The Deleterious Chemical Effects of Concentrated Deicing Solutions on Portland Cement Concrete, Technical Appendices, TR-480, 2008

This research project investigated the effects of concentrated brines of magnesium chloride, calcium chloride, sodium chloride, and calcium magnesium acetate on portland cement concrete. Although known to be effective at deicing and anti-icing, the deleterious effects these chemicals may have on concrete have not been well documented. As a result of this research, it was determined that there is significant evidence that magnesium chloride and calcium chloride chemically interact with hardened portland cement paste in concrete resulting in expansive cracking, increased permeability, and a significant loss in compressive strength. Although the same effects were not seen with sodium chloride brines, it was shown that sodium chloride brines have the highest rate of ingress into hardened concrete. This latter fact is significant with respect to corrosion of embedded steel. The mechanism for attack of hardened cement paste varies with deicer chemical but in general, a chemical reaction between chlorides and cement hydration products results in the dissolution of the hardened cement paste and formation of oxychloride phases, which are expansive. The chemical attack of the hardened cement paste is significantly reduced if supplementary cementitious materials are included in the concrete mixture. Both coal fly ash and ground granulated blast furnace slag were found to be effective at mitigating the chemical attack caused by the deicers tested. In the tests performed, ground granulated blast furnace slag performed better as a mitigation strategy as compared to coal fly ash. Additionally, siloxane and silane sealants were effective at slowing the ingress of deicing chemicals into the concrete and thereby reducing the observed distress. In general, the siloxane sealant appeared to be more effective than the silane, but both were effective and should be considered as a maintenance strategy.

Practical applications of a systematic approach to the chemical abatement of pollutants in water and air

The present dissertation is devoted to the systematic approach to the development of organic toxic and refractory pollutants abatement by chemical decomposition methods in aqueous and gaseous phases. The systematic approach outlines the basic scenario of chemical decomposition process applications with a step-by-step approximation to the most effective result with a predictable outcome for the full-scale application, confirmed by successful experience. The strategy includes the following steps: chemistry studies, reaction kinetic studies in interaction with the mass transfer processes under conditions of different control parameters, contact equipment design and studies, mathematical description of the process for its modelling and simulation, processes integration into treatment technology and its optimisation, and the treatment plant design. The main idea of the systematic approach for oxidation process introduction consists of a search for the most effective combination between the chemical reaction and the treatment device, in which the reaction is supposed to take place. Under this strategy,a knowledge of the reaction pathways, its products, stoichiometry and kinetics is fundamental and, unfortunately, often unavailable from the preliminary knowledge. Therefore, research made in chemistry on novel treatment methods, comprisesnowadays a substantial part of the efforts. Chemical decomposition methods in the aqueous phase include oxidation by ozonation, ozone-associated methods (O3/H2O2, O3/UV, O3/TiO2), Fenton reagent (H2O2/Fe2+/3+) and photocatalytic oxidation (PCO). In the gaseous phase, PCO and catalytic hydrolysis over zero valent ironsare developed. The experimental studies within the described methodology involve aqueous phase oxidation of natural organic matter (NOM) of potable water, phenolic and aromatic amino compounds, ethylene glycol and its derivatives as de-icing agents, and oxygenated motor fuel additives ¿ methyl tert-butyl ether (MTBE) ¿ in leachates and polluted groundwater. Gas-phase chemical decomposition includes PCO of volatile organic compounds and dechlorination of chlorinated methane derivatives. The results of the research summarised here are presented in fifteenattachments (publications and papers submitted for publication and under preparation).

Natural Products from Antarctic Colonial Ascidians of the Genera Aplidium and Synoicum: Variability and Defensive Role

Ascidians have developed multiple defensive strategies mostly related to physical, nutritional or chemical properties of the tunic. One of such is chemical defense based on secondary metabolites. We analyzed a series of colonial Antarctic ascidians from deep-water collections belonging to the genera Aplidium and Synoicum to evaluate the incidence of organic deterrents and their variability. The ether fractions from 15 samples including specimens of the species A. falklandicum, A. fuegiense, A. meridianum, A. millari and S. adareanum were subjected to feeding assays towards two relevant sympatric predators: the starfish Odontaster validus, and the amphipod Cheirimedon femoratus. All samples revealed repellency. Nonetheless, some colonies concentrated defensive chemicals in internal body-regions rather than in the tunic. Four ascidian-derived meroterpenoids, rossinones B and the three derivatives 2,3-epoxy-rossinone B, 3-epi-rossinone B, 5,6-epoxy-rossinone B, and the indole alkaloids meridianins A-G, along with other minoritary meridianin compounds were isolated from several samples. Some purified metabolites were tested in feeding assays exhibiting potent unpalatabilities, thus revealing their role in predation avoidance. Ascidian extracts and purified compound-fractions were further assessed in antibacterial tests against a marine Antarctic bacterium. Only the meridianins showed inhibition activity, demonstrating a multifunctional defensive role. According to their occurrence in nature and within our colonial specimens, the possible origin of both types of metabolites is discussed.

