Influence of dissolved gases on sonochemistry and sonoluminescence in a flow reactor.

In the present work, the influence of gas addition is investigated on both sonoluminescence (SL) and radical formation at 47 and 248 kHz. The frequencies chosen in this study generate two distinct bubble types, allowing to generalize the conclusions for other ultrasonic reactors. In this case, 47 kHz provides transient bubbles, while stable ones dominate at 248 kHz. For both bubble types, the hydroxyl radical and SL yield under gas addition followed the sequence: Ar>Air>N2>>CO2. A comprehensive interpretation is given for these results, based on a combination of thermal gas properties, chemical reactions occurring within the cavitation bubble, and the amount of bubbles. Furthermore, in the cases where argon, air and nitrogen were bubbled, a reasonable correlation existed between the OH-radical yield and the SL signal, being most pronounced under stable cavitation at 248 kHz. Presuming that SL and OH originate from different bubble populations, the results indicate that both populations respond similarly to a change in acoustic power and dissolved gas. Consequently, in the presence of non-volatile pollutants that do not quench SL, sonoluminescence can be used as an online tool to qualitatively monitor radical formation.

Characterization of stable and transient cavitation bubbles in a milliflow reactor using a multibubble sonoluminescence quenching technique.

The bubble type, generated by an ultrasonic field, was studied in a batch and flow reactor using a multibubble sonoluminescence (MBSL) quenching technique with propanol and acetone. The influence of frequency and transducer configuration was evaluated using the same piezoelectric element in both setups. Results show that the bubble type not only depends on the frequency, but also on the input power or transducer configuration. Additionally, the effect of flow on sonoluminescence yield and bubble type was studied in the continuous setup at various frequencies. As the flow becomes turbulent, the sonoluminescence signal reaches a plateau for three out of four frequencies, and a transition from transient to stable cavitation occurs for frequencies below 200 kHz.

Insights into ozone deposition patterns from decade-long ozone flux measurements over a mixed temperate forest.

Long-term fluxes of ozone (O(3)) were measured over a mixed temperate forest using the aerodynamic gradient method. The long-term average O(3) flux (F) was -366 ng m(-2) s(-1) for the period 2000-2010, corresponding to an average O(3) concentration of 48 µg m(-3) and a deposition velocity v(d) of 9 mm s(-1). Average nocturnal ozone deposition amounted to -190 ng m(-2) s(-1), which was about one third of the daytime flux. Also during the winter period substantial O(3) deposition was measured. In addition, total O(3) fluxes were found to differ significantly among canopy wetness categories. During the day, highest deposition fluxes were generally measured for a dry canopy, whereas a rain-wetted canopy constituted the best sink at night. Flux partitioning calculations revealed that the stomatal flux (F(s)) contributed 20% to the total F but the F(s)/F fraction was subject to seasonal and diurnal changes. The annual concentration-based index AOT40 (accumulated dose over a threshold of 40 ppb) and the Phytotoxic Ozone Dose (POD(1) or accumulated stomatal flux above a threshold of 1 nmol m(-2) s(-1)) were related in a curvilinear way. The O(3) deposition was found to be largely controlled by non-stomatal sinks, whose strength was enhanced by high friction velocities (u(*)), optimizing the mechanical mixing of O(3) into the canopy and the trunk space. The long-term geometrical mean of the non-stomatal resistance (R(ns)) was 136 s m(-1) but lower R(ns) values were encountered during the winter half-year due to higher u(*). The R(ns) was also subject to a marked diurnal variability, with low R(ns) in the morning hours, when turbulence took off. We speculate that non-stomatal deposition was largely driven by scavenging of ozone by biogenic volatile organic compounds (BVOCs) and especially NO emitted from the crown or the forest floor.

Response and potential of agroforestry crops under global change.

The use of agroforestry crops is a promising tool for reducing atmospheric carbon dioxide concentration through fossil fuel substitution. In particular, plantations characterised by high yields such as short rotation forestry (SRF) are becoming popular worldwide for biomass production and their role acknowledged in the Kyoto Protocol. While their contribution to climate change mitigation is being investigated, the impact of climate change itself on growth and productivity of these plantations needs particular attention, since their management might need to be modified accordingly. Besides the benefits deriving from the establishment of millions of hectares of these plantations, there is a risk of increased release into the atmosphere of volatile organic compounds (VOC) emitted in large amounts by most of the species commonly used. These hydrocarbons are known to play a crucial role in tropospheric ozone formation. This might represent a negative feedback, especially in regions already characterized by elevated ozone level.

