Radiative transfer corrections for accurate spectroscopic measurements of volcanic gas emissions

There is widespread use of passive remote sensing techniques to quantify trace gas column densities in volcanic plumes utilizing scattered sunlight as a light source. Examples include passive DOAS, COSPEC, and the SO₂ camera. In order to calculate trace gas concentrations or volcanic emission fluxes, knowledge about the optical path through the plume is necessary. In the past, a straight photon path through the plume has always been assumed although it was known that this is not always true. Here we present the results of model studies conducted specifically to quantify the effects of realistic radiative transfer in and around volcanic plumes on ground-based remote sensing measurements of SO₂. The results show that measurements conducted without additional information on average photon paths can be inaccurate under certain conditions, with possible errors spanning more than an order of magnitude. Both over and underestimation of the true column density can occur. Actual errors depend on parameters such as distance between instrument and plume, plume SO₂ concentration, plume aerosol load, as well as aerosol conditions in the ambient atmosphere. As an example, a measurement conducted with an SO₂ camera is discussed, the results of which can only be correctly interpreted if realistic radiative transfer is considered. Finally, a method is presented which for the first time allows the retrieval of actual average photon paths in spectroscopic (i.e. DOAS) measurements of adequate resolution. By allowing for a wavelength dependent column density during the evaluation of DOAS measurements, we show how radiative transfer effects can be corrected using information inherently available in the measured spectra, thus greatly enhancing the accuracy of DOAS measurements of volcanic emissions.     

Fluxes and Concentrations of Non-Conserved Scalars in the Atmospheric Surface Layer

We have carried out a theoretical study of the simplest possible, second-order, chemical destruction process in the atmospheric surface layer. The model describes the destruction of two gases emanating from the surface with the same molecular flux. Although this situation seems artificial with no counterpart in the real atmosphere, the results shed light on some fundamental problems. For example, it is possible to specify boundary conditions, with the concentrations and the fluxes at a given height away from the surface, which lead to unrealistic solutions with infinite surface fluxes. A method to describe and separate the consistent solutions for this process was developed. It is in general of particular interest from an experimental point of view since it is not possible to measure fluxes right at the surface: if a measurement of flux and concentration in a given height requires infinite surface fluxes there is something wrong with the data. We expect that such problems will be inherent in more complex reactions schemes, such as the NO-NO₂-O₃ triad. Just as in first-order destruction processes, the Damköhler ratio will enter the turbulent diffusivity, but where this ratio is concentration independent for first-order processes, the present second-order model implies that the Damköhler ratio is proportional to the concentration. In the study of first-order processes it was found that the Damköhler correction to the turbulent diffusivity is of minor importance from an experimental point of view. We arrive at the same conclusion in this particularly simple study of second-order destruction. In other words, this work may be considered a further development of a previous study of the first-order destruction of a passive scalar. The model and the method we develop to solve the corresponding nonlinear differential equations are considered a preliminary study for developing tools to deal with more complicated atmospheric processes. Also, the results obtained may serve as a “calibration case” for more elaborate simulations.     

Photochemical production of ammonium and transformation of dissolved organic matter in the Baltic Sea

The release of ammonium from the photochemical degradation of dissolved organic matter (DOM) has been proposed by earlier studies as a potentially important remineralisation pathway for refractory organic nitrogen. In this study the photochemical production of ammonium from Baltic Sea DOM was assessed in the laboratory. Filtered samples from the Bothnian Bay, the Gulf of Finland and the Arkona Sea were exposed to UVA light at environmentally relevant levels, and the developments in ammonium concentrations, light absorption, fluorescence and molecular size distribution were followed. The exposures resulted in a decrease in DOM absorption and loss of the larger sized fraction of DOM. Analysis of the fluorescence properties of DOM using parallel factor analysis (PARAFAC) identified 6 independent components. Five components decreased in intensity as a result of the UVA exposures. One component was produced as a result of the exposures and represents labile photoproducts derived from terrestrial DOM. The characteristics of DOM in samples from the Bothnian Bay and Gulf of Finland were similar and dominated by terrestrially derived material. The DOM from the Arkona Sea was more autochthonous in character. Photoammonification differed depending on the composition of DOM. Calculated photoammonification rates in surface waters varied between 121 and 382 μmol NH₄⁺ L^− 1 d^− 1. Estimated areal daily production rates ranged between 37 and 237 μmol NH₄⁺ m^− 2 d^− 1, which are comparable to atmospheric deposition rates and suggest that photochemical remineralisation of organic nitrogen may be a significant source of bioavailable nitrogen to surface waters during summer months with high irradiance and low inorganic nitrogen concentrations.     

