Measurement of biologically available naphthalene in gas and aqueous phases by use of a Pseudomonas putida biosensor.

Genetically constructed microbial biosensors for measuring organic pollutants are mostly applied in aqueous samples. Unfortunately, the detection limit of most biosensors is insufficient to detect pollutants at low but environmentally relevant concentrations. However, organic pollutants with low levels of water solubility often have significant gas-water partitioning coefficients, which in principle makes it possible to measure such compounds in the gas rather than the aqueous phase. Here we describe the first use of a microbial biosensor for measuring organic pollutants directly in the gas phase. For this purpose, we reconstructed a bioluminescent Pseudomonas putida naphthalene biosensor strain to carry the NAH7 plasmid and a chromosomally inserted gene fusion between the sal promoter and the luxAB genes. Specific calibration studies were performed with suspended and filter-immobilized biosensor cells, in aqueous solution and in the gas phase. Gas phase measurements with filter-immobilized biosensor cells in closed flasks, with a naphthalene-contaminated aqueous phase, showed that the biosensor cells can measure naphthalene effectively. The biosensor cells on the filter responded with increasing light output proportional to the naphthalene concentration added to the water phase, even though only a small proportion of the naphthalene was present in the gas phase. In fact, the biosensor cells could concentrate a larger proportion of naphthalene through the gas phase than in the aqueous suspension, probably due to faster transport of naphthalene to the cells in the gas phase. This led to a 10-fold lower detectable aqueous naphthalene concentration (50 nM instead of 0.5 micro M). Thus, the use of bacterial biosensors for measuring organic pollutants in the gas phase is a valid method for increasing the sensitivity of these valuable biological devices.

Comparison of flag leaf and ear photosynthesis with biomass and grain yield of durum wheat under various water conditions and genotypes

Photosynthetic activity of cereals has traditionally been studied using leaves, thus neglecting the role of other organs such as ears. Here, we studied the effects of water status and genotypes on the photosynthetic activity of the flag leaf blade and the ear of durum wheat. The various parameters related to the photosynthetic activity were analysed in relation to the total above-ground plant biomass and grain yield at maturity. Four local varieties plus two cultivars adapted to the semiarid areas of South Morocco were grown in pots in a greenhouse. Five different water treatments were maintained from the beginning of stem elongation to maturity, when shoot biomass and grain yield were recorded. The net photosynthesis (A), stomatal conductance (gs) and transpiration (T) of the ear and the flag leaf were measured at anthesis. In both organs these factors decreased significantly with water deficit, whereas the A/T and A/gs ratios increased. The genotype effect was also significant for all traits studied. Whole-organ photosynthesis was much higher in the ear than in the flag leaf in well-watered conditions. As water stress developed, photosynthesis decreased less in the ear than in the flag leaf. Whole-ear photosynthesis correlated better than flag leaf photosynthesis with biomass and yield. Nevertheless, the relationships of the whole flag leaf with biomass and yield improved as the water stress became more severe, suggesting a progressive shift of yield from sink to source limitation. For all water regimes the ratios A/gs and A/T of the ear also showed a higher (negative) correlation with both biomass and yield than those of the flag leaf. The results indicate that the ear has a greater photosynthetic role than the flag leaf in determining grain yield, not only in drought but also in the absence of stress.

Accuracy profile validation of a new analytical method for propane measurement using headspace-gas chromatography-mass spectrometry

Propane can be responsible for several types of lethal intoxication and explosions. Quantifying it would be very helpful to determine in some cases the cause of death. Some gas chromatography-mass spectrometry (GC-MS) methods of propane measurements do already exist. The main drawback of these GC-MS methods described in the literature is the absence of a specific propane internal standard necessary for accurate quantitative analysis. The main outcome of the following study was to provide an innovative Headspace-GC-MS method (HS-GC-MS) applicable to the routine determination of propane concentration in forensic toxicology laboratories. To date, no stable isotope of propane is commercially available. The development of an in situ generation of standards is thus presented. An internal-labeled standard gas (C3DH7) is generated in situ by the stoichiometric formation of propane by the reaction of deuterated water (D2O) with Grignard reagent propylmagnesium chloride (C3H7MgCl). The method aims to use this internal standard to quantify propane concentrations and, therefore, to obtain precise measurements. Consequently, a complete validation with an accuracy profile according to two different guidelines, the French Society of Pharmaceutical Sciences and Techniques (SFSTP) and the Gesellschaft für toxikologische und Forensische Chemie (GTFCh), is presented.