Chemical, physico-chemical and sensory characterization of mixed açai (Euterpe oleracea) and cocoa´s honey (Theobroma cacao) jellies

Four formulations of mixed açaí (Euterpe oleracea) (A) and cocoa´s honey (Theobroma cacao) (CH) jellies were prepared according to the following proportions: T1 (40% A:60% CH), T2 (50% A:50% CH), T3 (60% A: 40% CH) and T4 (100% A - control). All formulations were prepared using a rate 60:40 (w/w) of sucrose and pulp, plus 0.5% pectin and the products reached to average of 65% soluble solids content. The jellies were analyzed by chemical and physicochemical (titratable acidity, pH, soluble solid content, dry matter, total protein, lipids, vitamin C and calories) and sensory characteristics; also were evaluated levels of P, K, Ca, Mg, Fe, Zn, Cu and Mn. It was used a hedonic scale of 7 points to evaluate the attributes: overall impression, spreadability, brightness, flavor, texture and color, and also was verified the purchase intention score. The titratable acidity and pH ranged from 0.46 to 0.64% and 3.35 to 3.64, respectively, that are within the range found at most fruit jellies. The soluble solids content ranged between 65.2 and 65.5 ºBrix. The sensory acceptance results showed that all treatments (T1, T2, T3 and T4) presented means of sensory attributes above 4, demonstrating good acceptance of the product, but the treatment T1 presented the higher scores for the evaluated attributes. Cocoa´s honey added a positive influence on the attributes of color, texture and spreadability.

Assessment of the levels of degradation in fat co- and by-products for feed uses and their relationships with some lipid composition parameters

This paper discusses the levels of degradation of some co- and byproducts of the food chain intended for feed uses. As the first part of a research project, 'Feeding Fats Safety', financed by the sixth Framework Programme-EC, a total of 123 samples were collected from 10 European countries, corresponding to fat co- and byproducts such as animal fats, fish oils, acid oils from refining, recycled cooking oils, and other. Several composition and degradation parameters (moisture, acid value, diacylglycerols and monoacylglycerols, peroxides, secondary oxidation products, polymers of triacylglycerols, fatty acid composition, tocopherols, and tocotrienols) were evaluated. These findings led to the conclusion that some fat by- and coproducts, such as fish oils, lecithins, and acid oils, show poor, nonstandardized quality and that production processes need to be greatly improved. Conclusions are also put forward about the applicability and utility of each analytical parameter for characterization and quality control.

Imaging the time-integrated cerebral metabolic activity with subcellular resolution through nanometer-scale detection of biosynthetic products deriving from (13)C-glucose.

Glucose is the primary source of energy for the brain but also an important source of building blocks for proteins, lipids, and nucleic acids. Little is known about the use of glucose for biosynthesis in tissues at the cellular level. We demonstrate that local cerebral metabolic activity can be mapped in mouse brain tissue by quantitatively imaging the biosynthetic products deriving from [U-(13)C]glucose metabolism using a combination of in situ electron microscopy and secondary ion mass-spectroscopy (NanoSIMS). Images of the (13)C-label incorporated into cerebral ultrastructure with ca. 100nm resolution allowed us to determine the timescale on which the metabolic products of glucose are incorporated into different cells, their sub-compartments and organelles. These were mapped in astrocytes and neurons in the different layers of the motor cortex. We see evidence for high metabolic activity in neurons via the nucleus (13)C enrichment. We observe that in all the major cell compartments, such as e.g. nucleus and Golgi apparatus, neurons incorporate substantially higher concentrations of (13)C-label than astrocytes.

Identification of new transformation products during enzymatic treatment of tetracycline and erythromycin antibiotics at laboratory scale by an on-line turbulent flow liquid-chromatography coupled to a high resolution mass spectrometer LTQ-Orbitrap

This work describes the formation of transformation products (TPs) by the enzymatic degradation at laboratory scale of two highly consumed antibiotics: tetracycline (Tc) and erythromycin (ERY). The analysis of the samples was carried out by a fast and simple method based on the novel configuration of the on-line turbulent flow system coupled to a hybrid linear ion trap – high resolution mass spectrometer. The method was optimized and validated for the complete analysis of ERY, Tc and their transformation products within 10 min without any other sample manipulation. Furthermore, the applicability of the on-line procedure was evaluated for 25 additional antibiotics, covering a wide range of chemical classes in different environmental waters with satisfactory quality parameters. Degradation rates obtained for Tc by laccase enzyme and ERY by EreB esterase enzyme without the presence of mediators were ∼78% and ∼50%, respectively. Concerning the identification of TPs, three suspected compounds for Tc and five of ERY have been proposed. In the case of Tc, the tentative molecular formulas with errors mass within 2 ppm have been based on the hypothesis of dehydroxylation, (bi)demethylation and oxidation of the rings A and C as major reactions. In contrast, the major TP detected for ERY has been identified as the “dehydration ERY-A”, with the same molecular formula of its parent compound. In addition, the evaluation of the antibiotic activity of the samples along the enzymatic treatments showed a decrease around 100% in both cases

Identification of metabolites and thermal transformation products of quinolones in raw cow milk by liquid chromatography coupled to high resolution mass spectrometry

The presence of residues of antibiotics, metabolites, and thermal transformation products (TPs), produced during thermal treatment to eliminate pathogenic microorganisms in milk, could represent a risk for people. Cow"s milk samples spiked with enrofloxacin (ENR), ciprofloxacin (CIP), difloxacin (DIF), and sarafloxacin (SAR) and milk samples from cows medicated with ENR were submitted to several thermal treatments. The milk samples were analyzed by liquid chromatography-mass spectrometry (LC-MS) to find and identify TPs and metabolites. In this work, 27 TPs of 4 quinolones and 24 metabolites of ENR were found. Some of these compounds had been reported previously, but others were characterized for the first time, including lactose-conjugated CIP, the formamidation reaction for CIP and SAR, and hydroxylation or ketone formation to produce three different isomers for all quinolones studied.

Identification of metabolites and thermal transformation products of quinolones in raw cow milk by liquid chromatography coupled to high resolution mass spectrometry.

The presence of residues of antibiotics, metabolites, and thermal transformation products (TPs), produced during thermal treatment to eliminate pathogenic microorganisms in milk, could represent a risk for people. Cow"s milk samples spiked with enrofloxacin (ENR), ciprofloxacin (CIP), difloxacin (DIF), and sarafloxacin (SAR) and milk samples from cows medicated with ENR were submitted to several thermal treatments. The milk samples were analyzed by liquid chromatography-mass spectrometry (LC-MS) to find and identify TPs and metabolites. In this work, 27 TPs of 4 quinolones and 24 metabolites of ENR were found. Some of these compounds had been reported previously, but others were characterized for the first time, including lactose-conjugated CIP, the formamidation reaction for CIP and SAR, and hydroxylation or ketone formation to produce three different isomers for all quinolones studied.

Determination of polyphenol contents and antioxidant capacity of no-alcoholic red grape products (vitis labrusca) from conventional and organic crops

The polyphenol contents and antioxidant capacity of Brazilian red grape juices and wine vinegars were analyzed. Additionally, it was analyzed the human polyphenol absorption and acute effect in plasmatic oxidative metabolism biomarkers after juice ingestion. The organic Bordo grape juice (GBO) presented a higher level of trans-resveratrol, quercitin, rutin, gallic acid, caffeic acid and total flavonoids then other juices and vinegars as well as antioxidant capacity. The plasmatic polyphenol increased 27.2% after GBO juice ingestion. The results showed that juices and vinegars from Brazilian crops present similar chemical and functional properties described in studies performed in other countries.

Isolation and quantitative HPLC-PDA analysis of lupeol in phytopharmaceutical intermediate products from Vernonanthura ferruginea (Less.) H. Rob.

Prior to obtain a standardized dried extract from V. ferruginea, lupeol was first time isolated from leaves and used as chemical maker. An analytical method using HPLC-PDA for lupeol determination in V. ferruginea intermediate products was developed using a C8 reverse-phase column, acetonitrile-acetic acid (99.99:0.01, v/v) as mobile phase at 0.8 mL min-1, oven temperature at 23-25 ºC, sample injection volume at 30 µL and detection at 210 nm. The method presented linearity from 10 to 160 µg mL-1, accuracy, precision, robustness and suitable sensitivity proving to be a useful tool to the obtainment process of lupeol standardized dried extracts of V. ferruginea.