Chlorophyll a fluorescence imaging of ozone-stressed Brassica napus L. plants differing in glucosinolate concentrations.

Brassicaceae are characterised by glucosinolates (GS), which appear to be involved not only in biotic but also in abiotic stress responses of plants. We investigated the effect of O (3) stress on leaf GS concentrations in two lines of BRASSICA NAPUS L., differing in GS content. Ozone fumigation decreased GS concentrations in leaves of B. NAPUS of one line. In control conditions, chlorophyll content, rates of saturating photosynthesis, and quantum yield of photosystem 2 differed between the two BRASSICA lines, but differences were smaller in O (3)-stress conditions, suggesting that the relationship between leaf GS concentration and sensitivity to abiotic stress merits further research. In agreement with other ecophysiological measurements, chlorophyll fluorescence imaging clearly distinguished both lines and in some cases also treatments. A method for analysis of fluorescence images accounting for the two-dimensional leaf heterogeneity is presented.

Net carbon storage in a poplar plantation (POPFACE) after three years of free-air CO2 enrichment.

A high-density plantation of three genotypes of Populus was exposed to an elevated concentration of carbon dioxide ([CO(2)]; 550 micromol mol(-1)) from planting through canopy closure using a free-air CO(2) enrichment (FACE) technique. The FACE treatment stimulated gross primary productivity by 22 and 11% in the second and third years, respectively. Partitioning of extra carbon (C) among C pools of different turnover rates is of critical interest; thus, we calculated net ecosystem productivity (NEP) to determine whether elevated atmospheric [CO(2)] will enhance net plantation C storage capacity. Free-air CO(2) enrichment increased net primary productivity (NPP) of all genotypes by 21% in the second year and by 26% in the third year, mainly because of an increase in the size of C pools with relatively slow turnover rates (i.e., wood). In all genotypes in the FACE treatment, more new soil C was added to the total soil C pool compared with the control treatment. However, more old soil C loss was observed in the FACE treatment compared with the control treatment, possibly due to a priming effect from newly incorporated root litter. FACE did not significantly increase NEP, probably as a result of this priming effect.

Free-air CO2 enrichment (FACE) enhances biomass production in a short-rotation poplar plantation.

This paper investigates the possible contribution of Short Rotation Cultures (SRC) to carbon sequestration in both current and elevated atmospheric CO2 concentrations ([CO2]). A dense poplar plantation (1 x 1 m) was exposed to a [CO2] of 550 ppm in Central Italy using the free-air CO2 enrichment (FACE) technique. Three species of Populus were examined, namely P. alba L., P. nigra L. and P. x euramericana Dode (Guinier). Aboveground woody biomass of trees exposed to elevated [CO2] for three growing seasons increased by 15 to 27%, depending on species. As a result, light-use efficiency increased. Aboveground biomass allocation was unaffected, and belowground biomass also increased under elevated [CO2] conditions, by 22 to 38%. Populus nigra, with total biomass equal to 62.02 and 72.03 Mg ha-1 in ambient and elevated [CO2], respectively, was the most productive species, although its productivity was stimulated least by atmospheric CO2 enrichment. There was greater depletion of inorganic nitrogen from the soil after three growing seasons in elevated [CO2], but no effect of [CO2] on stem wood density, which differed significantly only among species.

A high-performance liquid chromatography/tandem mass spectrometric screening method for eight synthetic corticosteroids in bovine feces and the simultaneous differentiation between dexamethasone and betamethasone.

A screening method was developed to monitor the illegal use of synthetic corticosteroids in cattle. Diethyl ether extracts from spiked feces samples were cleaned-up by solid phase extraction followed by semipreparative reversed-phase chromatography (RPC). The fraction containing the corticosteroids was derivatized with ethoxyamine hydrochloride. The corresponding ethoximes were separated using silica-based C18 RPC and analyzed on-line in an ion trap mass spectrometer using atmospheric pressure positive chemical ionization. Ethoxime derivatives of dexamethasone and betamethasone were baseline resolved, allowing for the simultaneous mass spectrometric differentiation of both epimers in bovine feces by conventional non-chiral chromatography. At the lowest level tested (1 micro g/kg), corticosteroids (except triamcinolone) could be identified in compliance with the recent European criteria for residue identification. The quantitative performance of the method was best at residue levels > or = 2 micro g/kg.

Leaf area dynamics in a closed poplar plantation under free-air carbon dioxide enrichment.

