Electrochemical oxidation of indanthrene blue dye in a filter-press flow reactor and toxicity analyses with Raphidocelis subcapitata and Lactuca sativa.

Alternative routes to degrade dyes are of crucial importance for the environment. Hence, we report the electrochemical removal of indanthrene blue by using a boron-doped diamond anode, focusing on the toxicity of the treated solutions. Different operational conditions were studied, such as current density (5, 10, and 20 mA cm-2) and electrolyte composition (Na2SO4, Na2CO3, and NaNO3). Besides, the pH was monitored throughout the experiment to consider its direct influence on the ecotoxicity effects. The highest electrochemical oxidation efficiency, measured as color removal, was seen in the 180 min condition of electrolysis in 0.033 M Na2SO4, applying 20 mA cm-2, resulting in a color removal of nearly 91% and 40.51 kWh m-3 of energy consumption. The toxicity towards Lactuca sativa depends solely on pH variations being indifferent to color removal. While the inhibition concentration (IC50) for Raphidocelis subcapitata increases 20% after treatment (in optimized conditions), suggesting that the byproducts are more toxic for this specific organism. Our data highlight the importance of analyzing the toxicity towards various organisms to understand the toxic effect of the treatment applied.

Assessing the presence of endocrine disruptors and markers of anthropogenic activity in a water supply system in northeastern Brazil.

Several chemical substances known as micropollutants are used in daily activities, and they pose risks to both human health and the environment. Some of these substances disrupt the endocrine system in addition to being responsible for major public health issues and for endangering some aquatic species. The aim of this research is to investigate the frequency of endocrine disruptors and anthropogenic activity markers in a Water Supply System (SAA) in Sergipe State, Brazil. Twenty-two water samples were collected from five SAA points from 2016 to 2017. They were prepared through solid phase extraction and analyzed in a gas chromatographer coupled to a mass spectrometer. In total, 13 compounds (diethyl phthalate, dibutyl phthalate, nonylphenol, pentachlorophenol, bisphenol A, androstane, estrone, estradiol, 17 α-ethinyl estradiol, progesterone, coprostanol, cholesterol and caffeine) that are endocrine disruptors and antrophic activity markers were herein assessed - both in raw (underground and surface) and treated water (distribution system and reservoir) samples. Based on our results, 50% of the samples contained caffeine; 45.5%, cholesterol; 31.81%, diethyl phthalate; 31.81%, dibutyl phthalate; 18.18%, bisphenol A; and 4.54%, estradiol. Therefore, it is important to create and implement public policies focused on public health and on assuring the safety of aquatic ecosystems.

Detection of hormones in surface and drinking water in Brazil by LC-ESI-MS/MS and ecotoxicological assessment with Daphnia magna.

The growing use of pharmaceutical drug is mainly due to several diseases in human and in animal husbandry. As these drugs are discharged into waterways via wastewater, they cause a major impact on the environment. Many of these drugs are hormones; in which even at low concentrations can alter metabolic and physiological functions in many organisms. Hormones were found in surface water, groundwater, soil, and sediment at concentrations from nanograms to milligrams per liter of volume--quantities known to cause changes in the endocrine system of aquatic organisms. This study aimed to develop a methodology for hormone detection (estriol, estrone, 17ß-estradiol, 17α-ethinylestradiol, progesterone, and testosterone) on surface and treated water samples. Sample toxicity was assessed by ecotoxicology tests using Daphnia magna. A liquid chromatograph coupled to a mass spectrometer with an electrospray ionization source (LC-ESI-MS/MS) was used for the analysis. The results showed that samples were contaminated by the hormones estriol, estrone, progesterone, 17ß-estradiol, and 17α-ethinylestradiol during the sampling period, and the highest concentrations measured were 90, 28, 26, 137, and 194 ng · L(-1), respectively. This indicates the inflow of sewage containing these hormones at some points in the Piracicaba River in the State of Sao Paulo-Brazil. Results indicated little toxicity of the hormone estriol in D. magna, indicating that chronic studies with this microcrustacean are necessary.

Comparison of hybrid RNA-based models to predict the degradation and mineralization of the microcontaminant hormone 17ß-estradiol.

