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Investigation of aqueous biphasic systems for the separation of lignins from cellulose in the paper pulping process.

In efforts to apply a polymer-based aqueous biphasic system (ABS) extraction to the paper pulping process, the study of the distribution of various lignin and cellulosic fractions in ABS and the effects of temperature on system composition and solute partitioning have been investigated. The partitioning of three lignin species (Indulin AT, Indulin C, and Reax 85A) have been studied in ABS prepared from stock solutions of 40% (w/w) poly(ethylene glycol) (PEG)-2000 and increasing concentrations of K2CO3, (NH4)2SO4, and NaOH. The partitioning of these lignins is affected by the free energy of hydration of the salt forming the ABS, the tie line length, and the dissociation of the sulfonic acid and hydroxyl groups of the distributed solutes. The partitioning of fibrous cellulose and diethylaminoethyl cellulose have been studied in 40% (w/w) PEG-2000-(NH4)2SO4 ABS. The hydrophilic nature of these species is important in terms of their phase preference when designing a polymer-based aqueous biphasic extraction process for use in a paper pulping process. Both cellulosic samples do not dissolve, but rather report to the salt-rich phase of an ABS. In both chemical pulping and Organosolv pulping, temperatures in excess of 120 degrees C are needed to solubilize the lignin from the cellulose fraction of wood. To study the effects of temperature on the phase diagram and solute partitioning, phthalic acid and NH499TcO4 (as system probes) have been partitioned in 40% (w/w) PEG-2000-(NH4)2SO4 ABS at known tie line lengths as a function of temperature. Temperature does not appear to affect the partitioning results beyond the expected increase in phase divergence as temperature is increased. The PEG-2000 polymer itself appears to be stable to chemical pulping conditions.

Cellulose↗

Spectral analysis and fingerprinting for biomedia characterisation.

Classical culture media, as well as domestic and/or industrial wastewater treated by biological processes, have a complex composition. The on-line and/or in situ determination of some substances is possible, but expensive, as sample collection and pre-treatment are often necessary with strict rules of sterility. More global methods can be used to detect rapidly "accidents" such as the appearance of an undesirable by-product in a fermentation broth or of a toxic substance in wastewater. These methods combine a "hard" part, for sensing, and a "soft" part, for data treatment. Among potential "hard" candidates, spectroscopy can be the basis for non-invasive and non-destructive measuring systems. Some of them have been already tested in situ: ultra-violet-visible, infra-red (mid or near), fluorescence (mono-dimensional, two-dimensional or synchronous), dielectric, while others, more sophisticated, such as mass spectrometry, coupled or not to pyrolysis, nuclear magnetic resonance and Raman spectroscopy, have been proposed. All these methods provide spectra, i.e. large sets of data, from which meaningful information should be rapidly extracted, either for analysis or fingerprinting. The recourse to data-mining techniques (the "soft" part) such as principal components analysis, projection on latent structures or artificial neural networks, is a necessary step for that task. A review of techniques, mostly based on spectroscopy, with examples taken in the bioengineering field in general is proposed.

Biotechnology↗

Development of a reliable alkaline wastewater treatment process: optimization of the pre-treatment step.

Alkaline waters produced by caprolactam plants polymerizing the fibres of nylon-6 are characterized by a very high alkalinity, salinity and COD values, in addition to the presence of recalcitrant organic molecules. These characteristics make alkaline wastewaters very difficult to treat; so the development of the suitable sequence to carry out in a depuration process appears of great interest. The proposed general process consists of three main steps: first, pre-treatment for the acidification of the polluted stream, second, a successive extraction of the bio-recalcitrant compound (noted as cycloexanecarboxysulphonic acid (CECS)) and a final biological treatment. In particular, this paper deals with the pre-treatment step: it consists of an acidification process by means of sulphuric acid with the concomitant precipitation of black slurries in the presence of different substances, such as solvents, CaCl2, bentonite, several flocculants and coagulants. The aim of this study is to set an experimental procedure, which could minimize fouling problems during sludge filtration. The use of additives like bentonite seems to give the best results, because it allows good COD reductions and a filterable precipitate, which avoids excessive fouling problems of the experimental apparatus.