Water-filtered infrared-A radiation (wIRA) is not implicated in cellular degeneration of human skin.

BACKGROUND: Excessive exposure to solar ultraviolet radiation is involved in the complex biologic process of cutaneous aging. Wavelengths in the ultraviolet-A and -B range (UV-A and UV-B) have been shown to be responsible for the induction of proteases, e. g. the collagenase matrix metalloproteinase 1 (MMP-1), which are related to cell aging. As devices emitting longer wavelengths are widely used in therapeutic and cosmetic interventions and as the induction of MMP-1 by water-filtered infrared-A (wIRA) had been discussed, it was of interest to assess effects of wIRA on the cellular and molecular level known to be possibly involved in cutaneous degeneration. OBJECTIVES: Investigation of the biological implications of widely used water-filtered infrared-A (wIRA) radiators for clinical use on human skin fibroblasts assessed by MMP-1 gene expression (MMP-1 messenger ribonucleic acid (mRNA) expression).Methods: Human skin fibroblasts were irradiated with approximately 88% wIRA (780-1400 nm) and 12% red light (RL, 665-780 nm) with 380 mW/cm(2) wIRA(+RL) (333 mW/cm(2) wIRA) on the one hand and for comparison with UV-A (330-400 nm, mainly UV-A1) and a small amount of blue light (BL, 400-450 nm) with 28 mW/cm(2) UV-A(+BL) on the other hand. Survival curves were established by colony forming ability after single exposures between 15 minutes and 8 hours to wIRA(+RL) (340-10880 J/cm(2) wIRA(+RL), 300-9600 J/cm(2) wIRA) or 15-45 minutes to UV-A(+BL) (25-75 J/cm(2) UV-A(+BL)). Both conventional Reverse Transcriptase Polymerase Chain Reaction (RT-PCR) and quantitative real-time RT-PCR techniques were used to determine the induction of MMP-1 mRNA at two physiologic temperatures for skin fibroblasts (30 degrees C and 37 degrees C) in single exposure regimens (15-60 minutes wIRA(+RL), 340-1360 J/cm(2) wIRA(+RL), 300-1200 J/cm(2) wIRA; 30 minutes UV-A(+BL), 50 J/cm(2) UV-A(+BL)) and in addition at 30 degrees C in a repeated exposure protocol (up to 10 times 15 minutes wIRA(+RL) with 340 J/cm(2) wIRA(+RL), 300 J/cm(2) wIRA at each time). RESULTS: Single exposure of cultured human dermal fibroblasts to UV-A(+BL) radiation yielded a very high increase in MMP-1 mRNA expression (11 +/-1 fold expression for RT-PCR and 76 +/-2 fold expression for real-time RT-PCR both at 30 degrees C, 75 +/-1 fold expression for real-time RT-PCR at 37 degrees C) and a dose-dependent decrease in cell survival. In contrast, wIRA(+RL) did not produce cell death and did not induce a systematic increase in MMP-1 mRNA expression (less than twofold expression, within the laboratory range of fluctuation) detectable with the sensitive methods applied. Additionally, repeated exposure of human skin fibroblasts to wIRA(+RL) did not induce MMP-1 mRNA expression systematically (less than twofold expression by up to 10 consecutive wIRA(+RL) exposures and analysis with real-time RT-PCR). CONCLUSIONS: wIRA(+RL) even at the investigated disproportionally high irradiances does not induce cell death or a systematic increase of MMP-1 mRNA expression, both of which can be easily induced by UV-A radiation. Furthermore, these results support previous findings of in vivo investigations on collagenase induction by UV-A but not wIRA and show that infrared-A with appropriate irradiances does not seem to be involved in MMP-1 mediated photoaging of the skin. As suggested by previously published studies wIRA could even be implicated in a protective manner.

Health consultation : Iowa City former manufactured gas plant site, 505 Burlington Street, Iowa City, Johnson County, Iowa EPA facility ID: IAD984591172 (2006)

The United States Environmental Protection Agency (EPA) has requested the Iowa Department of Public Health (IDPH) Hazardous Waste Site Health Assessment Program to evaluate the health impacts of the proposed remedial strategy to be implemented at the Iowa City Former Manufactured Gas Plant Site (FMGP). The proposed remedial strategy to be implemented incorporates the following: 1) access restrictions through the continued operation of the Iowa-Illinois Manor and restriction on any future water well installation through continued implementation of a local environmental covenant; 2) previous site decommissioning activities that have restricted access to site contaminants; and 3) continued monitoring of the groundwater to ensure that contaminant levels in groundwater remain the same or are declining in concentration. This health consultation addresses potential health risks to people from exposure to the soil and vapors within the property. The information in this health consultation was current at the time of writing. Data that emerges later could alter this document’s conclusions and recommendations.

