Sergio Francisco de Aquino

Quantification of dissolved methane in UASB reactors treating domestic wastewater under different operating conditions.

This paper aimed at measuring the concentration of methane dissolved in effluents from different UASB reactors (pilot-, demo- and full-scale) treating domestic wastewater, in order to calculate the degree of saturation of such greenhouse gas and evaluate the losses of energetic potential in such systems. The results showed that methane saturation degrees, calculated according to Henrys law, varied from ∼1.4 to 1.7 in the different reactors, indicating that methane was oversaturated in the liquid phase. The overall results indicated that the losses of dissolved methane in the anaerobic effluents were considerably high, varying from 36 to 41% of total methane generated in the reactor. These results show that there is considerable uncontrolled loss of methane in anaerobic wastewater treatment plants, implying the need of research on technologies aimed at recovering such energetic greenhouse gas.

Photolysis and photocatalysis of ibuprofen in aqueous medium: characterization of by-products via liquid chromatography coupled to high-resolution mass spectrometry and assessment of their toxicities against Artemia Salina

The degradation of the pharmaceutical compound ibuprofen (IBP) in aqueous solution induced by direct photolysis (UV-A and UV-C radiation) and photocatalysis (TiO2 /UV-A and TiO2 /UV-C systems) was evaluated. Initially, we observed that whereas photocatalysis (both systems) and direct photolysis with UV-C radiation were able to cause an almost complete removal of IBP, the mineralization rates achieved for all the photodegradation processes were much smaller (the highest value being obtained for the TiO2 /UV-C system: 37.7%), even after an exposure time as long as 120 min. Chemical structures for the by-products formed under these oxidative conditions (11 of them were detected) were proposed based on the data from liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) analyses. Taking into account these results, an unprecedented route for the photodegradation of IBP could thus be proposed. Moreover, a fortunate result was achieved herein: tests against Artemia salina showed that the degradation products had no higher ecotoxicities than IBP, which possibly indicates that the photocatalytic (TiO2 /UV-A and TiO2 /UV-C systems) and photolytic (UV-C radiation) processes can be conveniently employed to deplete IBP in aqueous media.

Occurrence of endocrine disrupting compounds in water sources of Belo Horizonte Metropolitan Area, Brazil.

Endocrine disrupting compounds (EDCs) have attracted the attention of the scientific community because of the effects of EDCs on aquatic fauna and the potential threat they pose to human health. There are a handful of papers on the monitoring of EDCs in Brazilian surface waters, hence this research was aimed at assessing, by using liquid chromatography coupled to mass spectrometry (LC–MS), the presence of 17β‐estradiol, 17α‐ethynylestradiol and 4‐nonylphenol in surface waters used for supplying the Belo Horizonte Metropolitan Area, Minas Gerais state, Brazil. The one‐year monitoring period of three water sources showed that 4‐nonylphenol was detected in all samples in a concentration range of 44 to 1918 ng L−1, whilst the natural and synthetic estradiols were hardly detected (only in ∼15% of samples) and always in low concentrations (2 to 54 ng L−1). Samples of partially treated water, collected in three water treatment plants before the chlorination step, showed that the steps of prechlorination, flocculation–sedimentation and sand filtration did not efficiently remove the EDCs studied.

Metodologias para determinação da atividade metanogênica específica (AME) em lodos anaeróbios

This paper presents a review on the different methodologies to determine the specific methanogenic activity (SMA) of anaerobic sludges. The protocols available in the literature differ not only regarding the procedures adopted to incubate the sludge, but also in relation to the method utilized to quantify the methane produced during the test. This paper discusses the principles of manometric and volumetric methods, and briefly describes the protocols mostly used by the Brazilian research community for sludge incubation, methane measurement and calculation of SMA.