New alternatives for effluent decontamination, such as electrochemical oxidation, are being developed to provide adequate removal of endocrine disruptors such as 17ß-estradiol in wastewater. In this study, data-driven models of response surface methodology, artificial neural networks, wavelet neural networks, and adaptive neuro-fuzzy inference system will be used to predict the degradation and mineralization of the microcontaminant hormone 17ß-estradiol through an electrochemical process to contribute to the treatment of effluent containing urine. With the use of different statistical criteria and graphical analysis of the correlation between observed and predicted data, it was possible to conduct a comparative analysis of the performances of the data-driven approaches. The results point to the superiority of the adaptive neuro-fuzzy inference system (correlation coefficient, R2, ranged from 0.99330 to 0.99682 for TOC removal and from 0.95330 to 0.99223 for the degradation of the hormone 17ß-estradiol) techniques over the others. The remaining results obtained with the other metrics are consistent with this analysis.

Degradation of the antibiotic ciprofloxacin in urine by electrochemical oxidation with a DSA anode.

Ciprofloxacin (CIP) is a commonly prescribed fluoroquinolone antibiotic that, even after uptake, remains unmetabolized to a significant extent-over 70%. Unmetabolized CIP is excreted through both urine and feces. This persistent compound manages to evade removal in municipal wastewater facilities, leading to its substantial accumulation in aquatic environments. This accumulation raises concerns about potential risks to the health of various living organisms. Herein, we present a study on the remediation of CIP in synthetic urine by electrochemical oxidation in an undivided cell with a DSA (Ti/IrO2) anode and a stainless-steel cathode. Physisorbed hydroxyl radical formed at the anode surface from water discharge and free chlorine generated from Cl- oxidation were the main oxidizing agents. The effect of pH and current density (j) on CIP degradation was examined, and its total removal was easily achieved at pH ≥ 7.0 and j ≥ 60 mA cm-2 due to the action of free chlorine. The CIP decay always followed a pseudo-first-order kinetics. The components of the synthetic urine were also oxidized. The main nitrogenated species released was NH3. A very small concentration of free chlorine was quantified at the end of the treatment, thus demonstrating the good performance of electrochemical oxidation and its effectiveness to destroy all the organic pollutants. The present study demonstrates the simultaneous oxidation of the organic components of urine during CIP degradation, thus showing a unique perspective for its electrochemical oxidation that enhances the environmental remediation strategies.

Analysis of the occurrence of microplastics in beach sand on the Brazilian coast.

The occurrence of microplastics in coastal areas is a growing concern due to the increase in plastic waste pollution in recent decades. This study had as objective to evaluate the occurrence of microplastics in Brazilian beach sand, using a simple and fast methodology. In addition, possible microplastics were classified according to color, shape and chemical composition. The study was conducted on six beaches on the Brazilian coast: Pecado Beach (RJ), Castanheiras Beach (ES), Regência Beach (ES), Imbassaí Beach (BA), Viral Beach (SE) and Ponta dos Mangues Beach (SE). The methodology was adapted from international protocols, with section demarcation (100 m), where samples were collected from the superficial layer of the beach sand in ten quadrants (50 cm × 50 cm). The laboratory extraction procedure consisted of the density separation technique in two stages: the first used sodium chloride solution and the second used zinc chloride solution. For the visual inspection and screening procedures, a stereoscopic microscope was used. A total of 166 items of microplastics were collected on the six beaches on the Brazilian coast under study. The largest quantity of possible microplastics was recorded on the beaches of Viral (SE) and Ponta dos Mangues (SE) with 30.4 items/m2 and 17.4 items/m2, respectively. Regarding colour, white items were predominant (49.3%), and among particle types, fragments represented 85.1%. In addition, some microplastic particles were sent for FT-IR analysis, one of which was identified as being polyethylene. This study contributes to the knowledge of the presence of microplastics in different locations, and to supporting decision makers regarding coastal management.

Improved 4-nitrophenol removal at Ti/RuO2-Sb2O4-TiO2 laser-made anodes.

In this study, binary and ternary mixed metal oxide anodes of Ti/RuO2-Sb2O4 and Ti/RuO2-Sb2O4-TiO2 were prepared using two different heating methods: conventional furnace and alternative CO2 laser heating. The produced anodes were physically and electrochemically characterized by using different techniques. The main difference found in the laser-made anodes was their more compact morphology, without the common deep cracks found in anodes made by typical thermal decomposition, which showed an important correlation with the prolonged accelerated service life. The correlation between the physicochemical properties of the anodes with their performance towards the 4-nitrophenol oxidations is discussed. The results demonstrated that the ternary anode (Ti/RuO2-Sb2O4-TiO2) is very promising, presenting a kinetic 5.7 times faster than the respective binary anode and the highest removal efficiency when compared with conventionally made anodes. Also, the lowest energy consumption per unit of mass of contaminant removed is seen for the laser-made Ti/RuO2-Sb2O4-TiO2 anode, which evidences the excellent cost-benefit of this anode material. Finally, some by-products were identified, and a degradation route is proposed. Graphical abstract.

