Optimization of in situ derivatization SPME by experimental design for GC-MS multi-residue analysis of pharmaceutical drugs in wastewater

This paper presents the development of a procedure, which enables the analysis of nine pharmaceutical drugs in wastewater using gas chromatography-mass spectrometry (GC-MS) associated with solid-phase microextraction (SPME) for the sample preparation. Experimental design was applied to optimize the in situ derivatization and the SPME extraction conditions. Ethyl chloroformate (ECF) was employed as derivatizing agent and polydimethylsiloxane-divinylbenzene (PDMS-DVB) as the SPME fiber coating. A fractional factorial design was used to evaluate the main factors for the in situ derivatization and SPME extraction. Thereafter, a Doehlert matrix design was applied to find out the best experimental conditions. The method presented a linear range from 0.5 to 10 mu g/L, and the intraday and interday precision were lower than 16%. Applicability of the method was verified from real influent and effluent samples of a wastewater treatment plant, as well as from samples of an industry wastewater and a river.

Microcystis aeruginosa lipids as feedstock for biodiesel synthesis by enzymatic route

The cyanobacterium Microcystis aeruginosa strain NPCD-1, isolated from sewage treatment plant and characterized as a non-microcystin producer by mass spectrometry and molecular analysis, was found to be a source of lipid when cultivated in ASM-1 medium at 25 degrees C under constant white fluorescent illumination (109 mu mol photon m(-2) s(-1)). In these conditions, biomass productivity of 46.92 +/- 3.84 mg L-1 day(-1) and lipid content of 28.10 +/- 1.47% were obtained. Quantitative analysis of fatty acid methyl esters demonstrated high concentration of saturated fatty acids (50%), palmitic (24.34%) and lauric (13.21%) acids being the major components. The remaining 50% constituting unsaturated fatty acids showed higher concentrations of oleic (26.88%) and linoleic (12.53%) acids. The feasibility to produce biodiesel from this cyanobacterial lipid was demonstrated by running enzymatic transesterification reactions catalyzed by Novozym (R) 435 and using palm oil as feedstock control. Batch experiments were carried out using tert-butanol and iso-octane as solvent. Results showed similarity on the main ethyl esters formed for both feedstocks. The highest ethyl ester concentration was related to palmitate and oleate esters followed by laurate and linoleate esters. However, both reaction rates and ester yields were dependent on the solvent tested. Total ethyl ester concentrations varied in the range of 44.24-67.84 wt%, corresponding to ester yields from 80 to 100%. Iso-octane provided better solubility and miscibility, with ester yield of 98.10% obtained at 48 h for reaction using the cyanobacterium lipid, while full conversion was achieved in 12 h for reaction carried out with palm oil. These results demonstrated that cyanobacterial lipids from M. aeruginosa NPCD-1 have interesting properties for biofuel production. (c) 2012 Elsevier B.V. All rights reserved.

EX-SITU BIOREMEDIATION OF BRAZILIAN SOIL CONTAMINATED WITH PLASTICIZERS PROCESS WASTES

The aim of this research was to evaluate the bioremediation of a soil contaminated with wastes from a plasticizers industry, located in Sao Paulo, Brazil. A 100-kg soil sample containing alcohols, adipates and phthalates was treated in an aerobic slurry-phase reactor using indigenous and acclimated microorganisms from the sludge of a wastewater treatment plant of the plasticizers industry (11gVSS kg(-1) dry soil), during 120 days. The soil pH and temperature were not corrected during bioremediation; soil humidity was corrected weekly to maintain 40%. The biodegradation of the pollutants followed first-order kinetics; the removal efficiencies were above 61% and, among the analyzed plasticizers, adipate was removed to below the detection limit. Biological molecular analysis during bioremediation revealed a significant change in the dominant populations initially present in the reactor.

An integrated approach to evaluate emerging contaminants in drinking water

The chemical stock of emerging contaminants in Brazilian drinking water is of great interest due to the poor water quality at surface water intakes. In addition, little is known about the effect of some contaminants, such as endocrine disrupting chemicals (EDCs), which may be present in both raw and treated water. The aim of this work was to evaluate selected emerging contaminants in Brazilian waters using both chemical and biological analyses. Sampling sites were established in different municipalities based upon raw water quality data. Estrone, 17 beta-estradiol, estriol, 17 alpha-ethinylestradiol, bisphenol A, 4-n-octylphenol and 4-n-nonylphenol were determined in the samples by liquid chromatography-tandem mass spectrometry. A yeast assay using a Saccharomyces cerevisiae bioluminescent bioreporter was used to evaluate the estrogenic activity of the water samples. The first integrated results revealed similarities between the two individual approaches, since higher values for the bioassay were accompanied by significant concentrations of some selected compounds in surface water samples. No estrogenicity was observed for drinking water samples. Our results also indicate that the usual paradigm of evaluating water quality by measuring selected EDCs in a given water sample via chemical analysis, needs to be reviewed since the observed estrogenicity of a water sample is now a better guiding parameter to the selection of samples and substances to be chemically investigated in further analysis. So far, the data bank produced in this work, i.e., the comparison between chemical burden and observed estrogenicity, is not yet sufficiently robust to fully guide this decision. (C) 2011 Elsevier B.V. All rights reserved.