Acetates↗

Enzymatic and fungal treatments on sugarcane bagasse for the production of mechanical pulps.

Crude ligninolytic enzyme extracts from Phanerochaete chrysosporium fungi were applied to sugarcane bagasse, prior to thermomechanical (TMP) and chemithermomechanical pulping (CTMP), and their properties were compared with the normal TMP and CTMP and also with TMP and CTMP pretreated with Ceriporiopsis subvermispora and P. chrysosporium fungi. The sugarcane bagasse was impregnated with the crude enzyme extract containing lignin peroxidase (LiP), manganese peroxidase (MnP), and laccase (Lac). The results show that pretreatment with enzyme crude extract is an advantageous way to produce TMP and CTMP from sugarcane bagasse, as compared with only fungal pretreatment. Enzymatic pretreatments need only hours to enhance pulping and paper properties, compared with the weeks necessary for fungal treatments. Higher pulp yields were obtained compared with the fungal pretreatments. Enzymatic pretreatment reduced the energy consumption in a proportion similar to that of C. subvermispora fungal pretreatment and increased the pulp tensile index compared with the normal TMP and CTMP pulps, although the tensile strength was somewhat lower than that for pulps from C. subvermispora fungal pretreatment before CTMP processing. An advantage of enzymatic pretreatment is that brightness is increased compared with normal TMP and CTMP processes, whereas fungal pretreatments reduce the brightness.

Biomechanical Phenomena↗

Red Xylem and Higher Lignin Extractability by Down-Regulating a Cinnamyl Alcohol Dehydrogenase in Poplar.

Cinnamyl alcohol dehydrogenase (CAD) catalyzes the last step in the biosynthesis of the lignin precursors, the monolignols. We have down-regulated CAD in transgenic poplar (Populus tremula X Populus alba) by both antisense and co-suppression strategies. Several antisense and sense CAD transgenic poplars had an approximately 70% reduced CAD activity that was associated with a red coloration of the xylem tissue. Neither the lignin amount nor the lignin monomeric composition (syringyl/guaiacyl) were significantly modified. However, phloroglucinol-HCl staining was different in the down-regulated CAD plants, suggesting changes in the number of aldehyde units in the lignin. Furthermore, the reactivity of the cell wall toward alkali treatment was altered: a lower amount of lignin was found in the insoluble, saponified residue and more lignin could be precipitated from the soluble alkali fraction. Moreover, large amounts of phenolic compounds, vanillin and especially syringaldehyde, were detected in the soluble alkali fraction of the CAD down-regulated poplars. Alkaline pulping experiments on 3-month-old trees showed a reduction of the kappa number without affecting the degree of cellulose degradation. These results indicate that reducing the CAD activity in trees might be a valuable strategy to optimize certain processes of the wood industry, especially those of the pulp and paper industry.

Journal Article↗

Electrospray emission from nonwetting flat dielectric surfaces.

Electrosprays are devices in which nanometer sized droplets and/or solvated ions are electrically extracted from a liquid surface and accelerated to high velocities. They are usually constructed from conductive capillaries with one of the ends tapered down to a sharp tip with the purpose of enhancing the local electric field that produces the instability that develops into the Taylor cone structure from which emission occurs. In an alternative configuration, the conductive needles are replaced by small holes through a dielectric, nonwetting flat block. An electrostatic model shows that if the emitter material has low dielectric constant then the local electric field near the emission site is enhanced in a very similar way as with sharp metallic needles. Furthermore, the combination of the nonwetting property of the material and the sharp corner formed in the hole-surface interface effectively anchors the Taylor cone to the edge of the hole, thus simplifying the process of manufacturing. The possible microfabrication of this configuration makes it especially attractive for producing arrays of large numbers of individual emitters. Such arrays may find use as space propulsion thrusters and in the analytical industry to improve the characteristics of mass-spectrometric analyses.

Journal Article↗

Toxicity of hexavalent chromium and its reduction by bacteria isolated from soil contaminated with tannery waste.

