Hydrothermal co-liquefaction of microalgae, sugarcane bagasse, brewer's spent grain, and sludge from a paper recycling mill: Modeling and evaluation of biocrude and biochar yield.

Biomass can be used as an energy source to thermochemical conversion processes to biocrude production. However, the supply and dependence on only one biomass for biocrude production can be an obstacle due to its seasonality, availability, and logistics costs. In this way, biomass waste and agroindustrial residues can be mixture and used as feedstock to the hydrothermal co-liquefaction (co-HTL) process as an alternative to obtaining biocrude. In this sense, the present paper analyzed the biocrude yield influence of the co-HTL from a quaternary unprecedented blend of different biomasses, such as sugarcane bagasse, brewer's spent grain (BSG), sludge from a paper recycling mill (PRM), and microalgae (Chlorella vulgaris). In this way, a simplex lattice design was employed and co-HTL experiments were carried out in a 2000 mL high-pressure stirred autoclave reactor under 275 °C for 60 min, considering 15% of feedstock/water ratio. Significant effects in each feedstock and their blends were analyzed aiming to increase biocrude and biochar yield. It was found that the addition of microalgae is only significant when considered more than 50% into the blend with BSG and PRM sludge to increase biocrude yield.

Pharmaceuticals, natural and synthetic hormones and phenols in sediments from an eutrophic estuary, Jurujuba Sound, Guanabara Bay, Brazil.

A screening for microcontaminants performed by gas chromatography detected several microcontaminants in 12 sediment samples from the eutrophic estuary Guanabara Bay (GB) in southeastern Brazil. Bisphenol A (BPA) ranged from 1.4 to 20.3 ng g-1, 4-octylphenol, from

Low-temperature partitioning extraction followed by liquid chromatography tandem mass spectrometry determination of multiclass antibiotics in solid and soluble wastewater fractions.

An analytical method based on low-temperature partitioning extraction (LTPE) followed by high performance liquid chromatography coupled to triple quadrupole mass spectrometry analysis was developed and validated for the determination of eight multiclass antibiotics in wastewater. The analyzed target antibiotics included one ß-lactam, two sulfonamides, three fluoroquinolones, one macrolide and one diaminopyrimidine. LTPE parameters such as sample pH, volume ratio between sample and extractor solvent, ultra-sonic extraction time, extraction tube material, solvent and volume to reconstitute the sample extracts, were optimized. Additionally, the influence of solids on extraction efficiency was evaluated. Quantification of the target antibiotics was performed by double consecutive injection method, without the use of a labeled compound, in order to correct matrix effects. The whole samples were analyzed, including, liquid and solid fractions of wastewater. The results revealed that the filtration step can underestimate the total antibiotics concentration, particularly to the hydrophobic compounds that have higher affinity for solids, indicating that the suspended wastewater particulate should not be neglected. The method detection limit ranged from 18.54 ng L-1 (trimethoprim) to 78.49 ng L-1 (ciprofloxacin). Intra-day precision of less than 12.3% was achieved. The recoveries values ranged from 13.9% (sulfadiazine) to 48.9% (erythromycin) in influent samples and from 19.1% (sulfadiazine) to 57.2% (ciprofloxacin) in effluent samples. The method was applied to the measurement of antibiotic residues in influent and effluent from wastewater treatment plants. The majority target antibiotics were detected in wastewater samples. Their concentrations ranged from 237 to 9553 ng L-1 in influent and from 212 to 1660 ng L-1 in effluent. This work provides new insights on the applicability of LTPE for antibiotic residues extraction from wastewater. In addition, the performed analysis highlights the importance of measuring total concentrations of analytes in whole sample.

LED irradiated photo-Fenton for the removal of estrogenic activity and endocrine disruptors from wastewater treatment plant effluent.

The goal of this work was to evaluate the performance of the LED irradiated photo-Fenton process on the removal of (i) estrogenic activity and (ii) seven endocrine disruptors (EDs) (4-octylphenol, 4-nonylphenol, bisphenol A, estrone, 17ß-estradiol, 17α-ethinylestradiol, and estriol) from real wastewater treatment plant effluent (WWTPE). EDs are a group of contaminants of emerging concern present in WWTPE and which may be recognized by hormone receptors, thus harming animal and human health. The yeast estrogenic screen test (YES) was used to quantify estrogenic activity promoted by EDs in WWTPE samples before and after photo-Fenton treatment. Tests were performed following a factorial design with different iron (20, 40, and 60 mg L-1) and hydrogen peroxide (100, 200, and 300 mg L-1) concentrations in a laboratory scale LED photoreactor (λ = 455 nm, 1.5 L, 1.6 × 10-6 Einstein s-1). EDs were analyzed by gas chromatography coupled to a mass spectrometer. Control experiments consisted of Fenton process, iron only, LED irradiation only, and H2O2 only. Optimum experimental conditions for LED photo-Fenton resulted in 62% removal of estrogenic activity and 59% mineralization. In addition, treated WWTPE was not toxic to Aliivibrio fischeri and more than 80% of EDs were removed during LED irradiated photo-Fenton. Although Fenton process showed similar efficiency to that obtained by LED photo-Fenton, a higher volume of sludge was generated in the dark. Finally, results obtained in this study confirm the applicability of LED irradiated photo-Fenton process for improving the quality of WWTPE as an alternative to solar photo-Fenton in case solar radiation is not available, thus reducing hazards associated to WWTPE reuse or discharge.