Ex-situ bioremediation of Brazilian soil contaminated with plasticizers process wastes

The aim of this research was to evaluate the bioremediation of a soil contaminated with wastes from a plasticizers industry, located in São Paulo, Brazil. A 100-kg soil sample containing alcohols, adipates and phthalates was treated in an aerobic slurry-phase reactor using indigenous and acclimated microorganisms from the sludge of a wastewater treatment plant of the plasticizers industry (11gVSS kg-1 dry soil), during 120 days. The soil pH and temperature were not corrected during bioremediation; soil humidity was corrected weekly to maintain 40%. The biodegradation of the pollutants followed first-order kinetics; the removal efficiencies were above 61% and, among the analyzed plasticizers, adipate was removed to below the detection limit. Biological molecular analysis during bioremediation revealed a significant change in the dominant populations initially present in the reactor.

Enhancing spiral-wound ultrafiltration performance for direct drinking water treatment through operational procedures improvement: A feasible option for the Sao Paulo Metropolitan Region

This work aimed to evaluate the influence of specific operational conditions on the performance of a spiral-wound ultrafiltration pilot plant for direct drinking water treatment, installed at the Guarapiranga's reservoir, in the Sao Paulo Metropolitan Region. Results from operational tests showed that the volume of permeate produced in the combination of periodic relaxation with flushing and chlorine dosage procedures was 49% higher than the volume obtained when these procedures were not used. Two years of continuous operation demonstrated that the ultrafiltration pilot plant performed better during fall and winter seasons, higher permeate flow production and reduced chemical cleanings frequency. Observed behavior seems to be associated with the algae bloom events in the reservoir, which are more frequent during spring and summer seasons, confirmed by chlorophyll-a analysis results. Concentrate clarification using ferric chloride was quite effective in removing NOM and turbidity, allowing its recirculation to the ultrafiltration feed tank. This procedure made it possible to reach almost 99% water recovery considering a single 54-hour recirculation cycle. Water quality monitoring demonstrated that the ultrafiltration pilot plant was quite efficient, and that potential pathogenic organisms, Escherichia coil and total coliforms, turbidity and apparent color removals were 100%, 95.1%, and 91.5%, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Cannabidiol, a non-psychotropic plant-derived cannabinoid, decreases inflammation in a murine model of acute lung injury: Role for the adenosine A(2A) receptor

Acute lung injury is an inflammatory condition for which treatment is mainly supportive because effective therapies have not been developed. Cannabidiol, a non-psychotropic cannabinoid component of marijuana (Cannabis sativa), has potent immunosuppressive and anti-inflammatory properties. Therefore, we investigated the possible anti-inflammatory effect of cannabidiol in a murine model of acute lung injury. Analysis of total inflammatory cells and differential in bronchoalveolar lavage fluid was used to characterize leukocyte migration into the lungs; myeloperoxidase activity of lung tissue and albumin concentration in the bronchoalveolar lavage fluid were analyzed by colorimetric assays; cytokine/chemokine production in the bronchoalveolar lavage fluid was also analyzed by Cytometric Bead Arrays and Enzyme-Linked Immunosorbent Assay (ELISA). A single dose of cannabidiol (20 mg/kg) administered prior to the induction of LPS (lipopolysaccharide)-induced acute lung injury decreases leukocyte (specifically neutrophil) migration into the lungs, albumin concentration in the bronchoalveolar lavage fluid, myeloperoxidase activity in the lung tissue, and production of pro-inflammatory cytokines (TNF and IL-6) and chemokines (MCP-1 and MIP-2) 1, 2, and 4 days after the induction of LPS-induced acute lung injury. Additionally, adenosine A(2A) receptor is involved in the anti-inflammatory effects of cannabidiol on LPS-induced acute lung injury because ZM241385 (4-(2[7-Amino-2-(2-furyl)[1,2,4] triazolo[2,3-a][1,3,5]triazin-5-ylamino]ethyl) phenol) (a highly selective antagonist of adenosine A(2A) receptor) abrogated all of the anti-inflammatory effects of cannabidiol previously described. Thus, we show that cannabidiol has anti-inflammatory effects in a murine model of acute lung injury and that this effect is most likely associated with an increase in the extracellular adenosine offer and signaling through adenosine A(2A) receptor. (C) 2012 Elsevier B. V. All rights reserved.