Measurements of hydrocarbon emissions from a boreal fen using the REA technique

International audienceFluxes of biogenic volatile organic compounds (VOC) and methane were measured above a boreal fen. Vegetation on the fen is dominated by Sphagnum mosses and sedges. A relaxed eddy accumulation (REA) system with dynamic deadband was designed and constructed for the measurements. Methane, C2-C6 hydrocarbons and some halogenated hydrocarbons were analysed from the samples by gas chromatographs equipped with FID and ECD. A significant flux of isoprene and methane was detected during the growing seasons. Isoprene emission was found to follow the common isoprene emission algorithm. Average standard emission potential of isoprene was 680 ? g m-2h-1. Fluxes of other non-methane hydrocarbons were below detection limit

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

Stand type affects fluxes of volatile organic compounds from the forest floor in hemiboreal and boreal climates

The forest floor is a significant contributor to the stand-scale fluxes of biogenic volatile organic compounds. In this study, the effect of tree species (Scots pine vs. Norway spruce) on forest floor fluxes of volatile organic compounds (VOC) was compared in boreal and hemiboreal climates.Peer reviewe

Coarsening of Sand Ripples in Mass Transfer Models with Extinction

Coarsening of sand ripples is studied in a one-dimensional stochastic model, where neighboring ripples exchange mass with algebraic rates, $\Gamma(m) \sim m^\gamma$, and ripples of zero mass are removed from the system. For $\gamma < 0$ ripples vanish through rare fluctuations and the average ripples mass grows as \avem(t) \sim -\gamma^{-1} \ln (t). Temporal correlations decay as $t^{-1/2}$ or $t^{-2/3}$ depending on the symmetry of the mass transfer, and asymptotically the system is characterized by a product measure. The stationary ripple mass distribution is obtained exactly. For $\gamma > 0$ ripple evolution is linearly unstable, and the noise in the dynamics is irrelevant. For $\gamma = 1$ the problem is solved on the mean field level, but the mean-field theory does not adequately describe the full behavior of the coarsening. In particular, it fails to account for the numerically observed universality with respect to the initial ripple size distribution. The results are not restricted to sand ripple evolution since the model can be mapped to zero range processes, urn models, exclusion processes, and cluster-cluster aggregation.Comment: 10 pages, 8 figures, RevTeX4, submitted to Phys. Rev.

Boundary layer concentrations and landscape scale emissions of volatile organic compounds in early spring

International audienceBoundary layer concentrations of several volatile organic compounds (VOC) were measured during two campaigns in springs of 2003 and 2006. The measurements were conducted over boreal landscapes near SMEAR II measurement station in Hyytiälä, Southern Finland. In 2003 the measuremens were performed using a light aircraft and in 2006 using a hot air balloon. Isoprene concentrations were low, usually below detection limit. This can be explained by low biogenic production due to cold weather, phenological stage of the isoprene emitting plants, and snow cover. Monoterpenes were observed frequently. The average total monoterpene concentration in the boundary layer was 33 pptv. Many anthropogenic compounds such as benzene, xylene and toluene, were observed in high amounts. Ecosystem scale surface emissions were estimated using a simple mixed box budget methodology. Total monoterpene emissions varied up to 80 ?g m?2 h?1, ?-pinene contributing typically more than two thirds of that. These emissions were somewhat higher that those calculated using emission algorithm. The highest emissions of anthropogenic compounds were those of p/m xylene

No self-similar aggregates with sedimentation

Two-dimensional cluster-cluster aggregation is studied when clusters move both diffusively and sediment with a size dependent velocity. Sedimentation breaks the rotational symmetry and the ensuing clusters are not self-similar fractals: the mean cluster width perpendicular to the field direction grows faster than the height. The mean width exhibits power-law scaling with respect to the cluster size, ~ s^{l_x}, l_x = 0.61 +- 0.01, but the mean height does not. The clusters tend to become elongated in the sedimentation direction and the ratio of the single particle sedimentation velocity to single particle diffusivity controls the degree of orientation. These results are obtained using a simulation method, which becomes the more efficient the larger the moving clusters are.Comment: 10 pages, 10 figure

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

Persistence in Cluster--Cluster Aggregation

Persistence is considered in diffusion--limited cluster--cluster aggregation, in one dimension and when the diffusion coefficient of a cluster depends on its size $s$ as $D(s) \sim s^\gamma$. The empty and filled site persistences are defined as the probabilities, that a site has been either empty or covered by a cluster all the time whereas the cluster persistence gives the probability of a cluster to remain intact. The filled site one is nonuniversal. The empty site and cluster persistences are found to be universal, as supported by analytical arguments and simulations. The empty site case decays algebraically with the exponent $\theta_E = 2/(2 - \gamma)$. The cluster persistence is related to the small $s$ behavior of the cluster size distribution and behaves also algebraically for $0 \le \gamma < 2$ while for $\gamma < 0$ the behavior is stretched exponential. In the scaling limit $t \to \infty$ and $K(t) \to \infty$ with $t/K(t)$ fixed the distribution of intervals of size $k$ between persistent regions scales as $n(k;t) = K^{-2} f(k/K)$, where $K(t) \sim t^\theta$ is the average interval size and $f(y) = e^{-y}$. For finite $t$ the scaling is poor for $k \ll t^z$, due to the insufficient separation of the two length scales: the distances between clusters, $t^z$, and that between persistent regions, $t^\theta$. For the size distribution of persistent regions the time and size dependences separate, the latter being independent of the diffusion exponent $\gamma$ but depending on the initial cluster size distribution.Comment: 14 pages, 12 figures, RevTeX, submitted to Phys. Rev.

New insights into nocturnal nucleation

Formation of new aerosol particles by nucleation and growth is a significant source of aerosols in the atmosphere. New particle formation events usually take place during daytime, but in some locations they have been observed also at night. In the present study we have combined chamber experiments, quantum chemical calculations and aerosol dynamics models to study nocturnal new particle formation. All our approaches demonstrate, in a consistent manner, that the oxidation products of monoterpenes play an important role in nocturnal nucleation events. By varying the conditions in our chamber experiments, we were able to reproduce the very different types of nocturnal events observed earlier in the atmosphere. The exact strength, duration and shape of the events appears to be sensitive to the type and concentration of reacting monoterpenes, as well as the extent to which the monoterpenes are exposed to ozone and potentially other atmospheric oxidants