Chemical constituents from red algae Bostrychia radicans (Rhodomelaceae): new amides and phenolic compounds

This study describes the isolation and structural determination of two amides, isolated for the first time: N,4-dihydroxy-N-(2'-hydroxyethyl)-benzamide (0.019%) and N,4-dihydroxy-N-(2'-hydroxyethyl)-benzeneacetamide (0.023%). These amides, produced by the red macroalgae Bostrychia radicans, had their structures assigned by NMR spectral data and MS analyses. In addition, this chemical study led to the isolation of cholesterol, heptadecane, squalene, trans-phytol, neophytadiene, tetradecanoic and hexadecanoic acids, methyl hexadecanoate and methyl 9-octadecenoate, 4-(methoxymethyl)-phenol, 4-hydroxybenzaldehyde, methyl 4-hydroxybenzeneacetate, methyl 2-hydroxy-3-(4-hydroxyphenyl)-propanoate, hydroquinone, methyl 4-hydroxymandelate, methyl 4-hydroxybenzoate, 4-hydroxybenzeneacetic acid and (4-hydroxyphenyl)-oxo-acetaldehyde. This is the first report concerning these compounds in B. radicans, contributing by illustrating the chemical diversity within the Rhodomelaceae family.

CHEMICAL STUDY OF Hortia superba (Rutaceae) AND INVESTIGATION OF THE ANTIMYCOBACTERIAL ACTIVITY OF CRUDE EXTRACTS AND CONSTITUENTS ISOLATED FROM Hortia SPECIES

In this paper, the chemical study of Hortia superba and antimycobacterial potential of Hortia species were investigated. Crude extracts and limonoids, alkaloids, dihydrocinnamic acid derivatives and coumarins isolated from Hortia superba, Hortia oreadica and Hortia brasiliana were evaluated against Mycobacterium tuberculosis H37Rv, Mycobacterium kansasii and Mycobacterium avium. The results obtained demonstrated an inhibitory effect of the dichloromethane extract of leaves of H. oreadica (MIC 31.25 µg mL-1), indolequinazoline (15.62 µg mL-1) and furoquinoline (31.25 µg mL-1) alkaloids, and dihydrocinnamic acid derivatives (62.50 µg mL-1), on the growth of M. tuberculosis. These results are promising in relation to the search for biologically active natural products and could be useful in the development of effective new drugs against mycobacteria.

CHEMICAL COMPOSITION AND ANTI-INFLAMMATORY ACTIVITY OF Roldana platanifolia

The chemical study of Roldana platanifolia led to the isolation of β-caryophyllene, five eremophilanolides, chlorogenic acid, and a mixture of β-sitosterol-stigmasterol, β-sitosteryl glucopyranoside, and sucrose. The anti-inflammatory activities of the extracts and isolated products were tested using the 12-O-tetradecanoylphorbol-13-acetate (TPA) model of induced acute inflammation. The acetone and methanol extracts showed dose dependent activities (ID50 0.21 and 0.32 mg/ear, respectively), while none of the isolated compounds exhibited relevant edema inhibition. The active extracts were also evaluated with the myeloperoxidase assay technique (MPO) to determine their ability to prevent neutrophil infiltration. Results showed that the anti-inflammatory activity was related to the compound’s ability to inhibit pro-inflammatory mediators such as neutrophils.

Utilization of non-wood pulp in different fibers products

The correct utilization of non-wood raw material allows reducing tree cutting and reduces emissions of carbon dioxide from burning of non-wood plants on farmers fields. Also it allows increasing economical situation in regions that non-wood plants are grown and where they are converted into pulp and paper. Also it gives positive effect on population pressure of work by addition of working place. In the literature survey included an overview of the historical meaning of non-wood pulp on developing paper production and structure of non-wood pulps. Moreover, anatomical and chemical composition of straw, reed and bamboo were studied more detailed. Also, an overview of the utilization of non-wood pulp in papermaking was made. Especially tissue, tree-free and release papers were reviewed. In the experimental part the goal was to investigate suitability of non-wood pulp like wheat straw pulp and bamboo pulp for different fiber products. Finally release and tree-free paper products were selected for experimental studies. It was discovered that wheat straw, especially screened wheat straw, showed good results for release paper. Also utilization of wheat straw and bamboo pulp in tree-free paper showed good results and suitability of these non-wood pulps for tree-free paper production. Also it was noticed that addition of wheat straw pulp gave positive effect on initial wet strength for release and tree-free paper.