Toxicity assessment of sanitary landfill leachate before and after Fenton treatment process.

Sanitary landfills are widely accepted and promoted as the environmentally friendly way to properly dispose of solid waste. However, a harmful aspect is the leachate generation and management, which are currently recognized as one of the greatest challenges in the environmental engineering field. Due to the high leachate recalcitrance, Fenton treatment has been accepted as a viable and efficient treatment process, which significantly reduces the organic matter: 91 % of COD; 72 % of BOD5; and 74 % of DOC. However, the acute toxicity of leachate must be assessed, mainly after the Fenton process, with the view of performing a low-cost biological post-treatment of the effluent. Despite the high redox potential, degrading 185 organic chemicals compounds identified in raw leachate, the present work reports a removal efficiency of almost 84 %, counting 156 organic compounds removed, and almost 16 % of persistent compounds. After Fenton treatment, 109 organic compounds were identified, beyond the persistent fraction of almost 27 %, wherein 29 organic compounds remained unchanged after Fenton treatment, counting 80 new short chain and lower complexity organic compounds formed. Despite the biogas production ratio increase (3-6 times), and significant enhancement of the biodegradable fraction susceptible to oxidation in respirometric test, a higher reduction in the oxygen uptake rate (OUR) was identified after Fenton treatment due to persistent compounds and their bioaccumulation. Additionally, the D. magna bioindicator parameter indicated that treated leachate is three times more toxic than raw leachate.

A video processing and machine vision-based automatic analyzer to determine sequentially total suspended and settleable solids in wastewater.

The monitoring of total suspended (TSS) and settleable (SetS) solids in wastewater is essential to maintain the quality parameters for aquatic biota because they can transport pollutants and block light penetration. Determining them by their respective reference methods, however, is laborious, expensive, and time consuming. To overcome this, we developed a new analytical instrument called Solids in Wastewater's Machine Vision-based Automatic Analyzer (SWAMVA), which is equiped with an automatic sampler and a software for real-time digital movie capture to quantify sequentially the TSS and SetS contents in wastewater samples. The machine vision algorithm (MVA) coupled with the Red color plane (derived from color histograms in the Red-Green-Blue (RGB) system) showed the best prediction results with R2 of 0.988 and 0.964, and relative error of prediction (REP) of 6.133 and 9.115% for TSS and SetS, respectively. The constructed models were validated by Analysis of Variance (ANOVA), and the accuracy and precision of the predictions by the t- and F-tests, respectively, at a 0.05 significance level. The elliptical joint confidence region (EJCR) test confirmed the accuracy, while the coefficient of variation (CV) of 6.529 and 10.908% confirmed the good precisions, respectively. Compared with the reference method (Standard Methods For the Examination of Water and Wastewater), the proposed method reduced the analysis volume from 1.5 L to just 15 mL and the analysis time from 12 h to 24 s per sample. Therefore, SWAMVA can be considered an important alternative to the determination of TSS and SetS in wastewater as an automatic, fast, and low-cost analytical tool, following the principles of Green Chemistry and exploiting Industry 4.0 features such as intelligent processing, miniaturization, and machine vision.

Studies of the liposolubility and the ecotoxicity of MC-LR degradation by-products using computational molecular modeling and in-vivo tests with Chlorella vulgaris and Daphnia magna.

Computational molecular modelling, mass spectrometry and in-vivo tests with Chlorella vulgaris (C. vulgaris) and Daphnia magna (D. magna) were used to investigate the liposolubility and ecotoxicity of MC-LR degradation by-products generated after oxidation by OH• radicals in Fenton process. Exposure of MC-LR (5 µg.L-1) to the most severe oxidation conditions (Fe2+ 20 mM and H2O2 60 mM) resulted in a reduction in the toxin concentration of 96% (0.16 µg.L-1), however, with the formation of many by-products. The by-product of m/z 445 was the most resistant to degradation and retained a toxic structure of diene bonds present in the Adda amino acid. Computational modeling revealed that m/z 445 (tPSA = 132.88 Ų; KOW = 2.02) is more fat-soluble than MC-LR (tPSA = 340.64 Ų; KOW = 0.68), evidencing an easier transport process of this by-product. Given this, toxicity tests using C. vulgaris and D. magna indicated greater toxicity of the by-product m/z 445 compared to MC-LR. When the conversion of MC-LR to by-products was 77%, the growth inhibition of C. vulgaris and the D. magna immobility were, respectively, 6.14 and 0%, with 96% conversion; growth inhibition and the immobility were both 100%  for both species.