Health consultation : jet gas spill site, Lowell, Henry County, Iowa (2004)

An attorney representing seven property owners in Lowell, Iowa, requested the Iowa Department of Public Health (IDPH) Hazardous Waste Site Health Assessment Program to perform a health consultation for the Jet Gas Spill Site. The attorney asked the IDPH to provide comments concerning the potential and likely health effects to her clients due to exposure from the spill. The specific issues to be addressed are listed in this health consultation. The information in this health consultation was current at the time of writing. Data that emerges later could alter this document’s conclusions and recommendations.

Accuracy profile validation of a new analytical method for butane measurement using headspace-gas chromatography-mass spectrometry.

The aim of our study was to provide an innovative HS-GC/MS method applicable to the routine determination of butane concentration in forensic toxicology laboratories. The main drawback of the GC/MS methods discussed in literature concerning butane measurement was the absence of a specific butane internal standard necessary to perform quantification. Because no stable isotope of butane is commercially available, it is essential to develop a new approach by an in situ generation of standards. To avoid the manipulation of a stable isotope-labelled gas, we have chosen to generate in situ an internal labelled standard gas (C(4)H(9)D) following the basis of the stoichiometric formation of butane by the reaction of deuterated water (D(2)O) with Grignard reagent butylmagnesium chloride (C(4)H(9)MgCl). This method allows a precise measurement of butane concentration and therefore, a full validation by accuracy profile was presented.

Gas exchange rates, plant height, yield components, and productivity of upland rice as affected by plant regulators

The objective of this work was to evaluate gas exchange rates, plant height, yield components, and productivity of upland rice, as affected by type and application time of plant growth regulators. A randomized block design, in a 4x2 factorial arrangement, with four replicates was used. Treatments consisted of three growth regulators (mepiquat chloride, trinexapac-ethyl, and paclobutrazol), besides a control treatment applied at two different phenological stages: early tillering or panicle primordial differentiation. The experiment was performed under sprinkler-irrigated field conditions. Net CO2 assimilation, stomatal conductance, plant transpiration, and water-use efficiency were measured four times in Primavera upland rice cultivar, between booting and milky grain phenophases. Gas exchange rates were neither influenced by growth regulators nor by application time. There was, however, interaction between these factors on the other variables. Application of trinexapac-ethyl at both tillering and differentiation stages reduced plant height and negatively affected yield components and rice productivity. However, paclobutrazol and mepiquat chloride applied at tillering, reduced plant height without affecting rice yield. Mepiquat chloride acted as a growth stimulator when applied at the differentiation stage, and significantly increased plant height, panicle number, and grain yield of upland rice.

Effect of growth regulators on 'Brookfield' apple gas diffusion and metabolism under controlled atmosphere storage

The objective of this work was to evaluate the effect of growth regulators on gas diffusion and on metabolism of 'Brookfield' apple, and to determine their correlation with quality characteristics of fruit stored in controlled atmosphere. A completely randomized design was used with four replicates. After eight months of storage, the effects of water (control), aminoethoxyvinylglycine (AVG), AVG + ethephon, AVG + naphthaleneacetic acid (NAA), ethephon + NAA, sole NAA, 1-MCP, ethylene absorption by potassium permanganate (ABS), AVG + ABS, and of AVG + 1-MCP - applied at different rates and periods - were evaluated on: gas diffusion rate, ethylene production, respiratory rate, internal ethylene concentration, internal CO2 content, mealiness, and intercellular space. Fruit from the control and sole NAA treatments had the highest mealiness occurrence. Growth regulators significantly changed the gaseous diffusion through the pulp of 'Brookfield' apple, mainly in the treatment AVG + ABS, which kept the highest gas diffusion rate. NAA spraying in the field, with or without another growth regulator, increased ripening metabolism by rising ethylene production and respiration rate, and reduced gas diffusion during shelf life. AVG spraying cannot avoid the ethephon effect during the ripening process, and reduces both the internal space and mealiness incidence, but it is not able to induce ethylene production or to increase respiration rates.