Quantification, removal and potential ecological risk of emerging contaminants in different organic loads of swine wastewater treated by integrated biological reactors.

This study aims to evaluate the dynamics and their ecological risks for aquatic species of lipid regulator, nervous stimulant, anti-inflammatory and endocrine disrupters in an upflow anaerobic sludge blanket (UASB), submerged aerated biological filters (SABF) and horizontal subsurface flow constructed wetland (HSSF-CW) reactors that treat swine wastewater. Four organic loads of swine wastewater (SW) were used according to changing the chemical oxygen demand. 13 contaminants were quantified, standing out the endocrine disruptors, lipid regulator and anti-inflammatory. In phase III, 8318.4 ng L-1 of 4-ocylphenol was found at the influent of the UASB reactor and removal from 1877.1 to 13.7 ng L-1 in the bisphenol A system. With the maximum organic load, there was a reduction among all the treatment units, with concentrations between 1877.1 and 13.7 ng L-1 of bisphenol A and had naproxen removal of 94.5% and 2,7 ng L-1 after treating phases II and III. It was found that 24.6% of the contaminants presented a high ecological risk, with maximum values of 27.4 (4-nonylphenol, phase II), 24.6 and 5.9 (17ß-estradiol, phase IV and I, respectively), 13.4 (4-ocylphenol, phase III) and 4.4 (estrone, phase IV) in the influent system. The reduction of ecological risk potentials was optimized by SABF and HSSF-CW. The effect oxygen availability and microbiological activities optimized the reduction of ecological risks on zebrafish (Danio rerio) and cnidarian (Hydra attenuata) species, moreover, the reduction of mass flows and ecological risks of the emerging contaminants are associated with the use of biological reactors in series and organic stabilizations.

The golden mussel proteome and its response to niclosamide: Uncovering rational targets for control or elimination.

The Asian invasive species Limnoperna fortunei (Dunker, 1857), known as the golden mussel, causes great economic and environmental damage due to its fixative capacity and accelerated proliferation. Molecular studies for the control of larval and adult forms are of great economic, scientific and technological interest. Here, we first report on the compositional analysis of the L. fortunei proteome obtained through shotgun analysis using LC-MS/MS. Among those 2790 proteins identified, many of them related to secretory processes and membrane receptors. Our second approach consisted in exposing the mollusc to the molluscicide niclosamide to evaluate the induced proteomic alterations. Exposure to niclosamide at 0.25 mg/L for 24 h resulted in a pronounced differential abundance of proteins when compared to those obtained when exposure was reduced to 4 h at 2.3 mg/L. In total, 342 proteins were found differentially expressed in the responsive individuals as revealed by label-free quantitative proteomics. Regarding the affected cell processes were: cell division and differentiation, cytoskeletal organization and compartment acidification (upregulated), and energy metabolism (downregulated). Our findings constitute the first inventory of the expressed proteome of the golden mussel and have the potential to contribute with a more rational proposition of molecular targets for control and monitoring of this species. SIGNIFICANCE: With the recent availability of transcriptomic and genomic data applied to L. fortunei the timing is right to interrogate its putative gene repertoire using proteomic techniques. These have the potential to validate the existence of the predicted genes, infer their relative abundance and quantify their levels as a response to environmental stressors or various agents. Here we provided an inventory of the golden mussel proteome and evaluated its response to the molluscicide niclosamide. The obtained results open new avenues for intervention aimed at its control or elimination, particularly by targeting the various cellular processes that were uncovered.

Behavior of pharmaceuticals in UV photoreactors fed with sewage treated by anaerobic/aerobic system.

This work has assessed the seasonal changes and the dynamics in the concentration of six pharmaceutical compounds during photolysis as a tertiary treatment of sewage previously treated by an anaerobic/aerobic system comprising a UASB (Upflow Anaerobic Sludge Blanket) reactor and a trickling filter (TF). The target compounds were four antibiotics (ciprofloxacin (CPF), clindamycin (CLM), sulfamethoxazole (SMX), and trimetoprim), one ß-blocker (atenolol), and one anti-inflammatory (diclofenac (DCF)). Six hydraulic retention times (HRTs) were evaluated (5, 10, 20, 40, 80, and 160 min) with the intent of varying the ultraviolet C (UVC) radiation doses applied to the effluent from biological treatment containing the target contaminants. The concentrations of pharmaceutical compounds in the effluent of the UASB/TF system were in agreement with the concentration levels reported in the literature. Aside from DCF, the seasonality seems to be a preponderant characteristic regarding the pharmaceutical concentration found in the effluent of biological treatment systems. The radiation dose of 117 mJ cm-2 seemed to be most suited for the photolysis application to tertiary treatment of domestic effluents. It was observed that lower UVC doses led to deconjugation of pharmaceuticals, which can result in increased concentrations of target pollutants in the photoreactor effluent.

What's in SWAP? Abundance of the principal constituents in a soluble extract of Schistosoma mansoni revealed by shotgun proteomics.

BACKGROUND: The soluble antigen preparation of adult schistosomes (SWAP) has often been used to probe host responses against these blood-dwelling parasites. Despite its long-established use there is limited knowledge about its composition. The information we provide here on the molecular composition of SWAP may contribute as a guide for a rational selection of antigenic targets. METHODS: Label-free quantitative shotgun proteomics was employed to determine the composition and abundance of SWAP constituents. Briefly, paired adult Schistosoma mansoni worms were sonicated in PBS pH 7.2 and ultracentrifuged for recovery of the soluble supernatant. An aliquot was subjected to trypsin digestion. Resulting peptides were separated under ultra-high performance liquid chromatography and analysed using an orbitrap mass spectrometer. Spectral data were interrogated using SequestHT against an in-house S. mansoni database. Proteins were quantified by recording the mean area under curve obtained for up to three most intense detected peptides. Proteins within the 90(th) percentile of the total SWAP mass were categorized according to their sub-cellular/tissue location. RESULTS: In this work we expanded significantly the list of known SWAP constituents. Through application of stringent criteria, a total of 633 proteins were quantitatively identified. Only 18 proteins account to 50% of the total SWAP mass as revealed by their cumulative abundance. Among them, none is predicted as a secreted molecule reinforcing the point that SWAP is dominated by cytosolic and cytoskeletal proteins. In contrast, only 3% of the mass comprised proteins proposed to function at the host-parasite interfaces (tegument and gut), which could conceivably represent vulnerable targets of a protective immune response. Paradoxically, at least 11 SWAP proteins, comprising ~25% of its mass, have been tested as vaccine candidates. CONCLUSIONS: Our data suggest that use of SWAP to probe host responses has greatest value for diagnostic purposes or assessing intensity of infection. However, the preparation is of limited utility as an antigen source for investigating host responses to proteins expressed at or secreted from worm-host interfaces. The data also pose the question as to why vaccination with SWAP, containing so many proposed vaccine candidates, has no additive or even synergistic effects on the induction of protection.

Liquid-liquid extraction combined with high performance liquid chromatography-diode array-ultra-violet for simultaneous determination of antineoplastic drugs in plasma / Extracção líquido-líquido combinado com cromatografia líquida de alta eficiência de diodo matriz-ultra-violeta para a determinação simultânea de fármacos antineoplásicos no plasma

A liquid-liquid extraction (LLE) combined with high-performance liquid chromatography-diode array detection method for simultaneous analysis of four chemically and structurally different antineoplastic drugs (cyclophosphamide, doxorubicin, 5-fluorouracil and ifosfamide) was developed. The assay was performed by isocratic elution, with a C18 column (5 µm, 250 x 4.6 mm) and mobile phase constituted by water pH 4.0- acetonitrile-methanol (68:19:13, v/v/v), which allowed satisfactory separation of the compounds of interest. LLE, with ethyl acetate, was used for sample clean-up with recoveries ranging from 60 to 98 percent. The linear ranges were from 0.5 to 100 µg mL-1, for doxorubicin and 1 to 100 µg mL-1, for the other compounds. The relative standard deviations ranged from 5.5 to 17.7 percent. This method is a fast and simple alternative that can be used, simultaneously, for the determination of the four drugs in plasma, with a range enabling quantification of the drugs in pharmacokinetics, bioequivalence and therapeutic drug-monitoring studies.

Um método de extração líquido-líquido (ELL) combinado com cromatografia líquida de alta eficiência-detector de arranjo de diodos foi desenvolvido para análise simultânea de quatro fármacos antineoplásicos quimicamente e estruturalmente diferentes (ciclofosfamida, doxorrubicina, fluoruracila e ifosfamida). O estudo foi realizado sob condições isocráticas, com coluna C18 (5µm, 250 x 4.6 mm) e fase móvel constituída por água pH 4.0-acetonitrila-metanol (68:19:13, v/v/v), que permitiu separação satisfatória dos analitos de interesse. A ELL, com acetato de etila, foi utilizada para limpeza da amostra, com recuperação variando de 60 a 98 por cento. As faixas foram lineares de 0,5 a 100 µg mL-1 para doxorrubicina e 1 a 100 µg mL-1 para os outros compostos. O desvio padrão relativo variou de 5,5 a 17,7 por cento. Este método é uma alternativa rápida e simples que pode ser usado, simultaneamente, para a determinação dos quatro fármacos em plasma, com uma faixa que permite quantificá-los em estudos de farmacocinética, bioequivalência e monitorização terapêutica.