Characterization of a tubular electrochemical reactor for the degradation of the commercial diuron herbicide.

After designing and constructing an electrochemical reactor with concentric electrodes and tangential feed (RECT), it is necessary to characterize it and to study its performance. The experimental study of the residence time distribution (RTD) was conducted for flow rates of 2.78 × 10-6 m3 s-1, 8.33 × 10-6 m3 s-1 and 13.9 × 10-6 m3 s-1. According to the values obtained from the Pe number (0.67-1.52), the RECT fits as tubular with great dispersion. The determined empirical correlation (Sh = 18.16 Re0.50 Sc0.33) showed a laminar flow behavior in the range of Reynolds number (Re) between 23 and 117. In order to use RECT in effluent treatment, an electrochemical oxidation study of the Diuron model molecule (Nortox®) was performed to analyze reactor performance in a closed system with total reflux. A decay kinetics of pseudo-first order was associated with the decay of the concentration of diuron and 30% mineralization in 180 min of process were obtained, having a total volume of 4 × 10-3 m3 and an initial concentration of commercial Diuron in 215.83 mg dm-3. Eleven by-products were identified by HPLC-MS analysis and, from this, it was possible to propose a route of degradation of the diuron. From these observations, it can be inferred that the studied electrochemical reactor had applicability in the degradation of recalcitrant compounds, as is the case of commercial diuron. Make some changes in the electrochemical reactor studied and other advanced oxidative processes, such as electro-Fenton, can be associated with the studied system to achieve a better conversion efficiency.

Real textile effluents treatment using coagulation/flocculation followed by electrochemical oxidation process and ecotoxicological assessment.

As it is well known, the textile industry generates a large amount of wastewater with varied composition that need to be treated. In particular, the Sergipe state, in Brazil, is a region that requires attention due the presence of several local textile industries. In this study, the efficiency of electrochemical oxidation (EO) process applied in the samples of Brazilian textile industry effluents previously treated by physical-chemical process coagulation-flocculation (CF) was evaluated by the reduction in TOC parameter and by the ecotoxicity using Lactuca sativa and Raphidocelis subcapitata bioassays. The optimized experiments achieved for the CF ([Al2(SO4)3]0 = 1.5 mg L-1, pH = 6.0, alkalinity = 0.675 mg L-1, [flocculating agent] = 61 mg L-1, rapid mixing = 100 rpm for 1 min, slow stage = 20-60 rpm for 20 min) a reduction of 20% on TOC. The best results obtained for EO was using the DSA electrode (I = 300 mA) reaching a TOC removal efficiency of 82% after an electrolysis time of 180 min. The ecotoxicity experiments indicated that the proposed treatment (CF + EO, I = 300 mA) was effective to decrease the dissolved pollutants presented in the treated samples. In comparison with raw samples, the treatment achieved a reduction of 52% for IC5072h value using R. subcapitata as bioindicator, and a 98% reduction of LC50 (Lactuca sativa).

Electrochemical incineration of omeprazole in neutral aqueous medium using a platinum or boron-doped diamond anode: degradation kinetics and oxidation products.