Phytochemical composition, antifungal activity, in vitro and in vivo toxicity of Syzygium cumini (L) Skeels leaves extract / Composición fitoquímica, actividad antifúngica, toxicidad in vitro e in vivo del extracto de hojas de Syzygium cumini (L) Skeels

This study determined phytochemical composition, antifungal activity and toxicity in vitro and in vivo of Syzygium cumini leaves extract (Sc). Thus, was characterized by gas chromatography coupled to mass spectrometry and submitted to determination of Minimum Inhibitory (MIC) and Fungicidal concentrations (MFC) on reference and clinical strains of Candida spp. and by growth kinetics assays. Toxicity was verified using in vitro assays of hemolysis, osmotic fragility, oxidant and antioxidant activity in human erythrocytes and by in vivo acute systemic toxicity in Galleria mellonella larvae. Fourteen different compounds were identified in Sc, which showed antifungal activity (MIC between 31.25-125µg/mL) with fungistatic effect on Candida. At antifungal concentrations, it demonstrated low cytotoxicity, antioxidant activity and neglible in vivotoxicity. Thus, Sc demonstrated a promising antifungal potential, with low toxicity, indicating that this extract can be a safe and effective alternative antifungal agent.

Este estudio determinó la composición fitoquímica, la actividad antifúngica y la toxicidad in vitro e in vivo del extracto de hojas de Syzygium cumini (Sc). Así, se caracterizó mediante cromatografía de gases acoplada a espectrometría de masas y se sometió a determinación de Concentraciones Mínimas Inhibitorias (CMI) y Fungicidas (MFC) sobre cepas de referencia y clínicas de Candida spp. y mediante ensayos de cinética de crecimiento. La toxicidad se verificó mediante ensayos in vitro de hemólisis, fragilidad osmótica, actividad oxidante y antioxidante en eritrocitos humanos y por toxicidad sistémica aguda in vivo en larvas de Galleria mellonella. Se identificaron catorce compuestos diferentes en Sc, que mostraron actividad antifúngica (CMI entre 31.25-125 µg/mL) con efecto fungistático sobre Candida. En concentraciones antifúngicas, demostró baja citotoxicidad, actividad antioxidante y toxicidad in vivo insignificante. Por lo tanto, Sc demostró un potencial antifúngico prometedor, con baja toxicidad, lo que indica que este extracto puede ser un agente antifúngico alternativo seguro y eficaz.

Chemical safety assessment of transformation products of landfill leachate formed during the Fenton process.

Organic chemicals identified in raw landfill leachate (LL) and their transformation products (TPs), formed during Fenton treatment, were analyzed for chemical safety following REACH guidelines. The raw LL was located in the metropolitan region of Campina Grande, in northeast Brazil. We elucidated 197 unique chemical structures, including 154 compounds that were present in raw LL and 82 compounds that were detected in the treated LL, totaling 39 persistent compounds and 43 TPs. In silico models were developed to identify and prioritize the potential level of hazard/risk these compounds pose to the environment and society. The models revealed that the Fenton process improved the biodegradability of TPs. Still, a slight increase in ecotoxicological effects was observed among the compounds in treated LL compared with those present in raw LL. No differences were observed for aryl hydrocarbon receptor (AhR) and antioxidant response element (ARE) mutagenicity. Similar behavior among both raw and treated LL samples was observed for biodegradability; Tetrahymena pyriformis, Daphnia magna, Pimephales promelas and ARE, AhR, and Ames mutagenicity. Overall, our results suggest that raw and treated LL samples have similar activity profiles for all endpoints other than biodegradability.

Alkaline and acid solubilisation of waste activated sludge.

