Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

Turning climate change information into economic and health impacts

The PRUDENCE project has generated a set of spatially and temporally high-resolution climate data, which provides new opportunities for assessing the impacts of climate variability and change on economic and human systems in Europe. In this context, we initiated the development of new approaches for linking climate change information and economic studies. We have considered a number of case studies that illustrate how linkages can be established between geographically detailed climate data and economic information. The case studies included wheat production in agriculture, where regional climate data has been linked to farm enterprise data in an integrated model of physical conditions, production inputs and outputs, and farm management practices. Similarly, temperature data were used to assess consequences of extreme heat and excess mortality in urban areas. We give an introduction of an analytical approach for assessing economic impacts of climate change and discuss how economic concepts and valuation paradigms can be applied to climate change impact evaluation. A number of methodological difficulties encountered in economic assessments of climate change impacts are described and a number of issues related to social and private aspects of costs are highlighted. It is argued that, in particular, detailed climate information matters in relation to understanding how private agents react to observed climate data.     

A simple model for the adjustment of velocity spectra in unstable conditions downstream of an abrupt change in roughness and heat flux

A simple model for the equilibrium spectra of velocity fluctuations in the unstable surface layer is developed. All three component spectra are written as a sum of two spectra For the horizontal spectra, the two parts scale with % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaacIcacaWGUb% GaamOEamaaBaaaleaacaWGPbaabeaakiaac+cacaWG1bGaaiilaiaa% dQhadaWgaaWcbaGaamyAaaqabaGccaGGVaGaamitaiaacMcaaaa!4232!\[(nz_i /u,z_i /L)\]and % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaad6gacaWG6b% Gaai4laiaadwhaaaa!3B5E!\[nz/u\], respectively; the vertical spectrum can be written entirely as a function of % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaad6gacaWG6b% Gaai4laiaadwhaaaa!3B5E!\[nz/u\] and % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9Lq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9W8qr0-vr% 0-viWZqaceaabiGaciaacaqabeaadaqaaqaaaOqaaiaadQhacaGGVa% Gaamitaaaa!3A42!\[z/L\].The equilibrium spectra are utilized as part of a model describing the development of velocity spectra downwind of a change in surface roughness and heat flux.Results are shown for the streamwise component and compared with hotwire measurements from the RISØ 78 experiment. The model shows excellent agreement with the measurements.on leave of absence from RISØ National Laboratory Roskilde, Denmark.     

Palaeomagnetic evidence for large-scale dextral movement along the Trollfjord-Komagelv Fault,Finnmark, north Norway

Palaeomagnetic data from Late Precambrian dykes from the northern part of Varanger peninsula, north Norway, suggest a two-axis magnetization structure. The dominant component is considered to be syn- to late-tectonic and probably acquired at around 640 m.y. B.P. Superposed on this magnetization is a minor component which is compatible with the relative Lower-Middle Palaeozoic field; i.e. it was most likely imposed during the climax of the Caledonian orogenic movements in north Norway. The estimated relative Late Precambrian palaeopole cannot easily be reconciled with the European Late Precambrian polar path. This disagreement can be accounted for by assuming a post-magnetization dextral megashear, of the order of 500–1000 km, along the Trollfjord-Komagelv fracture zone. This type of displacement is in line with geological evidence and the palaeomagnetic reconstruction supports the long-held view of there having been continuity between the depositional environments of the Varanger Peninsula Barents Sea Group, the Eleonore Bay Group of east Greenland and the Hecla Hoek Formation of east Spitsbergen. The character and age of the horizontal displacement, post-640 to pre-500 m.y. B.P., is seen in conjunction with the opening up of the lapetus Ocean and reactivation of ancient deep-seated fractures during both the spreading and the contraction phases of ocean development.     

Hydrography of the Santee River during moderate discharge conditions

To harness hydroelectric power, most of the flow of the Santee River, SC was diverted in 1942 into Charleston Harbor, where shoaling promptly became a major problem. For this reason, most of the diverted flow is scheduled to be rediverted to the Santee within the next decade, increasing the mean discharge of the Santee from 74 to 428 m³s^?1. To assess the present hydrogrpahy of the Santee estuary under conditions of moderate discharge, we determined 226 vertical profiles of velocity, salinity, and temperature distributed over 17 stations in February, 1975. We found that 73 and 27% of the discharge reached the ocean via the North and South distributaries, respectively. The 1 ppt isohaline was found no further than 8 km upstream from the mouth, indicating the limited extent of the estuarine zone. The Santee is a partially mixed estuary classified as type 2b. The circulation parameter is approximately 3 and the stratification parameter approximately 0.3. The bulk parameters indicate the importance of tidal, mixing and a weakly developed gravitational circulation. When rediversion is completed, the net salinity in the lower Santee River can be expected to decrease drastically, which in turn is likely to terminate the lucrative oyster and clam fishery.     

