively. In the case of Gramacho landfill leachate toxicity, the EC50 value of the raw leachate was 13%, whereas after the dark Fenton and solar photo Fenton processes the corresponding values were 54% and 59%, respectively. These results indicate that the Fenton process (especially solar photo-Fenton), was efficient in terms of increasing the biodegradability and reducing the toxicity of the leachate. This is important in relation to protecting the microbiological community in the activated sludge process.

Evaluation of humic substances removal from leachates originating from solid waste landfills in Rio de Janeiro State, Brazil

ABSTRACT This study aimed to evaluate the use of coagulation/flocculation and Fenton processes for the removal of the recalcitrant component, in particular humic substances, from two different leachates generated in the Gericinó and Gramacho landfills in Rio de Janeiro State (Brazil). A coagulation/flocculation process, using FeCl3·6H2O as the coagulant, was applied to the two leachate samples. In the case of the leachate from Gericinó landfill, the treatment removed 93% of color, 71% of TOC, 69% of COD, 76% of HS, 73% of humic acids (HA) and 82% of fulvic acids (FA). In addition, there was a 75% reduction in the absorbance at 254 nm, using 3,000 mg L−1 of coagulant. In the case of the leachate from Gramacho landfill, the treatment removed 91% of color, 69% of TOC, 68% of COD, 77% of HS, 75% of HA and 80% of FA. In addition, there was a 70% reduction in the absorbance at 254 nm using the same concentration of coagulant (3,000 mg L−1). The Fenton processes, using FeSO4·7H2O and H2O2 in a ratio of 1:5, were also applied to the two leachate samples. In the case of the Gericinó leachate, the Fenton treatment removed 95% of color, 75% of TOC, 68% of COD, 82% of HS, 77% of HA and 93% of FA. In addition, there was a 93% reduction in the absorbance at 254 nm. In the case of the Gramacho leachate, the Fenton treatment removed 93% of color, 73% of TOC, 71% of COD, 81% of HS, 76% of HA, 90% of FA, and there was an 84% reduction in the absorbance at 254 nm. The results of humic substances, color, organic matter and aromatic organic matter (absorbance at 254 nm) demonstrate that the coagulation/flocculation and Fenton processes were efficient in the removal of recalcitrant organic matter from landfill leachates.

Ammonium and BPA Sorption for GCL

The trend of using GCL for liners from MSW landfill in developing countries is growing. Leachate in general presents high ammonium and chlorides concentrations and there are noticeable with high migration possibility. Recent studies indicate a presence of several emerging organic compounds, among them bisphenol A (BPA) which is considered an endocrine disrupting chemical (EDCs). This article presents batch tests for bentonite and geotextile, carried out separately using ammonium and BPA mono solutions with maximum concentrations in the range of 1600–1800 mg.L−1 and 1000 pg.L−1, respectively. The maximum value of ammonium adsorbed by bentonite was 10,61 mg.L−1, and no sorption for geotextile. The BPA sorption tended to 3,72 mg.L−1 for bentonite whereas for the geotextile BPA adsorbed was in order of 6,52 pg.L−1.

Evaluation of reduction estrogenic activity in the combined treatment of landfill leachate and sanitary sewage

Combined treatment of urban solid waste leachate and domestic sewage has emerged in Brazil and worldwide as an alternative to minimize the difficulties of treating landfill leachate. Landfill leachate is a complex matrix of organic and inorganic substances, recalcitrant material and xenobiotic organic compounds that are considered to be highly toxic, as well as endocrine disrupting compounds (EDC) that contribute to increased estrogenic activity. Although combined treatment is feasible for removal of organic matter, ammonia and toxicity, the efficiency of the removal of estrogenic substance is poorly investigated. In this study, the activated sludge process in batch and continuous modes was used for the combined treatment of 2% and 5% leachate/sewage mixtures. Estrogenic activity was reduced in reactors in both batch and continuous modes. The activated sludge process achieved average reductions of the estradiol equivalent (EQ-E2) values in the combined treatment of 94.5, 60.8 and 66.4% for the sanitary sewage, 2% mixture leachate in sewage and 5% mixture leachate in sewage reactors, respectively, in batch mode. For continuous reactors, 86%, 72%, and 65% of reduction of EQ-E2were achieved for sanitary sewage, 2 and 5% mixture with sanitary sewage. As for EQ-E2, the increase in the concentration of leachate in the sewage mixture was detrimental to the removal of estrogenic compounds during the biological process. Therefore, a limit on the % leachate/sewage mixtures should be established to achieve efficiency in the combined treatment of leachate in a Wastewater Treatment Plant (WWTP).

Use of reverse osmosis as a polish for the cationic surfactant after electro-oxidative treatment: Acute and chronic toxicity assessment

The main purpose of this work was to evaluate the performance of a commercial reverse osmosis (RO) membrane regarding selectivity (rejection) and productivity (permeate flux) of the treatment of quaternary ammonium compounds (QAC) after electro-Fenton (EF) treatment. Pollutants treated after the EF process should be investigated for ecotoxicity, since excess ions and high conductivity are harmful to aquatic and terrestrial biota. The use of the membrane system after EF treatment acts as final polishing since some electro-oxidative treatments leave the sample with high conductivity. In this study, RO was operated with a constant flow of 1 L min-1 and feed pressures of 1 MPa, 2 MPa and 3 MPa to reject ions (sodium and iron) and to decrease the level of toxicity using representative species from different taxonomic groups: freshwater algae (Pseudokirchneriella subcapitata), microcrustaceans (Daphnia similis) and lettuce seeds (Lactuca sativa). Experiments carried out at different pressures showed that increased pressure caused a rise in rejection and permeate flux. At the applied pressure of 3 MPa, after 180 min, conductivity removal efficiency of 83% was obtained, 85% for sodium and 99% for iron at a flow of 13.87 L/h m2. In all bioassays, the use of the membrane was efficient to decrease the toxicity by rejecting the ions. The microcrustacean tested was the most sensitive organism, while alga was the most tolerant organism. The germination of lettuce seeds and the relative growth rate of the radicle after the combined EF+RO process was satisfactory.