An Arthrobacter sp. and a Bacillus sp., isolated from a long-term tannery waste contaminated soil, were examined for their tolerance to hexavalent chromium [Cr(VI)] and their ability to reduce Cr(VI) to Cr(III), a detoxification process in cell suspensions and cell extracts. Both bacteria tolerated Cr(VI) at 100 mg/ml on a minimal salts agar medium supplemented with 0.5% glucose, but only Arthrobacter could grow in liquid medium at this concentration. Arthrobacter sp. could reduce Cr(VI) up to 50 microg/ml, while Bacillus sp. was not able to reduce Cr(VI) beyond 20 microg/ml. Arthrobacter sp. was distinctly superior to the Bacillus sp. in terms of their Cr(VI)-reducing ability and resistance to Cr(VI). Assays with permeabilized (treated with toluene or Triton X 100) cells and crude extracts demonstrated that the Cr(VI) reduction was mainly associated with the soluble protein fraction of the cell. Arthrobacter sp. has a great potential for bioremediation of Cr(VI)-containing waste.

Arthrobacter↗

Coliforms, Escherichia coli and Salmonella serovars associated with a citrus-processing facility implicated in a salmonellosis outbreak.

A salmonellosis outbreak occurred during the summer of 1995 among individuals who consumed nonpasteurized orange juice from a Florida citrus-processing facility. Clinical isolates were identified by the Centers for Disease Control as Salmonella serovars Hartford, Gaminara, and Rubislaw. At the processing facility, 70 samples (equipment swabs, fruit surface swabs, juice, and miscellaneous environmental samples) were collected before, during, and after processing runs on two different dates. Bottled juice samples from eight previous extraction dates were also collected. Total plate counts, fecal coliforms, and Escherichia coli were enumerated from each sample. Analysis for Salmonella cells were conducted on all juice samples, fruit surface swabs, environmental samples, and selected equipment swabs using direct enrichment and pre-enrichment techniques. Salmonella serovars Hartford, Rubislaw, Saintpaul, and Newport were detected from either juice, unwashed fruit surfaces, or amphibians (Hyla cinerea and Bufo terrestris) captured outside the processing building. Salmonella cells in juice were associated with population levels of fecal coliforms and E. coli above the upper most probable number (MPN) limits of detection (> 110/ml).

Animals↗

Study on the development of pomegranate juice processing technology: clarification of pomegranate juice.

The effects of clarification agents and methods on pomegranate juice quality were studied. Fruits were pressed as whole, and extracted juice was clarified with gelatin, polyvinylypolypyrrolidone (PVPP) and natural sedimentation. In order to determine the effects of these clarifying techniques on product quality, pH, total phenolic substances (TPS), anthocyanin, turbidity, and total colour density tests were applied to each sample. In clarification, the main purpose was to reduce the amount of phenolic substances. Phenolic substances were controlled in each clarification method. The most effective method was the application of 1 g/L gelatine for clarification. Sensory evaluation also applied for clarified juices and gelatin application was selected by panelists to be superior.

Anthocyanins↗

Human impacts on the stream-groundwater exchange zone.

Active exchanges of water and dissolved material between the stream and groundwater in many porous sand- and gravel-bed rivers create a dynamic ecotone called the hyporheic zone. Because it lies between two heavily exploited freshwater resources-rivers and groundwater-the hyporheic zone is vulnerable to impacts coming to it through both of these habitats. This review focuses on the direct and indirect effects of human activity on ecosystem functions of the hyporheic zone. River regulation, mining, agriculture, urban, and industrial activities all have the potential to impair interstitial bacterial and invertebrate biota and disrupt the hydrological connections between the hyporheic zone and stream, groundwater, riparian, and floodplain ecosystems. Until recently, our scientific ignorance of hyporheic processes has perhaps excused the inclusion of this ecotone in river management policy. However, this no longer is the case as we become increasingly aware of the central role that the hyporheic zone plays in the maintenance of water quality and as a habitat and refuge for fauna. To fully understand the impacts of human activity on the hyporheic zone, river managers need to work with scientists to conduct long-term studies over large stretches of river. River rehabilitation and protection strategies need to prevent the degradation of linkages between the hyporheic zone and surrounding habitats while ensuring that it remains isolated from toxicants. Strategies that prevent anthropogenic restriction of exchanges may include the periodic release of environmental flows to flush silt and reoxygenate sediments, maintenance of riparian buffers, effective land use practices, and suitable groundwater and surface water extraction policies.

