Measurements of OVOC fluxes by eddy covariance using a proton-transfer-reaction mass spectrometer – method development at a coastal site

We present here vertical fluxes of oxygenated volatile organic compounds (OVOCs) measured with eddy covariance (EC) during the period of March to July 2012 near the southwest coast of the United Kingdom. The performance of the proton-transfer-reaction mass spectrometer (PTR-MS) for flux measurement is characterized, with additional considerations given to the homogeneity and stationarity assumptions required by EC. Observed mixing ratios and fluxes of OVOCs (specifically methanol, acetaldehyde, and acetone) vary significantly with time of day and wind direction. Higher mixing ratios and fluxes of acetaldehyde and acetone are found in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol mixing ratio and flux do not demonstrate consistent diel variability, suggesting sources in addition to plants. We estimate air-sea exchange and photochemical rates of these compounds, which are compared to measured vertical fluxes. For acetaldehyde, the mean (1 sigma) mixing ratio of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction out-paces production during the day. Air-sea exchange and photochemistry are probably net sinks of methanol and acetone in this region. Their nighttime mixing ratios of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long-distance transport, respectively

Diffraction and boundary conditions in semi-classical open billiards

The conductance through open quantum dots or quantum billiards shows fluctuations, that can be explained as interference between waves following different paths between the leads of the billiard. We examine such systems by the use of a semi-classical Green's functions. In this paper we examine how the choice of boundary conditions at the lead mouths affect the diffraction. We derive a new formula for the S-matrix element. Finally we compare semi-classical simulations to quantum mechanical ones, and show that this new formula yield superior results.Comment: 7 pages, 4 figure

Geometry-dependent scattering through quantum billiards: Experiment and theory

We present experimental studies of the geometry-specific quantum scattering in microwave billiards of a given shape. We perform full quantum mechanical scattering calculations and find an excellent agreement with the experimental results. We also carry out the semiclassical calculations where the conductance is given as a sum of all classical trajectories between the leads, each of them carrying the quantum-mechanical phase. We unambiguously demonstrate that the characteristic frequencies of the oscillations in the transmission and reflection amplitudes are related to the length distribution of the classical trajectories between the leads, whereas the frequencies of the probabilities can be understood in terms of the length difference distribution in the pairs of classical trajectories. We also discuss the effect of non-classical "ghost" trajectories that include classically forbidden reflection off the lead mouths.Comment: 4 pages, 4 figure

Improved microscopic-macroscopic approach incorporating the effects of continuum states

The Woods-Saxon-Strutinsky method (the microscopic-macroscopic method) combined with Kruppa's prescription for positive energy levels, which is necessary to treat neutron rich nuclei, is studied to clarify the reason for its success and to propose improvements for its shortcomings. The reason why the plateau condition is met for the Nilsson model but not for the Woods-Saxon model is understood in a new interpretation of the Strutinsky smoothing procedure as a low-pass filter. Essential features of Kruppa's level density is extracted in terms of the Thomas-Fermi approximation modified to describe spectra obtained from diagonalization in truncated oscillator bases. A method is proposed which weakens the dependence on the smoothing width by applying the Strutinsky smoothing only to the deviations from a reference level density. The BCS equations are modified for the Kruppa's spectrum, which is necessary to treat the pairing correlation properly in the presence of continuum. The potential depth is adjusted for the consistency between the microscopic and macroscopic Fermi energies. It is shown, with these improvements, that the microscopic-macroscopic method is now capable to reliably calculate binding energies of nuclei far from stability.Comment: 66 pages, 29 figures, 1 tabl

Air-sea transfer of gas phase controlled compounds

Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ~30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the "zero bubble" waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer

Lagrangian evolution of DMS during the Southern Ocean gas exchange experiment: The effects of vertical mixing and biological community shift

Concentrations of dimethylsulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) are highly variable in time and space. What is driving the variability in DMS(P), and can those variability be explained by physical processes and changes in the biological community? During the Southern Ocean Gas Exchange Experiment (SO GasEx) in the austral fall of 2008, two 3He/SF6 labeled patches were created in the surface water. SF6 and DMS were surveyed continuously in a Lagrangian framework, while direct measurements of air-sea exchange further constrained the gas budgets. Turbulent diffusivity at the base of the mixed layer was estimated from SF6 profiles and used to calculate the vertical fluxes of DMS and nutrients. Increasing mixed layer nutrient concentrations due to mixing were associated with a shift in the phytoplankton community structure, which in turned likely affected the sulfur dynamics on timescales of days. DMS concentration as well as air-sea DMS flux appeared to be decoupled from the DMSP concentration, possibly due to grazing and bacterial DMS production. Contrary to expectations, in an environment with high winds and modest productivity, physical processes (air-sea exchange, photochemistry, vertical mixing) only accounted for a small fraction of DMS loss from the surface water. Among the DMS sinks, inferred biological consumption most likely dominated during SO GasEx

Vertical fluxes and atmospheric cycling of methanol, acetaldehyde, and acetone in a coastal environment

We present here vertical fluxes of methanol, acetaldehyde, and acetone measured directly with eddy covariance (EC) during March to July 2012 near the southwest coast of the UK. The performance of the proton-transfer reaction mass spectrometer (PTR-MS) for flux measurement is characterized, with additional considerations given to the homogeneity and stationarity assumptions required by EC. Concentrations and fluxes of these compounds vary significantly with time of day and wind direction. Higher values of acetaldehyde and acetone are usually observed in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol concentration and flux do not demonstrate clear diel variability, suggesting sources in addition to plants. We estimate air–sea exchange and photochemical rates of these compounds, which are compared to measured vertical fluxes. For acetaldehyde, the mean (1�) concentration of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction outpaces production during the day. Air-sea exchange and photochemistry are probably net sinks of methanol and acetone in this region. Their nighttime concentrations of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long distance transport, respectively

Integrated water resources management as a new approach to water security

Access to safe water is a worldwide problem facing three quarters of a billion people every day. The problem of access to water is not primarily due to an overall scarcity of water, but rather the unequal geographical and seasonal distribution of the water resources. The key issue at stake here is, how to make water available. The new approach presented by international institutions for improving water access is Integrated Water Resource Management. This chapter questions this new approach and highlights the depoliticizing implications

Air-Sea Exchange of Biogenic Volatile Organic Compounds and the Impact on Aerosol Particle Size Distributions

We report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea-to-air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea-to-air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (PSOA) for mean isoprene and monoterpene emission rates sampled here indicate that PSOA is on average <0.1 μg m−3 d−1. Despite modest PSOA, low particle number concentrations permit a sizable role for condensational growth of monoterpene oxidation products in altering particle size distributions and the concentration of cloud condensation nuclei during episodic monoterpene emission events from the ocean