Partitioning of iron and magnesium between crystals and partial melts in peridotite upper mantle

The iron-magnesium distribution coefficient, $$K'_D = (X_{\Sigma {\text{FeO}}} /X_{{\text{MgO}}} )^{{\text{olivine}}} (X_{{\text{MgO}}} /X_{\Sigma {\text{FeO}}} )^{{\text{liquid}}} ,$$ has frequently been used as a means of testing whether experimental and natural silicate liquids could have been in equilibrium with olivine of mantle composition. It is shown here that this K′ _D decreases with increasing oxygen fugacity (xxx) for a hydrous partial melt in equilibrium with a natural spinel peridotite assemblage under pressure and temperature conditions corresponding to those of the upper mantle (from 0.52 at the xxx of the iron-wüstite buffer to 0.04 at the xxx of the magnetite-hematite buffer). K′ _D also increases with increasing pressure, with decreasing temperature, and probably with increasing Mg/(Mg+∑ Fe) of the parental peridotite, suggesting that $$K_D = (X_{{\text{FeO}}} /X_{{\text{MgO}}} )^{{\text{olivine}}} (X_{{\text{MgO}}} /X_{{\text{FeO}}} )^{{\text{liquid}}}$$ also increases with increasing pressure and decreasing temperature. Thus, unless these four variables (P, T, xxx, silicate composition) are known for a natural magma, K′ _D and probably K _D are variables, and the Mg/(Mg+∑ Fe) of such a magma cannot be correlated to that of the parent. The K _D determined at 1 atm pressure by Roeder and Emslie has frequently been used to test whether the Mg/(Mg+∑ Fe) ratios of experimentally formed liquids at high pressure in equilibrium with olivine of known Fo content represent the equilibrium Mg/(Mg+Fe²⁺) of this liquid, assuming that ∑Fe=Fe²⁺ and that K′ _D does not vary with P, T, and composition of the system. Published data demonstrate that the oxygen fugacities of the experimental designs employed by different laboratories vary between those of the magnetite-hematite and magnetite-wüstite buffers (6 orders of magnitude), resulting in K′ _D between 0.04 and 0.31 at 1050° C and 15 kbar, for example. Thus, published arguments as to whether the quenched liquids represent equilibrium compositions based on iron-magnesium partitioning are inadequate. The effects of P, T, xxx, and the composition of the starting material must also be considered.     

Pressure dependence of nickel partitioning between forsterite and aluminous silicate melts

Nickel partitioning between forsterite and aluminosilicate melt of fixed bulk composition has been determined at 1300°C to 20 kbar pressure. The value of the forsterite-liquid nickel partition coefficient is lowered from >20 at pressures equal to or less than 15 kbar to <10 at pressures above 15 kbar.Published data indicate that melts on the join Na₂O-Al₂O₃-SiO₂ become depolymerized in the pressure range 10–20 kbar as a result of Al shifting from four-coordination at low pressure to higher coordination as the pressure is increased. This coordination shift results in a decreasing number of bridging oxygens in the melt. It is suggested that the activity coefficient of nickel decreases with this decrease in the number of bridging oxygens. As a result, the nickel partition coefficient for olivine and liquid is lowered.Magma genesis in the upper mantle occurs in the pressure range where the suggested change in aluminum coordination occurs in silicate melts. It is suggested, therefore, that data on nickel partitioning obtained at low pressure are not applicable to calculation of the nickel distribution between crystals and melts during partial melting in the upper mantle. Application of high-pressure experimental data determined here for Al-rich melts to the partial melting process indicates that the melts would contain about twice as much nickel as indicated by the data for the low-pressure experiments. If, as suggested here, the polymerization with pressure is related to the Al content of the melt, the difference in the crystal-liquid partition coefficient for nickel at low and high pressure is reduced with decreasing Al content of the melt. Consequently, the change ofD_Ni^{ol-andesite melt} is greater than that ofD_Ni^{ol-basalt melt}, for example.     

Risø 1978: Further investigations into the effects of local terrain irregularities on tower-measured wind profiles

Observations of flow over complex terrain taken at Risø during June–July 1978 and numerical studies confirm earlier findings that small variations in surface elevation have significant effects on mean wind profiles. Measured shear stresses in the nonequilibrium region of the flow are consistent with theory but quite different from those obtained assuming simple flux-profile relationships. These findings imply that flux-profile relationships can be quite complicated over other than simple homogeneous terrain.