The electrochemical incineration of omeprazole, a widely prescribed gastrointestinal drug which is detected in natural waters, has been studied in a phosphate buffer of pH 7.0 by anodic oxidation with electrogenerated H(2)O(2) (AO-H(2)O(2)) operating at constant current density (j). The experiments were carried out in a cell equipped with either a Pt or a boron-doped diamond (BDD) anode and an air-diffusion cathode to continuously produce H(2)O(2). In these systems, organics are mainly oxidized by hydroxyl radicals formed at the Pt or BDD surface from water oxidation. A partial total organic carbon (TOC) abatement close to 78% for omeprazole was achieved by AO-H(2)O(2) with a BDD anode after consumption of 18 Ah L(-1) at 100 mA cm(-2), whereas the alternative use of Pt did not allow mineralizing the drug. However, the drug was totally removed using both anodes, although it decayed more rapidly using BDD. In this latter system, increasing j accelerated the degradation process, but lowering the mineralization current efficiency. Greater drug content also enhanced the degradation rate with higher mineralization degree and current efficiency. The kinetics for omeprazole decay always followed a pseudo-first-order reaction and its rate constant increased with increasing j and with decreasing its concentration. Seven heteroaromatic intermediates and four hydroxylated derivatives were detected by LC-MS, while nine short-linear carboxylic acids were identified and quantified by ion-exclusion HPLC. These acids were largely accumulated using Pt and rapidly removed using BDD, thus explaining the partial mineralization of omeprazole achieved by AO-H(2)O(2) with the latter anode. The release of inorganic ions such as NO(3)(-), NH(4)(+) and SO(4)(2-) was followed by ionic chromatography. A plausible reaction sequence for omeprazole mineralization involving all intermediates detected is proposed.

Aplicação de índices para avaliação da qualidade da água da Bacia Costeira do Sapucaia em Sergipe / Application of indexes to assess the water quality of coastal basin of the Sapucaia in Sergipe

RESUMO A redução da disponibilidade qualiquantitativa da água no mundo está diretamente relacionada às formas de uso e ocupação do solo, aos processos produtivos da agricultura e da pecuária, ao processo de urbanização e à geração de efluentes domésticos e industriais. Por isso, é importante a realização de diagnósticos de bacias hidrográficas, sobre o uso e a ocupação de seu solo e sobre a qualidade da água como ferramenta para a gestão hídrica. Este estudo teve como objetivo caracterizar e monitorar a qualidade da água da Bacia Costeira do Sapucaia, Sergipe. As coletas foram realizadas em oito pontos, com periodicidade trimestral, de agosto de 2014 a setembro de 2015. Na avaliação da qualidade da água foram utilizados: o Índice de Qualidade da Água (IQA) e o Índice de Estado Trófico (IET). As análises das amostras foram realizadas de acordo com os procedimentos estabelecidos no Standard Methods, sendo analisados os seguintes parâmetros: coliformes totais e termotolerantes, turbidez, pH, oxigênio dissolvido, sólidos totais, fósforo total, nitrogênio total, temperatura, condutividade, demanda bioquímica de oxigênio e clorofila. Os resultados do IQA classificam os corpos d'água em aceitável (2,5%), bom (92,5%) e ótimo (5,0%). Os resultados do IET classificaram as amostras como: ultraoligotrófico (67,5%), oligotrófico (20,0%), mesotrófico (2,5%), eutrófico (7,5%) e supereutrófico (2,5%). Os resultados obtidos permitem afirmar que os rios Aningas, Sapucaia e a Lagoa Redonda apresentam baixo grau de degradação, com menor conservação do ponto amostral localizado no Rio Sapucaia, dentro da Reserva Santa Isabel, por ser uma área bastante visitada nos finais de semana e feriados.

ABSTRACT The reduction of quali-quantitative availability of water in the world is directly related to the forms of land use and occupation, the productive processes of agriculture and cattle raising, the process of urbanization and the generation of domestic and industrial effluents. Thus, it is important to evaluate hydrographic basins regarding the use and occupation of their land and water quality as a tool for water management. This study aimed to characterize and monitor the quality of water of the Sapucaia Coastal Basin in the state of Sergipe, Brazil. The collections were performed quarterly in eight points of the basin, from August 2014 to September 2015. In the assessment of water quality, the Water Quality Index (WQI) and the Trophic State Index (TSI) were used. The analyzes of the samples were carried out according to the procedures outlined in Standard Methods; the following parameters were analyzed: total and fecal coliforms, turbidity, pH, dissolved oxygen, total solids, total phosphorus, total nitrogen, temperature, conductivity, biochemical oxygen demand and chlorophyll. The results from the application of the WQI classified water bodies as acceptable (2.5%), good (92.5%) and very good (5.0%). The results of the TSI ranked the samples as ultraoligotrophic (67.5%), oligotrophic (20.0%), mesotrophic (2.5%), eutrophic (7.5%) and supereutrophic (2.5%). The results allow to affirm that Aningas and Sapucaia rivers and Lagoa Redonda pond, belonging to the Sapucaia Coastal Basin, in Sergipe, have a low degree of degradation, with lower conservation of the sample point located in Sapucaia river, within the Reserva Santa Isabel reserve, that being a widely visited area on weekends and holidays.