Lag time determination in DEC measurements with PTR-MS

The disjunct eddy covariance (DEC) method has emerged as a popular technique for micrometeorological flux measurements of volatile organic compounds (VOCs). It has usually been combined with proton transfer reaction mass spectrometry (PTR-MS), an online technique for VOC concentration measurements. However, the determination of the lag time between wind and concentration measurements has remained an important challenge. To address this issue, we studied the effect of different lag time methods on DEC fluxes. The analysis was based on both actual DEC measurements with PTR-MS and simulated DEC data derived from high frequency H<sub>2</sub>O measurements with an infrared gas analyzer. Conventional eddy covariance fluxes of H<sub>2</sub>O served as a reference in the DEC simulation. The individual flux measurements with PTR-MS were rather sensitive to the lag time methods, but typically this effect averaged out when the median fluxes were considered. The DEC simulation revealed that the maximum covariance method was prone to overestimation of the absolute values of fluxes. The constant lag time methods, one based on a value calculated from the sampling flow and the sampling line dimensions and the other on a typical daytime value, had a tendency to underestimate. The visual assessment method and our new averaging approach utilizing running averaged covariance functions did not yield statistically significant errors and thus fared better than the habitual choice, the maximum covariance method. Given this feature and the potential for automatic flux calculation, we recommend using the averaging approach in DEC measurements with PTR-MS. It also seems well suited to conventional eddy covariance applications when measuring fluxes near the detection limit

Hard photon production rate of a quark-gluon plasma at finite quark chemical potential

We compute the photon production rate of a quark-gluon plasma (QGP) at finite quark chemical potential $\mu$ using the Braaten-Pisarski method, thus continuing the work of Kapusta, Lichard, and Seibert who did the calculation for $\mu =0$.Comment: 9 pages, revtex, no figures, error in soft part corrected, figures available at ftp://theorie.physik.uni-giessen.de/usr/users/ftp/photon

Carbonyl compounds in boreal coniferous forest air in Hyytiälä, Southern Finland

International audienceA variety of C1-C12 carbonyl compounds were measured in the air of a boreal coniferous forest located in Hyytiälä, Southern Finland. 24-h samples were collected during March and April in 2003 using DNPH (2,4-dinitrophenyl hydrazine) coated C18-cartridges and analyzed by liquid chromatography-mass spectrometry (LC-MS). Altogether 22 carbonyl compounds were quantified. The most abundant carbonyls were acetone (24-h average 1340 ng/m3), formaldehyde (480 ng/m3) and acetaldehyde (360 ng/m3). In contrast, scaling of concentrations against reactivity with the hydroxyl (OH) radical significantly increased the contribution of larger aldehydes and ketones (e.g. decanal, octanal and 6-methyl-5-hepten-2-one). Concentrations of monoterpene reaction products nopinone (9 ng/m3) and limona ketone (5 ng/m3) were low compared to the most abundant low molecular weight carbonyls. The total concentration of carbonyl compounds in Hyytiälä in April/March 2003 was much higher than the concentration of aromatic hydrocarbons and monoterpenes in April 2002. Lifetimes of the measured carbonyls with respect to reactions with OH radicals, ozone (O3), and nitrate (NO3) radicals as well as photolysis were estimated. The main sinks for most of the carbonyl compounds in Hyytiälä in springtime are expected to be reactions with the OH radical and photolysis. For 6-methyl-5-hepten-2-one and limona ketone also reactions with ozone are important. The sources of carbonyl compounds are presently highly uncertain. Due to the relatively short lifetimes of aldehydes and ketones, secondary biogenic and anthropogenic sources, that is oxidation of volatile organic compounds, and primary biogenic sources are expected to dominate in Hyytiälä

Technical Note: Quantitative long-term measurements of VOC concentrations by PTR-MS ? measurement, calibration, and volume mixing ratio calculation methods