Determination of endocrine‐disrupting compounds in waters from Rio das Velhas, Brazil, by liquid chromatography/high resolution mass spectrometry (ESI‐LC‐IT‐TOF/MS)

Some organic microcontaminants, known as endocrine‐disrupting compounds (EDC), are frequently found in surface waters and are of concern because of their ability to alter the normal functioning of the endocrine system. In this study five of these EDCs (estradiol, ethynylestradiol, bisphenol A, nonylphenol and diethylphthalate) in surface water samples, collected at the upper part of Rio das Velhas river (located between Ouro Preto and Nova Lima, Minas Gerais state, Brazil) were analysed. The analytical methodology, which employed solid‐phase extraction and high‐performance liquid chromatography coupled to high resolution mass spectrometry (HPLC‐MS/MS), was properly validated and resulted in limits of quantification (LOQ, S/N = 10) of 4.3 ng/L for diethylphtalate, 3.9 ng/L for nonylphenol, 3.6 ng/L for estradiol, 4.7 ng/L for ethynylestradiol and 2.5 ng/L for bisphenol. The five compounds were monitored for eight months, from sites where the hormones were occasionally found. Ethynylestradiol and estradiol concentrations varied from 5.6 to 63.8 ng/L. Bisphenol was present in all samples in a concentration that ranged from 8.6 to 168.3 ng/L. The other two compounds were at quantifiable levels in all collected samples, with nonylphenol varying from 25.9 to 1435.3 ng/L and diethylphthalate from 5.0 to 410.9 ng/L. The study showed that nonylphenol pollution seemed to originate from agricultural run‐off, while diethylphthalate pollution originated from the discharge of domestic sewage. Risk analysis studies showed that the environmental concentrations of nonylphenol and diethylphthalate do not present risks to human health; however, the concentrations found for bisphenol and ethinylestradiol could be toxic to humans, especially infants, if such compounds are not effectively removed at water treatment plants.

Degradation of a model azo dye in submerged anaerobic membrane bioreactor (SAMBR) operated with powdered activated carbon (PAC).

This work investigated the anaerobic degradation of the model azo dye Remazol Yellow Gold RNL in an upflow anaerobic sludge blanket reactor (UASB) and two submerged anaerobic membrane (SAMBR) bioreactors, one of which (SAMBR-1) was operated with powdered activated carbon (PAC) in its interior. The reactors were operated at 35 °C with a hydraulic retention time of 24 h in three operational phases, aimed to assess the effect of external sources of carbon (glucose) or redox mediator (yeast extract) on the removal or color and organic matter. The results showed that removal efficiencies of COD (73-94%) and color (90-94%) were higher for SAMBR-1 when compared to SAMBR-2 (operated without PAC) and UASB reactors. In addition, the presence of PAC in SAMBR-1 increased reactor stability, thereby leading to a lower accumulation of volatile fatty acids (VFA). The microfiltration membrane was responsible for an additional removal of ~50% of soluble residual COD in the form of VFA, thus improving permeate quality. On its turn, PAC exhibited the ability to adsorb byproducts (aromatic amines) of azo dye degradation as well as to act as source of immobilized redox mediator (quinone groups on its surface), thereby enhancing color removal.

Behaviour of pharmaceuticals and endocrine disrupting chemicals in simplified sewage treatment systems.

This work assessed the behaviour of nine pharmaceuticals and/or endocrine disrupting chemicals (EDCs) in demo-scale upflow anaerobic sludge blanket reactors (UASB reactors) coupled to distinct simplified post-treatment units (submerged bed, polishing ponds, and trickling filters) fed on raw sewage taken from a municipality in Brazil. The dissolved concentration of the studied micropollutants in the raw and treated sewage was obtained using solid phase extraction (SPE) followed by analysis in a liquid chromatography system coupled to a hybrid high resolution mass spectrometer consisting of an ion-trap and time of flight (LC-MS-IT-TOF). The UASB reactors demonstrated that they were not appropriate for efficiently removing the assessed compounds from the sewage. Furthermore, this study demonstrated that the hydraulic retention time (HRT) was an important parameter for the removal of the hydrophilic and less biodegradable compounds, such as trimethoprim and sulfamethoxazole. The post-treatment units substantially increased the removal of most target micropollutants present in the anaerobic effluents, with a greater removal of micropollutants in simplified systems that require a large construction area, such as the submerged bed and polishing ponds, probably because of the higher HRT employed. Alternatively, compact post-treatment systems, such as trickling filters, tended to be less effective at removing most of the micropollutants studied, and the type of packing proved to be crucial for determining the fate of such compounds using trickling filters.