Conservation of Natural Resources↗

Polar organic pollutants in the Elbe river. Liquid chromatographic-mass spectrometric and flow-injection analysis-mass spectrometric analyses demonstrating changes in quality and concentration during the unification process in Germany.

During the unification process of the two German states from 1989 to 1994, water extracts from the Elbe river were analyzed by gas chromatography-mass spectrometry (GC-MS) and by high-performance liquid chromatography (HPLC) combined with ultraviolet (UV) and/or mass spectrometric detection (MS) in order to monitor the pollutants in one of the most contaminated European rivers. After column chromatography (LC) or flow-injection analysis (FIA) bypassing the analytical column, ionization was performed by a thermospray interface (TSP). Semiquantitative estimations of the pollution of the Elbe were made from the total-ion current traces (TIC) of the extracts. Determination of the total dissolved organic carbon (DOC) indicated a reduction of more than 55% of pollutants in the water phase. The pollutants were identified by tandem mass spectrometry (MS-MS), generating daughter-ion spectra by collision-induced dissociation (CID) using either column chromatography or direct mixture analysis. Compound-specific analyses indicated a reduction in the amount of pollutants as well as a change in their composition. This could be explained by reduced industrial production and by intensified construction of biological sewage treatment plants.

Chromatography, High Pressure Liquid↗

Production in large quantities of highly purified hydroxytyrosol from liquid-solid waste of two-phase olive oil processing or "Alperujo".

The effect of hydrothermal treatment of two-phase olive waste (alperujo) on the solubilization of hydroxytyrosol was studied. Different conditions of saturated steam were assayed. A high amount of hydroxytyrosol was solubilized and increased with increasing steaming temperature and time, reaching 1.4-1.7 g/100 g of dry alperujo. The effect of acidic (H(2)SO(4)) and basic (NaOH) catalysts was also evaluated. Acid-catalyzed treatment was more effective at milder conditions, whereas the alkali-catalyzed conditions were not very suitable. In the present study, the extracted hydroxytyrosol was purified by means of a new, simple, and inexpensive chromatographic system, under international patent application (PCT/ES02/00058). From 1000 kg of alperujo, with 70% humidity, can be obtained approximately 4.5-5 kg of hydroxytyrosol. After a purification process, at least 3 kg of hydroxytyrosol, at 90-95% purity, would be obtained. The purified compound was identified by HPLC/UV and (1)H and (13)C NMR analyses, and its antioxidant activity was tested on refined olive oil without antioxidants by Rancimat method. The oxidative stability of refined olive oil was increased by a factor of 1.71 in the presence of 100 ppm of hydroxytyrosol.

Chromatography, High Pressure Liquid↗

Natural plant chemicals: sources of industrial and medicinal materials.

Many higher plants produce economically important organic compounds such as oils, resins, tannins, natural rubber, gums, waxes, dyes, flavors and fragrances, pharmaceuticals, and pesticides. However, most species of higher plants have never been described, much less surveyed for chemical or biologically active constituents, and new sources of commercially valuable materials remain to be discovered. Advances in biotechnology, particularly methods for culturing plant cells and tissues, should provide new means for the commercial processing of even rare plants and the chemicals they produce. These new technologies will extend and enhance the usefulness of plants as renewable resources of valuable chemicals. In the future, biologically active plant-derived chemicals can be expected to play an increasingly significant role in the commercial development of new products for regulating plant growth and for insect and weed control.

Antineoplastic Agents, Phytogenic↗

Immunologic findings in confectionary workers.