The influence of acidic and alkaline conditions on the solubilisation process of waste activated sludge (WAS) was investigated using HCl and NaOH at pH 2, 10, 11 and 12. The rise in concentration of solubilised compounds, the influence of reaction time, and the influence of the concentration of total solids (TS) during the solubilisation process were determined. Physical and chemical tests demonstrated that pre-treatment provided a release of compounds from the sludge floc matrix into the soluble fraction, characterising the solubilisation process. The highest degree of WAS solubilisation was observed when a pH of 12 was applied. Although largest effects were already attained after 0.25 h, WAS solubilisation continued reaching an increase in total dissolved solids by a factor 10.4 after 720 hrs. Under these conditions, the dissolved organic carbon (DOC), proteins, and carbohydrates resulted in releases up to 15, 40 and 41 times, respectively; phosphorus increased 5.7 times. Results indicate that by applying alkaline pre-treatment, higher TS concentrations can be treated per reactor volume compared to non-pre-treated WAS. Aerobic and anaerobic biodegradability tests showed increased bioconversion potentials in full-scale treatment plants. The respirometry tests ratify the improvement in solubilisation, with O2 consumption rates increasing 1.4 times, concomitant with an additional 261 mg·L-1 of the COD used, which represents 90% bioconversion of waste activated sludge. Biomethanisation test indicated an increase of 3.6 times relative to the blank.

Phytochemistry, antifungal and antioxidant activity, and cytotoxicity of byrsonima gardneriana (A. Juss) extract.

OBJECTIVE: To determine the phytochemical composition of Byrsonima gardneriana (A. Juss) leaf extract (BGE) and its antifungal activity against Candida spp., antioxidant potential and in vitro cytotoxicity. MATERIAL AND METHODS: BGE was obtained and submitted to Gas Chromatography Coupled to Mass Spectrometry for phytochemical analysis. The ethanolic extract was tested for its antifungal activity against C. albicans and non-albicans reference strains and clinical isolates in addition to inhibition of C. albicans growth kinetics. It was also tested for antioxidant potential in the presence of phenylhydrazine and reactive oxygen species (ROS). And cytoxicity in human erythrocytes. The data were analyzed by one-way Analysis of Variance (ANOVA) followed by Tukey's or Dunnett's post-hoc test, with α = 0.05. RESULTS: Pyroglutamic acid (90.77 %), eucalyptol (89.61 %) and octanoic acid (76.22 %) were the major compounds detected in BGE, P (%) is the percent probability of compound identification, according to the mass spectra library. The extract showed fungistatic activity, with MIC of 125 µg/mL against most tested strains. While BGE showed low hemolytic activity on all blood types tested herein, it could not prevent osmotic stress in human erythrocytes. The extract did not have oxidizing effects in the presence of phenylhydrazine, but it showed antioxidant potential against ROS when tested at 31 µg/mL and 62 µg/mL. CONCLUSION: B. gardneriana extract showed antifungal activity against Candida spp., demonstrated low hemolytic potential, no oxidant activity in human erythrocytes and antioxidant activity against ROS. This study opens avenues for the study of BGE as a promising biocompatible antifungal agent.

Predictive Computational Tools for Assessment of Ecotoxicological Activity of Organic Micropollutants in Various Water Sources in Brazil.

The increase of chemical pollutants detected in different aquatic environments over the past few years has been in the focus of several studies related to their occurrence, transport, fate, and hazards, or risks to human and environmental health. In Brazil, recent studies have been conducted on the occurrence of a series of organic micropollutants (OMPs) in aquatic environments. Nevertheless, the toxicological information and environmental behavior for most of these pollutants are still difficult to evaluate. We obtained consensus models using a combination of VolSurf and Dragon descriptors and Random Forest approach to predict the toxicity against Daphnia magna and Pimephales promelas for compounds identified in different sources of water in Brazil. The models showed satisfactory performance when compared with other approaches, such as Toxicity Estimation Software Tool (T.E.S.T.), etc. Both models can be used as complementary tools to aid in the prediction of organic compounds against both organisms.

Predictive ecotoxicity of MoA 1 of organic chemicals using in silico approaches.