Cenomanian-Turonian transition in a shallow water sequence of the Sinai, Egypt

Environmental and depositional changes across the Late Cenomanian oceanic anoxic event (OAE2) in the Sinai, Egypt, are examined based on biostratigraphy, mineralogy, delta(13)C values and phosphorus analyses. Comparison with the Pueblo, Colorado, stratotype section reveals the Whadi El Ghaib section as stratigraphically complete across the late Cenomanian-early Turonian. Foraminifera are dominated by high-stress planktic and benthic assemblages characterized by low diversity, low-oxygen and low-salinity tolerant species, which mark shallow-water oceanic dysoxic conditions during OAE2. Oyster biostromes suggest deposition occurred in less than 50 m depths in low-oxygen, brackish, and nutrient-rich waters. Their demise prior to the peak delta(13)C excursion is likely due to a rising sea-level. Characteristic OAE2 anoxic conditions reached this coastal region only at the end of the delta(13)C plateau in deeper waters near the end of the Cenomanian. Increased phosphorus accumulations before and after the delta(13)C excursion suggest higher oxic conditions and increased detrital input. Bulk-rock and clay mineralogy indicate humid climate conditions, increased continental runoff and a rising sea up to the first delta(13)C peak. Above this interval, a dryer and seasonally well-contrasted climate with intermittently dry conditions prevailed. These results reveal the globally synchronous delta(13)C shift, but delayed effects of OAE2 dependent on water depth.

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).

Improvements in Air Intake on Frame 6 Gas Turbines

Työssä tarkastellaan kahta kaasuturbiinin imuilman sisäänottojärjestelmän kehitysmenetelmää, imuilman jäähdytystä ja sähköstaattista suodatusta. Imuilman jäähdytysmenetelmien tarkastelussa käytettiin kahta kaasuturbiinin tehonlisäystekniikoiden laskentatyökalua. Arviointi kohdistettiin Glanford Brigg Generating Station -voimalaitoksen kaasuturbiinityyppiin ja paikallisiin englantilaisiin ilmasto-olosuhteisiin. Tarkastelussa olivat kostutusjäähdytys ja overspray. Tuloksia vertailtiin keskenään ja näiden perusteella arvioitiin menetelmien vaikutuksia tehoon, hyötysuhteeseen sekä veden kulutukseen. Sähköstaattisen suodattimen prototyyppi oli rakennettu Briggin voimalaitokselle. Järjestelmää kehitetään kaupalliseksi tuotteeksi ja tätä varten kerättiin tekninen dokumentaatio kokonaisuudeksi, jota voitiin hyödyntää tuotteistusprosessissa. Imuilman jäähdyttämisellä voidaan saavuttaa merkittävä tehonlisäys ilmasto-olosuhteista riippuen. Menetelmällä voidaan myös tasata lämpötilan vuorokausi-vaihtelusta aiheutuvia tehoeroja. Sähköstaattisen suodattimen prototyyppi saavutti kehitysvaiheelle asetetut tavoitteet. Sähköstaattinen suodatus tarjoaa useita etuja perinteiseen mekaaniseen suodatukseen verrattuna.

Gas exchange, phisiological indexes and ionic accumulation in Annona emarginata (Schltdl.) H. Rainer seedlings in nutrients solution

"Araticum-de-terra-fria" (Annona emarginata (Schltdl.) H. Rainer) has been consider a good alternative in rootstock production for the main commercial Annonaceae species. Although this species develops in different soil and climate conditions, there is no understanding by the physiological responses of this species at different nutritional levels. Thus, the objective of this study was to evaluate the influence of different ionic strengths on development of vegetative species known as "Araticum-de-terra-fria". It was evaluated in seedlings grown in different ionic strengths (25% I, 50% I, 75% I and 100% I) of the complete nutrient solution Hoagland and Arnon (1950) nº 2, for 140 days, the following characteristics: Gas Exchange (CO2 assimilation rate, stomatal conductance, internal CO2 concentration, transpiration rate, water use efficiency, Rubisco carboxylation efficiency); Vegetative growth characteristics (diameter, leaf number, dry matter); Physiological Indexes (leaf area ratio, specific leaf area, relative growth rate, net assimilation rate, leaf weight ratio) and Ionic Accumulation (nutrients leaf analysis). Seedlings grown under 50% I showed the highest values of Leaf CO2 assimilation rate, water use efficiency, carboxylation efficiency, growth, relative growth rate, net assimilation rate and ionic accumulation in the total dry matter. So it is concluded that "Araticum-de-terra-fria" seedlings grown under intermediate nutrient concentrations of complete nutrient solution Hoagland and Arnon (1950) nº 2, explored more adequately their physiological potential that justify their adaptation in different nutritional conditions and allow reducing the amount of mineral nutrition of seedlings production.