BACKGROUND: Food allergies are frequent in the general population. There are however, few studies of immunologic responses among workers in the confectionary industry. OBJECTIVE: To assess immunologic and clinical findings of workers in a confectionary plant. METHODS: Immunologic (skin tests and serum IgE) and respiratory findings (symptoms and lung function) were studied in a group of 71 confectionary workers (mean age: 35 years and mean exposure: 11 years). RESULTS: Skin prick testing with food extracts used in the manufacturing of candies and pastries demonstrated that the most frequent positive skin reaction occurred with extracts of cacao (31%), followed by reactions to chocolate (9%), cocoa (6%), hazelnut (6%), and sugar (2%). Increased serum IgE levels were found in 13.0% and increased IgM serum levels in 52.1% of these confectionary workers. The prevalence of asthma (26.1%) and dyspnea (26.1%) in workers with positive skin tests was significantly higher than in workers with negative skin tests (asthma: 2.0%, P = .004; dyspnea: 4.1%, P = .001). There was a high prevalence of acute respiratory symptoms during the work shift, but no significant association with immunologic tests was found. Similarly, both skin test positive and skin test negative workers exhibited significant across shift changes in lung function; however, no significant differences in baseline lung function or across-shift changes were noted between skin test positive and negative workers. Pre-shift administration of disodium cromoglycate (DSCG) significantly diminished across-shift reductions in FEF50 and FEF25 for both skin test positive and skin test negative workers. CONCLUSIONS: These data suggest that exposure to environmental factors in confectionary plants is associated with frequent respiratory symptoms of an irritative nature. Specific skin testing may be useful in characterizing confectionary workers at risk for the development of occupational asthma.

Adult↗

Ethidium bromide stimulated hyper laccase production from bird's nest fungus Cyathus bulleri.

AIMS: Effect of ethidium bromide, a DNA intercalating agent, on laccase production from Cyathus bulleri was studied. METHODS AND RESULTS: The bird's nest fungus, Cyathus bulleri was grown on 2% (w/v) malt extract agar (MEA) supplemented with 1.5 microg ml(-1) of the phenanthridine dye ethidium bromide (EtBr) for 7 d and when grown subsequently in malt extract broth (MEB), produced a 4.2-fold increase in laccase production as compared to the untreated fungus. The fungal cultures following a single EtBr treatment, when regrown on MEA devoid of EtBr, produced a sixfold increase in laccase in MEB. However, on subsequent culturing on MEA in the absence of EtBr, only a 2.5-fold increase in laccase production could be maintained. In another attempt, the initial EtBr-treated cultures, when subjected to a second EtBr treatment (1.5 microg ml(-1)) on MEA for 7 d, produced a 1.4-fold increase in laccase production in MEB. CONCLUSIONS: The white-rot fungus Cyathus bulleri, when treated with EtBr at a concentration of 1.5 microg ml(-1) and regrown on MEA devoid of EtBr, produced a sixfold increase in laccase production in MEB. SIGNIFICANCE AND THE IMPACT OF THE STUDY: The variable form of C. bulleri capable of hyper laccase production can improve the economic feasibility of environmentally benign processes involving use of fungal laccases in cosmetics (including hair dyes), food and beverages, clinical diagnostics, pulp and paper industry, industrial effluent treatment, animal biotechnology and biotransformations.

Animals↗

Wood smoke contribution to winter aerosol in Fresno, CA.