Three Populus genotypes (P. alba L. (Clone 2AS-11), P. nigra L. (Clone Jean Pourtet) and P. x euramericana (Clone I-214)) growing in a managed, high-density forest plantation were exposed to free-air CO(2) enrichment (FACE) at CO(2) concentrations expected to occur in the future (550 ppm). Leaf area index (optical LAI), measured with a fish-eye-type plant canopy analyzer, was not significantly affected by FACE after canopy closure in the second growing season. However, when stands of similar size were compared, optical LAI and number of main stem leaves were reduced by FACE. Allometric relationships, which were established to scale-up leaf area to the stand level (allometric LAI), did not differ between the FACE and control plots. Allometric LAI increased in response to FACE, as a result of increased tree dimensions and increased individual leaf size. We postulate that, although FACE increased allometric LAI, FACE had no effect on optical LAI after canopy closure, because FACE caused increased shading and competition resulting in enhanced leaf fall or leaf turnover. Specific leaf area (SLA) was unaffected by FACE. Allometric relationships and relative responses to atmospheric CO(2) enrichment were genotype-dependent.

The likely impact of rising atmospheric CO2 on natural and managed Populus: a literature review.

Because of their prominent role in global biomass productivity, as well as their complex structure and function, forests and tree species deserve particular attention in studies on the likely impact of elevated atmospheric CO2 on terrestrial vegetation. Poplar (Populus) has proven to be an interesting study object due to its fast response to a changing environment, and the growing importance of managed forests in the carbon balance. Results of both chamber and field experiments with different poplar species and hybrids are reviewed in this contribution. Despite the variability between experiments and species, and the remaining uncertainty over the long term, poplar is likely to profit from a rising atmospheric CO2 concentration with a mean biomass stimulation of 33%. Environmental conditions and pollutants (e.g. O3) may counteract this stimulation but with managed plantations, environmental constraints might not occur. The predicted responses of poplar to rising atmospheric CO2 have implications for future forest management and the expected forest carbon sequestration.

Long-term esophageal manometry in healthy subjects. Evaluation of normal values and influence of age.

Although long-term esophageal manometry is increasingly used in clinical practice, the normal values of contraction parameters are poorly defined. In addition, limited data are available on the effect of age on esophageal motility. Therefore, 44 healthy subjects (age range: 22-85 years) were investigated with a probe combining two pressure transducers 10 cm apart. All subjects were asked to follow their normal daily routine. The characteristics of contraction events (amplitude, duration) and type of propagation (propulsive, simultaneous) were analyzed for the total time and predefined periods: meal, daytime (interprandial), and supine. Equally high distal and proximal median pressure amplitudes (39.5 and 37 hPa) and durations (3.4 and 3.2 sec) were observed. The median percentages of propulsive and simultaneous waves were 56% and 10%. The individual contraction characteristics differed significantly in these three selected periods for most motility parameters: distal and proximal pressure amplitudes, distal duration, and propulsive contractions. To evaluate the influence of age on normal values, the subjects were divided into two age groups (median age: 28.5 and 62.4 years). In the elderly group the distal pressure amplitude, the distal duration, and the percentage of simultaneous waves increased, whereas the percentage of propulsive waves, the proximal pressure amplitude, and the proximal duration decreased. However, the differences observed were only minor and rarely reached the level of statistical significance (distal pressure amplitude and duration in the supine period). In conclusion, the physiological motor activity of the esophagus is characterized by significant diurnal variation. Furthermore the motility data are little influenced by age.(ABSTRACT TRUNCATED AT 250 WORDS)

Metabolites of 4-chlorotestosterone acetate in cattle urine as diagnostic markers for its illegal use.

Seven metabolites of 4-chlorotestosterone acetate were identified in urine of cattle that received a single injection of the drug. The steroids were isolated by means of a series of clean-up steps carried out before and after enzymatic hydrolysis. The obtained extract was fractionated by high-performance liquid chromatography and each fraction was examined both by high-performance thin-layer chromatography and by capillary gas chromatography-mass spectrometry of the m-ethoxime-trimethylsilyl derivatives. The metabolites were tentatively identified by studying the mass spectra of selected peaks not found in blank samples. The structures of two metabolites, viz. 4-chloroandrost-4-ene-3,17-dione and 4-chloroandrost-4-ene-3 alpha,17 beta-diol were confirmed by chemical synthesis. The synthesized metabolites and 4-chloro-17 alpha-testosterone, a third metabolite which was identified tentatively, were located on the thin-layer chromatograms obtained. This study led to the conclusion that the illegal use of 4-chlorotestosterone acetate can be detected by identifying one or more of its metabolites in urine.