Redox Processes in Groundwater Impacted by Landfill Leachate

Groundwater downgradient from Trandum municipallandfill was investigated in summer 1996, with a viewto assessing the distribution of redox-sensitivespecies. The water table at Trandum is 10–26 metersbelow the surface. Monitoring well filters have beeninstalled at depths of up to 15 m below water table,covering an area of 400 m by 200 m. Groundwaterinfluenced by the landfill seems to be confined tothis area. Pristine groundwater has a chemicalsignature indicative of calcite and pyrite weathering.Groundwater influenced by leachate from the landfillexhibits an excess of alkalinity relative to calcium,which is likely to be derived from degradation oforganic matter in the landfill. Groundwaterimmediately below and downstream of the landfillcontains elevated concentrations of Fe and Mn, largelymobilized under reducing conditions from the aquifermatrix and reflected in depleted HNO₃-extractable Feand Mn in sediment samples from the same area.Groundwater samples allow the tentative identificationof redox zones based on oxidized and reduced forms ofFe, Mn, N and S. A methanogenic zone is notobserved.     

Single lunation <Emphasis Type="Italic">N</Emphasis>-observation orbits

Initial orbit determination by least squares of N observations is essentially a linear problem if the coordinates x ₀ and x ₁ at two standard epochs are used as elements. The orbit of a main belt object is approximated within the observational errors by a third degree polynomial during a month. A 4-observation orbit is useful for the initial linking between two nights. Parallax is treated rigorously and future simultaneous space and Earth based observations determine the critical distance directly. The N-observation method is a great simplification of the classical 3-observation orbit followed by a differential correction by N observations.     

Mesozoic rift magmatism in the North Sea region: <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar geochronology of Scanian basalts and geochemical constraints

More than 100 volcanic necks composed of basanites and melanephelinites occur in Scania, southern Sweden, at the junction of two major tectonic lineaments, the Phanerozoic Sorgenfrei-Tornquist Zone (STZ) and the Proterozoic Protogine Zone. New ⁴⁰Ar/³⁹Ar isotope analyses of whole rock fragments of nine selected basalt necks suggest that the Mesozoic alkaline volcanism in the Scanian province commenced earlier than previously reported and comprised three separate volcanic episodes that span a total period of ca. 80 Myr: a first Jurassic (191–178 Ma), a second at the Jurassic/Cretaceous boundary (ca. 145 Ma), and a final middle Cretaceous episode (ca. 110 Ma). The new results allow for precise time correlations between eruption events in the Scanian and those in the North Sea volcanic provinces. The older, early Jurassic event in Scania is largely synchronous with that in the Egersund Basin and the Forties field whereas the event at ca. 145 Ma is correlated with activity in the Central Graben. These volcanic episodes also correlate in age with Kimmerian tectonic activity. Volcanic activity in the middle Cretaceous period has also been dated in the triple junction in the North Sea and offshore in the Netherland Sector. The correlation of basalt volcanism in Scania with the Egersund nephelinites strongly suggest that volcanism was triggered by repeated tectonic activity along the STZ. Geochemical data of alkaline mafic rocks in the Scanian and the North Sea volcanic provinces imply that different provinces have largely unique geochemical signatures in favour of a heterogeneous mantle in the North Sea volcanic region. However, basalts of different generations in one and the same province cannot be readily separated on the basis of geochemistry, suggesting that the same lithospheric mantle was the source of repeated volcanism over time in each province. The data suggest a low degree of melting of a volatile-bearing mantle lherzolite enriched in incompatible elements with the exception of the Forties basalts in the rift centre, produced by larger degree of melting and evolved by fractional crystallization.     

A numerical study of boundary-layer dynamics in a mountain valley

The characteristics of dynamics and thermodynamics of the atmospheric boundary layer in a part of the Colorado River Valley, centered around Lake Mohave, have been investigated by analysis of measurements conducted during a field program in late spring and early summer of 1986 and a series of numerical simulations by a three-dimensional second-moment turbulence-closure model. The model was validated against measurements described in a companion article (Engeret al., 1993). According to airsonde measurements performed on eight nights, the depth of the surface inversion was around 200 m with an average temperature gradient of about 30 K km^–1. Analysis of acoustic sounder data collected during one month revealed significant diurnal variations ofU andV wind-speed components related to slope and valley flows, respectively. Some of the dynamics properties have been explained by the simulation results. It has been shown that the appearance of supergeostrophic southerly valley flow is associated with the westerly component of the geostrophic flow. Since a westerly component of the geostrophic wind is quite common for this area in summer, this effect also explains the frequently observed southerly valley flow in summer. Elevated minima of the measured wind speed around valley ridges appear to be related to the interaction of conservation of momentum in theX andY directions. The critical direction of the geostrophic wind relevant for reversal of up-valley flow to down-valley flow has also been studied. The critical direction is about 300° for one of the measurement sites and, depending on the angle between valley axis and south-north direction, the critical direction is expected to vary by about 15–20°. The scale analysis of the simulated equations of motion and turbulence kinetic energy emphasizes the strong impact of meandering of the flow due to actual topographic complexity.