In an effort to better quantify wintertime particulate matter (PM) and the contribution of wood smoke to air pollution events in Fresno, CA, a field campaign was conducted in winter 2003-2004. Coarse and fine daily PM samples were collected at five locations in Fresno, including residential, urban, and industrial areas. Measurements of collected samples included gravimetric mass determination, organic and elemental carbon analysis, and trace organic compound analysis by gas chromatograph mass spectrometry (GC/MS). The wood smoke tracer levoglucosan was also measured in aqueous aerosol extracts using high-performance anion exchange chromatography coupled with pulsed amperometric detection. Sample preparation and analysis by this technique is much simpler and less expensive than derivatized levoglucosan analysis by GC/MS, permitting analysis of daily PM samples from all five of the measurement locations. Analyses revealed low spatial variability and similar temporal patterns of PM2.5 mass, organic carbon (OC), and levoglucosan. Daily mass concentrations appear to have been strongly influenced by meteorological conditions, including precipitation, wind, and fog events. Fine PM (PM2.5) concentrations are uncommonly low during the study period, reflecting frequent precipitation events. During the first portion of the study, levoglucosan had a strong relationship to the concentrations of PM2.5 and OC. In the later portion of the study, there was a significant reduction in levoglucosan relative to PM2.5 and OC. This may indicate a change in particle removal processes, perhaps because of fog events, which were more common in the latter period. Combined, the emissions from wood smoke, meat cooking, and motor vehicles appear to contribute approximately 65-80% to measured OC, with wood smoke, on average, accounting for approximately 41% of OC and approximately 18% of PM2.5 mass. Two residential sites exhibit somewhat higher contributions of wood smoke to OC than other locations.

Aerosols↗

In vivo kinetics of trichloroacetate in male Fischer 344 rats.

Trichloroacetate (TCA) is a toxicologically important metabolite of the industrial solvents trichloroethylene and tetrachloroethylene, and a by-product of the chlorination of drinking water. Tissue disposition and elimination of 14C-TCA were investigated in male Fischer 344 rats injected iv with 6.1, 61, or 306 micromol TCA/kg body weight. Blood and tissues were collected at various time points up to 24 h. No metabolites were observed in plasma, urine, or tissue extracts. Overall TCA kinetics in tissues were similar at all doses. Based on similar terminal elimination rate constants, tissues could be divided into three classes: plasma, RBC, muscle, and fat; kidney and skin; and liver, small intestine, and large intestine. Nonextractable radiolabel, assumed to be biologically incorporated metabolites in both liver and plasma, increased with time, peaking at 6-9 h postinjection. The fraction of the initial dose excreted in the urine at 24 h increased from 67% to 84% as the dose increased, whereas fecal excretion decreased from 7% to 4%. The cumulative elimination of TCA as CO2 at 24 h decreased from 12% to 8% of the total dose. Two important kinetic processes were identified: a) hepatic intracellular concentrations of TCA were significantly greater than free plasma concentrations, indicating concentrative transport at the hepatic sinusoidal plasma membrane, and b) TCA appears to be reabsorbed from urine postfiltration at the glomerulus, either in the renal tubules or in the bladder. These processes have an impact on the effective tissue dosimetry in liver and kidney and may play an important role in TCA toxicity.

Animals↗

Childhood cancers and atmospheric carcinogens.

STUDY OBJECTIVES: To retest previous findings that childhood cancers are probably initiated by prenatal exposures to combustion process gases and to volatile organic compounds (VOCs); and to identify specific chemical hazards. DESIGN: Birth and death addresses of fatal child cancers in Great Britain between 1966 and 1980, were linked with high local atmospheric emissions of different chemical species. Among migrant children, distances from each address to the nearest emissions "hotspot" were compared. Excesses of outward over inward migrations show an increased prenatal or early infancy risk. SETTING AND SUBJECTS: Maps of emissions of many different substances were published on the internet by the National Atmospheric Emissions Inventory and "hotspots" for 2001 were translated to map coordinates. Child cancer addresses were extracted from an earlier inquiry into the carcinogenic effects of obstetric radiographs; and their postcodes translated to map references. MAIN RESULTS: Significant birth proximity relative risks were found within 1.0 km of hotspots for carbon monoxide, PM10 particles, VOCs, nitrogen oxides, benzene, dioxins, 1,3-butadiene, and benz(a)pyrene. Calculated attributable risks showed that most child cancers and leukaemias are probably initiated by such exposures. CONCLUSIONS: Reported associations of cancer birth places with sites of industrial combustion, VOCs uses, and associated engine exhausts, are confirmed. Newly identified specific hazards include the known carcinogens 1,3-butadiene, dioxins, and benz(a)pyrene. The mother probably inhales these or related materials and passes them to the fetus across the placenta.

Adolescent↗