Gas-phase photocatalytic oxidation of volatile organic compounds

Substances emitted into the atmosphere by human activities in urban and industrial areas cause environmental problems such as air quality degradation, respiratory diseases, climate change, global warming, and stratospheric ozone depletion. Volatile organic compounds (VOCs) are major air pollutants, emitted largely by industry, transportation and households. Many VOCs are toxic, and some are considered to be carcinogenic, mutagenic, or teratogenic. A wide spectrum of VOCs is readily oxidized photocatalytically. Photocatalytic oxidation (PCO) over titanium dioxide may present a potential alternative to air treatment strategies currently in use, such as adsorption and thermal treatment, due to its advantageous activity under ambient conditions, although higher but still mild temperatures may also be applied. The objective of the present research was to disclose routes of chemical reactions, estimate the kinetics and the sensitivity of gas-phase PCO to reaction conditions in respect of air pollutants containing heteroatoms in their molecules. Deactivation of the photocatalyst and restoration of its activity was also taken under consideration to assess the practical possibility of the application of PCO to the treatment of air polluted with VOCs. UV-irradiated titanium dioxide was selected as a photocatalyst for its chemical inertness, non-toxic character and low cost. In the present work Degussa P25 TiO2 photocatalyst was mostly used. In transient studies platinized TiO2 was also studied. The experimental research into PCO of following VOCs was undertaken: - methyl tert-butyl ether (MTBE) as the basic oxygenated motor fuel additive and, thus, a major non-biodegradable pollutant of groundwater; - tert-butyl alcohol (TBA) as the primary product of MTBE hydrolysis and PCO; - ethyl mercaptan (ethanethiol) as one of the reduced sulphur pungent air pollutants in the pulp-and-paper industry; - methylamine (MA) and dimethylamine (DMA) as the amino compounds often emitted by various industries. The PCO of VOCs was studied using a continuous-flow mode. The PCO of MTBE and TBA was also studied by transient mode, in which carbon dioxide, water, and acetone were identified as the main gas-phase products. The volatile products of thermal catalytic oxidation (TCO) of MTBE included 2-methyl-1-propene (2-MP), carbon monoxide, carbon dioxide and water; TBA decomposed to 2-MP and water. Continuous PCO of 4 TBA proceeded faster in humid air than dry air. MTBE oxidation, however, was less sensitive to humidity. The TiO2 catalyst was stable during continuous PCO of MTBE and TBA above 373 K, but gradually lost activity below 373 K; the catalyst could be regenerated by UV irradiation in the absence of gas-phase VOCs. Sulphur dioxide, carbon monoxide, carbon dioxide and water were identified as ultimate products of PCO of ethanethiol. Acetic acid was identified as a photocatalytic oxidation by-product. The limits of ethanethiol concentration and temperature, at which the reactor performance was stable for indefinite time, were established. The apparent reaction kinetics appeared to be independent of the reaction temperature within the studied limits, 373 to 453 K. The catalyst was completely and irreversibly deactivated with ethanethiol TCO. Volatile PCO products of MA included ammonia, nitrogen dioxide, nitrous oxide, carbon dioxide and water. Formamide was observed among DMA PCO products together with others similar to the ones of MA. TCO for both substances resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide and water. No deactivation of the photocatalyst during the multiple long-run experiments was observed at the concentrations and temperatures used in the study. PCO of MA was also studied in the aqueous phase. Maximum efficiency was achieved in an alkaline media, where MA exhibited high fugitivity. Two mechanisms of aqueous PCO – decomposition to formate and ammonia, and oxidation of organic nitrogen directly to nitrite - lead ultimately to carbon dioxide, water, ammonia and nitrate: formate and nitrite were observed as intermediates. A part of the ammonia formed in the reaction was oxidized to nitrite and nitrate. This finding helped in better understanding of the gasphase PCO pathways. The PCO kinetic data for VOCs fitted well to the monomolecular Langmuir- Hinshelwood (L-H) model, whereas TCO kinetic behaviour matched the first order process for volatile amines and the L-H model for others. It should be noted that both LH and the first order equations were only the data fit, not the real description of the reaction kinetics. The dependence of the kinetic constants on temperature was established in the form of an Arrhenius equation.

Photocatalytic Activity of Nanostructured Anatase Coatings Obtained by Cold Gas Spray

This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS)supported on titanium sub-oxide (TiO22x) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO22x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25 photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.