International audienceProton transfer reaction mass spectrometry (PTR-MS) is a technique for online measurements of atmospheric concentrations, or volume mixing ratios, of volatile organic compounds (VOCs). The aim of this paper is to give a detailed description of our measurement, calibration, and volume mixing ratio calculation methods, which have been designed for long-term stand-alone field measurements by PTR-MS. We also show how the information obtained from a calibration can be used to determine the instrument specific relative transmission curve, which enables quantitative mixing ratio calculation for VOCs which are not present in a calibration gas standard. To illustrate the functionality of our measurement, calibration, and calculation methods, we present a one-month period of ambient mixing ratio data measured in a boreal forest ecosystem at the SMEAR II station in southern Finland. During the measurement period 27 March?26 April 2007, the hourly averages of mixing ratios were 0.1?0.5 ppbv for formaldehyde, 0.2?3.0 ppbv for methanol, 0.04?0.39 ppbv for benzene, and 0.03?1.25 ppbv for monoterpenes

Hydrocarbon fluxes above a Scots pine forest canopy: Measurements and modeling

International audienceWe measured the fluxes of several hydrocarbon species above a Scots pine (Pinus sylvestris) stand using disjunct eddy covariance technique with proton transfer reaction ? mass spectrometry. The measurements were conducted during four days in July at SMEAR II research station in Hyytiälä, Finland. Compounds which showed significant emission fluxes were methanol, acetaldehyde, acetone, and monoterpenes. A stochastic Lagrangian transport model with simple chemical degradation was applied to assess the sensitivity of the above canopy fluxes to chemistry. According to the model, the chemical degradation had a minor effect on the fluxes measured in this study but has a major effect on the vertical flux profiles of more reactive compounds, such as sesquiterpenes. The monoterpene fluxes followed the traditional exponential temperature dependent emission algorithm but were considerably higher than the fluxes measured before at the same site. The normalized emission potential (30°C) was 2.5 ?g gdw?1 h?1 obtained using the temperature dependence coefficient of 0.09°C?1

Thermal quark production in ultra-relativistic nuclear collisions

We calculate thermal production of u, d, s, c and b quarks in ultra-relativistic heavy ion collisions. The following processes are taken into account: thermal gluon decay (g to ibar i), gluon fusion (g g to ibar i), and quark-antiquark annihilation (jbar j to ibar i), where i and j represent quark species. We use the thermal quark masses, $m_i^2(T)\simeq m_i^2 + (2g^2/9)T^2$, in all the rates. At small mass ($m_i(T)<2T$), the production is largely dominated by the thermal gluon decay channel. We obtain numerical and analytic solutions of one-dimensional hydrodynamic expansion of an initially pure glue plasma. Our results show that even in a quite optimistic scenario, all quarks are far from chemical equilibrium throughout the expansion. Thermal production of light quarks (u, d and s) is nearly independent of species. Heavy quark (c and b) production is quite independent of the transition temperature and could serve as a very good probe of the initial temperature. Thermal quark production measurements could also be used to determine the gluon damping rate, or equivalently the magnetic mass.Comment: 14 pages (latex) plus 6 figures (uuencoded postscript files); CERN-TH.7038/9

Testing the short-and long-term effects of elevated prenatal exposure to different forms of thyroid hormones

Maternal thyroid hormones (THs) are known to be crucial in embryonic development in humans, but their influence on other, especially wild, animals remains poorly understood. So far, the studies that experimentally investigated the consequences of maternal THs focused on short-term effects, while early organisational effects with long-term consequences, as shown for other prenatal hormones, could also be expected. In this study, we aimed at investigating both the short- and long-term effects of prenatal THs in a bird species, the Japanese quail Coturnix japonica. We experimentally elevated yolk TH content (the prohormone T-4, and its active metabolite T-3, as well as a combination of both hormones). We analysed hatching success, embryonic development, offspring growth and oxidative stress as well as their potential organisational effects on reproduction, moult and oxidative stress in adulthood. We found that eggs injected with T-4 had a higher hatching success compared with control eggs, suggesting conversion of T-4 into T-3 by the embryo. We detected no evidence for other short-term or long-term effects of yolk THs. These results suggest that yolk THs are important in the embryonic stage of precocial birds, but other short- and long-term consequences remain unclear. Research on maternal THs will greatly benefit from studies investigating how embryos use and respond to this maternal signalling. Long-term studies on prenatal THs in other taxa in the wild are needed for a better understanding of this hormone-mediated maternal pathway

Effect of chemical degradation on fluxes of reactive compounds – a study with a stochastic Lagrangian transport model

In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the exchange at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters