First-Order Chemistry in the Surface-Flux Layer

We have discussed the behavior of a non-conserved scalar in the stationary, horizontally homogeneous, neutral surface-flux layer and, on the basis of conventional second-order closure, derived analytic expressions for flux and for mean concentration of a gas, subjected to a first-order removal process. The analytic flux solution showed a clear deviation from the constant flux, characterizing a conserved scalar in the surface-flux layer. It decreases with height and is reduced by an order of magnitude of the surface flux at a height equal to about the typical mean distance a molecule can travel before destruction. The predicted mean concentration profile, however, shows only a small deviation from the logarithmic behavior of a conserved scalar. The solution is consistent with assuming a flux-gradient relationship with a turbulent diffusivity corrected by the Damköhler ratio, the ratio of a characteristic turbulent time scale and the scalar mean lifetime. We show that if we use only first-order closure and neglect the effect of the Damköhler ratio on the turbulent diffusivity we obtain another analytic solution for the profiles of the flux and the mean concentration which, from an experimental point of view, is indistinguishable from the first analytic solution. We have discussed two cases where the model should apply, namely NO which, by night, is irreversibly destroyed by interaction with mainly O₃ and the radioactive ²²⁰Rn. Only in the last case was it possible to find data to shed light on the validity of our predictions. The agreement seemed such that a falsification of our model was impossible. It is shown how the model can be used to predict the surface flux of ²²⁰Rn from measured concentration profiles.     

On the Spatial Distribution and Seasonal Variation of Lower-Troposphere Ozone over Europe

Surface ozone data from 25 Europeanlow-altitude sites and mountain sites located between79°N and 28°N were studied. The analysiscovered the time period March 1989–February 1993.Average summer and winter O₃ concentrations inthe boundary layer over the continent gave rise togradients that were strongest in the north-west tosouth-east direction and west-east direction, respectively. WintertimeO₃ ranged from 19 to 27 ppbover the continent, compared to about 32 ppb at thewestern border, while for summer the continentalO₃ values ranged between 39 and 56 ppb and theoceanic mixing ratios were around 37 ppb. In the lowerfree troposphere average wintertime O₃ mixingratios were around 38 ppb, with only an 8 ppbdifference between 28°N and 79°N. For summerthe average O₃ levels decreased from about 55 ppbover Central Europe to 32 ppb at 79°N. Inaddition, O₃ and O_x(= O₃ + NO₂)in polluted and clean air were compared. Theamplitudes of the seasonal ozone variations increasedin the north-west to south-east direction, while thetime of the annual maximum was shifted from spring (atthe northerly sites) to late summer (at sites inAustria and Hungary), which reflected the contributionof photochemical ozone production in the lower partsof the troposphere.     

Reactive Nitrogen Compounds at Spitsbergen in the Norwegian Arctic

Simultaneousindependent measurements of NO_y and NO_x(NO_x= NO + NO₂) by high-sensitivitychemiluminescence systems and of PAN (peroxyacetylnitrate) and PPN (peroxypropionyl nitrate) by GC-ECDwere made at Spitsbergen in the Norwegian Arcticduring the first half year of 1994. The average mixingratio of the sum of PAN and PPN (denoted PANs)increased from around 150 pptv in early winter to amaximum of around 500 pptv in late March, whereasepisodic peak values reached 800 pptv. This occurredsimultaneously with a maximum in ozone which increasedto 45–50 ppbv in March–April. The average NO_xmixing ratio was 27 pptv and did not show any cyclethrough the period. The NO_y mixing ratio showeda maximum in late March, while the difference betweenNO_y and PAN decreased during spring. This is anindication of the dominance of PAN in the NO_ybudget in the Arctic, but possible changes in theefficiency of the NO_y converter could alsocontribute to this. Although most PAN in theArctic is believed to be due to long range transport,the observations indicate local loss and formationrates of up to 1–2 pptv h^-1 in April–May.Measurements of carbonyl compounds suggest thatacetaldehyde was the dominant, local precursor ofPAN.Now at 1.     

The phase lag of temperature behind global solar radiation over Egypt

Summary The relation between the air temperature and the global solar radiation, which can be conveniently represented by the three characteristics: mean, amplitude and phase lag of the first harmonic of global radiation and air temperatures. A good correlation between the air temperature and the solar radiation has been found when the phase lag between them is nearly of 30 days.With 6 Figures     

A Mid Cretaceous origin for the Galápagos hotspot: volcanological, petrological and geochemical evidence from Costa Rican oceanic crustal segments

The Quepos, Nicoya and Herradura oceanic igneous terranes in Costa Rica are conspicuous features of a Mid to Late Cretaceous regional magmatic event that encompasses similar terranes in Central America, Colombia, Ecuador and the Caribbean. The Quepos terrane (66?Ma), which consists of ol-cpx phyric, tholeiitic pillow lavas overlain by highly vesicular hyaloclastites, breccias and conglomerates, is interpreted as an uplifted seamount/ocean island complex. The Nicoya (～90?Ma) and Herradura terranes consist of fault-bounded sequences of sediments, tholeiitic volcanics (pillow lavas and massive sheet flows) and plutonic rocks. The volcanic rocks were emplaced at relatively high eruption rates in moderate to deep water, possibly forming part of an oceanic plateau. Major and trace element data from Nicoya/Herradura tholeiites indicate higher melting temperatures than inferred for normal mid-ocean-ridge basalts (MORB) and/or a different source composition. Sr–Nd–Pb isotopic ratios from all three terranes are distinct from MORB but resemble those from the Galápagos hotspot. The volcanological, petrological and geochemical data from Costa Rican volcanic terranes, combined with published age data, paleomagnetic results and plate tectonic reconstructions of this region, provide strong evidence for a Mid Cretaceous (～90Ma) age for the Galápagos hotspot, making it one of the oldest known, active hotspots on Earth. Our results also support an origin of the Caribbean Plate through melting of the head of the Galápagos starting plume.     

Cell-zonal textures of tinguaites from the Kola Peninsula

Textures of tinguaite dykes cutting the alkaline Khibiny massif in the Kola Peninsula, Russia, are described. They are characterized by a combination of a fractal microfracture network dividing rock into pencil-like cells and of a concentric rhythmical zonation in almost all of them. The latter is formed by interchange of volatile-enriched and volatile-depleted mineral zones. The location of the textures only where dykes contact host khibinites appears to point out the contraction nature of the microfracture network. The cooling time calculated agrees well with this hypothesis. The zonation appears to have arisen through autometamorphic processes with two main competing factors, namely (a) overall cooling of the system and (b) periodic depletion of it in some elements, mainly Na and K. Another mechanism which may be applied to explain the zonation is the known Marangoni Instability effect at the early stage of evolution of the volatile-saturated phonolite melt. Thus, tinguaite textures are caused by nonspecific influences external to the system and may be regarded as an example of self-organization in nature.     

Comparison of source rock geochemistry of selected rocks from the Schei Point group and Ringnes formation, Sverdrup basin, arctic Canada

Organic-rich from the Schei Point group (middle to late Triassic in age) and the Ringnes formation (late Jurassic) from the Sverdrup basin of the Canadian arctic archipelago have been geochemically evaluated for source rock characterization. Most samples from the Schei Point group are organic-rich (> 2% TOC and are considered as immature to mature oil-prone source rocks [kerogen types I, I–II (IIA) and II (IIA)]. These kerogen types contain abundant AOM1, AOM2 and alginite (Tasmanales, Nostocopsis, Leiosphaeridia, acritarch and dinoflagellate) with variable amounts of vitrinite, inertinite and exinite. Samples from the Ringnes formation contain dominant vitrinite and inertinite with partially oxidized AOM2, alginite and exinite forming mostly immature to mature condensate- and gas-prone source rocks [kerogen type II–III (IIB), III and a few II (IIA)]. Schei Point samples contain higher bitumen extract, saturate hydrocarbons and saturate/ aromatic ratio than the Ringnes samples. Triterpane and sterane (dominant C₃₀) distribution patterns and stable carbon isotope of bitumen and kerogen suggest that the analyzed samples from the Schei Point group are at the onset of oil generation and contain a mixture of sapropelic (algal) and minor terrestrial humic organic matter. Sterane carbon number distributions in the Ringnes formation also suggest a mixed algal and terrestrial organic matter type. There are some variations in hopane carbon number distributions, but these are apparently a function of thermal maturity rather than significant genetic differences among samples. Pyrolysis-gas chromatography/mass spectrometry of the two samples with similar maturity shows that the Schei Point sample generates three times more pyrolyzate than the Ringnes sample. Both samples have a dominant aliphatic character, although the Ringnes sample contains phenol and an aromaticity that is higher than that of the Schei Point sample.