Optimization of sugarcane bagasse autohydrolysis for methane production from hemicellulose hydrolyzates in a biorefinery concept.

This study aimed to optimize through design of experiments, the process variables (temperature - T, time - t and solid-to-liquid ratio - SLR) for sugarcane bagasse (SB) autohydrolysis (AH) to obtain hemicellulose hydrolyzates (HH) prone to anaerobic digestion (AD) and biochemical methane production (BMP). The results indicated that severe AH conditions, which lead to maximum hemicelluloses dissolution and sugar content in the HH, were not the best for BMP, probably due to the accumulation of toxic/recalcitrant compounds (furans and lignin). Mild AH conditions (170°C, 35min and SLR=0.33) led to the highest BMP (0.79Nm(3)kg TOC(-1)), which was confirmed by the desirability tool. HH produced by AH carried out at the desired condition DC2 (178.6°C, 43.6min and SLR=0.24) showed the lowest accumulation of inhibitory compounds and volatile fatty acids (VFA) and highest BMP (1.56Nm(3)kg TOC(-1)). The modified Gompertz model best fit the experimental data and led to a maximum methane production rate (R) of 2.6mmol CH4d(-1) in the best condition.

Implications of volatile fatty acid profile on the metabolic pathway during continuous sulfate reduction

Volatile fatty acid (VFA) profile is an important parameter in anaerobic reactors because it enables the assessment of metabolic pathways. Volatile fatty acids were monitored during sulfate reduction in a UASB (upflow anaerobic sludge blanket) reactor treating 2g/L sulfate concentration and with the organic loading increasing from 3.5 kg COD/m(3)d to 5.9 kg COD/m(3)d, for a 1-day residence time. In the absence of recirculation, the best outcome (65% reduction) was noticed with the lowest organic loading (3.55 kg/m(3)d). When recirculation was applied, sulfate reduction yields increased to 89%, corresponding to a sulfate removal rate of 1.94 kg SO(4)(2-)/m(3)d. The reactor performance was discussed in relation to microbial diversity and metabolic pathways. At high organic loading, two metabolic pathways account for lactate degradation: (i) lactate is oxidized to acetate and carbon dioxide by the incomplete-oxidizer SRB (sulfate-reducing bacteria) Desulfomonas, Desulfovibrio, Desulfolobus, Desulfobulbus and Desulfotomaculum spp.; (ii) lactate is converted to acetate by fermenting bacteria such as Clostridium sp. High propionate concentrations imply that there are low sulfate reduction efficiencies.

Soluble microbial product (SMP) characterization in bench-scale aerobic and anaerobic CSTRS under different operational conditions.

Abstract - This work presents results on the production and characterization (by both mass spectrometry and conventional chemical analyses) of Soluble Microbial Products (SMP) that accumulated in aerobic and anaerobic bench scale completely stirred tank reactors (CSTRs) fed with glucose or acetate under different hydraulic retention times (HRT) and temperatures. SMP accumulation varied from 2 to 68% of the influent COD in the aerobic reactor and from 9 to 27% in the anaerobic reactor and increased with the decrease in temperature and with the HRT reduction in the aerobic reactor. On the other hand, in the anaerobic reactor, the organic loading rate and the temperature had little impact on SMP production, implying that the SMP originated from different mechanisms in each system. For both reactors, a higher accumulation of SMPs was observed as the substrate was acetate when compared to glucose, and the chemical analysis showed that the majority of the SMP did not seem to be proteins or carbohydrates. Principal component analysis (PCA) of the mass spectra from positive and negative mode electron-spray ionization (LC-IT-TOF-MS) and results from matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS) confirmed the chemical analyses and showed the absence of proteins in the effluents and the predominance of low molecular weight SMP. The PCA analysis also showed that the majority of the SMP from aerobic and anaerobic reactors did not seem to originate from soluble extracellular polymeric substances (EPS) or cell lysis products.