Persistent organic products are compounds used for various purposes, such as personal care products, surfactants, colorants, industrial additives, food, pesticides and pharmaceuticals. These substances are constantly introduced into the environment and many of these pollutants are difficult to degrade. Toxic compounds classified as MoA 1 (Mode of Action 1) are low toxicity compounds that comprise nonreactive chemicals. In silico methods such as Quantitative Structure-Activity Relationships (QSARs) have been used to develop important models for prediction in several areas of science, as well as aquatic toxicity studies. The aim of the present study was to build a QSAR model-based set of theoretical Volsurf molecular descriptors using the fish acute toxicity values of compounds defined as MoA 1 to identify the molecular properties related to this mechanism. The selected Partial Least Squares (PLS) results based on the values of cross-validation coefficients of determination (Qcv2) show the following values: Qcv2 = 0.793, coefficient of determination (R2) = 0.823, explained variance in external prediction (Qext2) = 0.87. From the selected descriptors, not only the hydrophobicity is related to the toxicity as already mentioned in previously published studies but other physicochemical properties combined contribute to the activity of these compounds. The symmetric distribution of the hydrophobic moieties in the structure of the compounds as well as the shape, as branched chains, are important features that are related to the toxicity. This information from the model can be useful in predicting so as to minimize the toxicity of organic compounds.

Recovery of elemental sulphur from anaerobic effluents through the biological oxidation of sulphides.

The aim of the present study was to evaluate the biological oxidation of sulphide in two different UASB reactors by assessing the occurrence of oxidized forms of sulphur in the effluents and the amount of S0 that could be recovered in the process. The bioreactors employed were an anaerobic hybrid (AH) reactor employing porous polyurethane foam as support media and a micro-aerated UASB reactor equipped with an aeration device above the digestion zone. The AH reactor produced a final effluent containing low concentrations of S2- (3.87% of total sulphur load). It was achieved due to a complete oxidation of 56.1% of total sulphur. The partial biological oxidation that occurred in the AH reactor allowed the recovery of 30% of the sulphur load as S0. The effluent from the micro-aerated UASB reactor contained 5% of the sulphur load in the form of S2-, while 20.9% was present as dissolved SO42- and 46% was precipitated as S0. It is concluded that the AH reactor or micro-aeration carried out above the digestion zone of the UASB reactor favoured the biological oxidation of S2- and the release of odourless effluents. Both technologies represent feasible and low-cost alternatives for the anaerobic treatment of domestic sewage.

Surface water disinfection by chlorination and advanced oxidation processes: Inactivation of an antibiotic resistant E. coli strain and cytotoxicity evaluation.

The release of antibiotics into the environment can result in antibiotic resistance (AR) spread, which in turn can seriously affect human health. Antibiotic resistant bacteria have been detected in different aquatic environments used as drinking water source. Water disinfection may be a possible solution to minimize AR spread but conventional processes, such as chlorination, result in the formation of dangerous disinfection by-products. In this study advanced oxidation processes (AOPs), namely H2O2/UV, TiO2/UV and N-TiO2/UV, have been compared with chlorination in the inactivation of an AR Escherichia coli (E. coli) strain in surface water. TiO2 P25 and nitrogen doped TiO2 (N-TiO2), prepared by sol-gel method at two different synthesis temperatures (0 and -20°C), were investigated in heterogeneous photocatalysis experiments. Under the investigated conditions, chlorination (1.0 mg L(-1)) was the faster process (2.5 min) to achieve total inactivation (6 Log). Among AOPs, H2O2/UV resulted in the best inactivation rate: total inactivation (6 Log) was achieved in 45 min treatment. Total inactivation was not observed (4.5 Log), also after 120 min treatment, only for N-doped TiO2 synthesized at 0°C. Moreover, H2O2/UV and chlorination processes were evaluated in terms of cytotoxicity potential by means of 3-(4,5-dime-thylthiazol-2-yl)-2,5-diphenylte-trazolium colorimetric test on a human-derived cell line and they similarly affected HepG2 cells viability.

Remoção de microcistina-LR de águas eutrofizadas por clarificação e filtração seguidas de adsorção em carvão ativado granular / Removal of microcystin-LR from eutrophic waters through clarification and filtration followed by adsorption on granular activated carbon

RESUMO Usualmente, o tratamento convencional de águas com altas densidades de cianobactérias e concentração de cianotoxinas não garante efluente consoante o padrão de potabilidade vigente (1,0 µg.L-1 de microcistina). Etapas adicionais fazem-se necessárias, destacando-se a adsorção por carvão ativado granular ou pulverizado. Neste contexto, o objetivo geral deste trabalho foi avaliar em escala de bancada a remoção de microcistina em água natural por adsorção em colunas de carvão ativado granular de casca de coco, após as etapas de clarificação e filtração em areia. Os resultados mostraram que o transpasse no carvão de maior granulometria ocorreu em menor tempo de contato (2 h), quando comparado ao de menor granulometria. Tais resultados abrem perspectiva de emprego em escala real por garantir efluente com concentração inferior ao que estabelece a Portaria 2914 por mais tempo e utilizando menor massa de carvão.

ABSTRACT Conventional treatment process of natural waters with high densities of cyanobacteria and cyanotoxins usually presents low efficiency according to the present drinking water standard (maximum permissible value of 1.0 µg.L-1 of microcystin). Additional steps, such as activated carbon, commonly become necessary to achieve the maximum permissible value of microcystin (1.0 µg.L-1) set up by Brazilian Drinking Water Regulation 2914. In this context, the main objective of this work was to evaluate microcystin removal from natural waters by means of two granular activated carbons after clarification and sand filtration in bench scale. The results pointed out that the breakthrough happened in activated carbon with highest grain sizes in lower contact time (2 h) , when compared with that with smaller grain sizes. These results open the perspective of an application of the activated carbon in actual scale, assuring the treated water quality in compliance with the Brazilian Drinking Water Standards Regulation 2914.

Treatment of wastewater using a sequencing batch reactor.

The aim of this study was to evaluate the efficiency of two sequencing batch reactors (R1 and R2) at removing nutrient (N and P) and chemical oxygen demand (COD). The two reactors (R1 and R2) were of the same design, operating under identical cycles and had a sludge retention time of 5 d. In R1, the substrate was sewage enriched with cooked and triturated cereals. In R2, the substrate was raw sewage mixed with triturated discarded excess sludge. Respirometry tests were performed to compare the biodegradability of the substrates used during the experimental period. The efficiency of R1 in removing soluble P and N-ammonia was considerably higher (90.4 and 97.2%, respectively) than reactor R2 (60 and 39.2%, respectively). While the effluent generated by R1 contained only minor amounts of N-nitrite and N-nitrate (0.5 +/- 0.4 and 1.7 +/- 0.8 mg L(-1), respectively). The concentrations of nitrite and nitrate in the effluent from R2 were 2 and 7 times higher. The lack of biodegradable COD available for denitrification was responsible for the high concentrations of nitrite and nitrate in the effluent of R2.

Tratamento anaeróbio de resíduos orgânicos com baixa concentração de sólidos / Anaerobic treatment of organic wastes with low concentration of solids

O processo de digestão anaeróbia de resíduos sólidos orgânicos com baixa concentração de sólidos é realizado com substrato contendo em média cerca de 5 por cento (percentagem em peso) de sólidos totais. Os problemas de ordem técnica associados a este tipo de tratamento, estão relacionados ao estudo das configurações de reatores que possam viabilizar uma boa eficiência de transformação do material carbonáceo em um período relativamente curto de tempo. Portanto, neste trabalho foi estudado o processo de digestão anaeróbia de resíduos sólidos orgânicos (RSO) com baixa concentração de sólidos em um reator anaeróbio compartimentado (RAC). O reator anaeróbio compartimentado tinha capacidade unitária de 2200 litros e foi operado com tempo de retenção de sólidos de 90 dias. A eficiência de transformação média de STV foi de 75 por cento e o biogás produzido continha em média 60 por cento de gás metano.

Influence of inoculum on performance of anaerobic reactors for treating municipal solid waste.

The influence of bovine rumen fluid inoculum during anaerobic treatment of the organic fraction of municipal solid waste (MSW) was studied in this work. The parameters adopted for evaluation were the biostabilization constant of total volatile solids (TVS) and the biostabilization time of the chemical oxygen demand (COD) applied to the reactors. The work was realized in four anaerobic batch reactors of 20 l capacity each, during a period of 365 days. The proportions between MSW/inoculum loaded in the reactors were Reactor A (100%/0%), Reactor B (95%/5%), Reactor C (90%/10%) and Reactor D (85%/15%). The necessary time for biostabilization of half of the applied COD was 459, 347, 302 and 234 days and the average of methane concentration in the biogas produced was 3.6%, 13.0%, 25.0% and 42.6% for Reactors A, B, C and D, respectively. The data obtained affirm that the inoculum used substantially improved the performance of the process.