Electrical resistivity and 57Fe Mössbauer spectra of Fe-bearing calcic amphiboles

Electrical resistivity and ⁵⁷Fe Mössbauer spectra are reported for three calcic amphiboles with different Fe concentrations. AC measurements (20?Hz–1?MHz) were performed, applying impedance spectroscopy between 100 and 785?°C in an N₂ gas atmosphere. It was found that up to three semiconducting charge transport processes can be distinguished, which in part changed slightly when several runs were carried out to higher temperatures. The extrapolated DC resistivity is much smaller for an amphibole with high Fe content than for the two with lower Fe concentrations. The derived activation energies are between ～0.48 and ～1.06?eV. For temperatures ≤600?°C the results are compatible with a charge transport mechanism due to electron hopping between Fe²⁺ and Fe³⁺. Above 600?°C, dehydrogenation and/or beginning amphibole decomposition obviously alter the conduction mechanism. From Mössbauer spectra it was established that in all amphibole samples Fe²⁺ and Fe³⁺ are simultaneously present. Mössbauer parameters were derived by fitting the observed spectra to models taking the occupation of various M sites into account.     

Lower and Middle Ordovician conodonts of Laurentian affinity from blocks of limestone in the Rosroe Formation,South Mayo Trough,western Ireland and their palaeogeographic implication

The Middle Ordovician Rosroe Formation consists of some 1350 m of coarse, mainly siliciclastic to volcaniclastic sedimentary rocks, deposited in a submarine fan environment, and is restricted to the southern limb of the South Mayo Trough, western Ireland. Discrete allochthonous blocks, reaching 5 m in size, are present in the formation at several localities. Conodonts recovered from these blocks, collected from two separate locations, are of late Early and mid Mid Ordovician age. The conodonts have high conodont‐alteration indices (CAI 5) indicative of temperatures as high as 300^o to max. 480 °C; some found in the Lough Nafooey area have abnormally high indices (CAI 6), which correspond to temperatures of about 360^o to max. 550 °C. The oldest fauna is dominated by Periodon aff. aculeatus and characterized by Oepikodus evae typical of the Oepikodus evae Zone (Floian Stage; Stage Slices Fl2–3, Lower Ordovician). The younger conodont assemblage, characterized by Periodon macrodentatus associated with Oistodella pulchra, is referred to the P. macrodentatus conodont Biozone (lower Darriwilian; Stage Slices Dw1–2). The Rosroe conodont assemblages are of Laurentian affinity; comparable faunas are well known from several locations along the east to south‐eastern platform margin of Laurentia and the Notre Dame subzone of central Newfoundland, Canada. The faunal composition from the limestone blocks suggests a shelf edge to slope (or fringing carbonate) setting. The faunal assemblages are coeval with, respectively, the Tourmakeady Formation (Floian–Dapingian) and Srah Formation (Darriwilian) in the Tourmakeady Volcanic Group in the eastern part of the South Mayo Trough and probably are derived from the same or similar laterally equivalent short‐lived carbonate successions that accumulated at offshore ‘peri‐Laurentian’ islands, close to and along the Laurentian margin. During collapse of the carbonate system in the late Mid Ordovician, the blocks were transported down a steep slope and into deep‐water by debris flows, mixing with other rock types now found in the coarse polymict clastics of the Rosroe Formation. The faunas fill the stratigraphical ‘gap’ between the Lower Ordovician Lough Nafooey Volcanic Group and the upper Middle Ordovician Rosroe Formation in the South Mayo Trough and represent a brief interval conducive to carbonate accumulation in an otherwise siliciclastic‐ and volcaniclastic‐dominated sedimentary environment. Copyright © 2015 John Wiley & Sons, Ltd.     

Climatic bisection of the last interglacial warm period in the Polar North Atlantic

New multiproxy marine data of the Eemian interglacial (MIS5e) from the Norwegian Sea manifest a cold event with near-glacial surface ocean summer temperatures (3–4 °C). This mid-Eemian cooling divided the otherwise relatively warm interglacial climate and was associated with widespread expansions of winter sea-ice and polar water masses due to changes in atmospheric circulation and ocean stability. While the data also verify a late rather than early last interglacial warm peak, which is in general disharmony with northern hemisphere insolation maximum and the regional climatic progression of the early Holocene, the cold event itself was likely instrumental for delaying the last interglacial climate development in the Polar North when compared with regions farther south. Such a ‘climatic decoupling’ of the Polar region may bear profound implications for the employment of Eemian conditions to help evaluate the present and future state of the Arctic cryosphere during a warming interglacial.     

ISA model: A constitutive model for soils with yield surface in the intergranular strain space

In this article, a new constitutive model for soils is proposed. It is formulated by means of plasticity, but in contrast to the precedent works, it presents a yield function describing a surface within the intergranular strain space. This latter is a state variable providing information of the recent strain history. An expression for the plastic strain rate has been proposed to guarantee the stress rate continuity. Under the application of medium or large strain amplitudes, the constitutive equation becomes independent of the intergranular strain and delivers a mathematical structure similar to some Karlsruhe hypoplastic models. Some simulations of monotonic and cyclic triaxial test are provided to evaluate and analyze the model performance. Copyright © 2015 John Wiley & Sons, Ltd.     

Crustal observations beneath the southern North Sea and their tectonic and geological implications

In 1991, a deep seismic reflection line, MPNI-9101, was acquired in the southern North Sea from the Mesozoic Broad Fourteens Basin, across the West Netherlands Basin onto the London-Brabant Massif (LBM). The resultant section shows a strongly reflective lower crust beneath the area of Mesozoic basin development. This lower crustal reflectivity continues to be strong beneath the LBM. The travel time to the base of the reflective zone increases from approximately 11.0 s beneath the Mesozoic basins to 12.5 s beneath the LBM, suggesting a southward thickening of the crust (Rijkers et al., 1993). Based on these travel times and information from deep wells and refraction surveys. Moho depth is estimated to increase from about 31 km beneath the Mesozoic basins to about 38 km beneath the LBM. This difference in depth to the Moho can partly be explained by coaxial stretching of the crust beneath the Mesozoic basins. In comparison with the Mesozoic basins, the crust beneath the LBM was thickened during the Caledonian and Variscan orogenies.     

Very high CO2 cordierite from Norwegian Lapland: Mineralogy,petrology, and carbon isotopes

The most CO₂-rich cordierite thus far encountered in nature with about 2.2 wt.% CO₂ and 0.3 wt.% H₂O occurs as large poikiloblasts in a strange non-foliated reaction rock that dissects well-foliated granulites being part of the classical Lapland granulite area described by Eskola. The cordierite is optically positive with the highest optic angle 2V _x (106°) and birefringence (– = 0.017) ever measured on natural cordierites, but it is also optically very heterogeneous due to secondary loss of CO₂ along fractures and zones paralleling the fluid-bearing channels. Based on the optical properties of the degassed Lapland cordierite and on literature data a ternary diagram is given, which shows the variations of this cordierite in 2V _x and birefringence as a function of channel-filling with both CO₂ and H₂O.Following Losert (1971) the cordierite coexists with calcite, a thus far unique mineral assemblage that is probably only stable at very high CO₂ pressures. In the present case, the of the cordierite (0.75) indicates, on the basis of literature data, a coexisting fluid with >0.95.The carbon isotope composition ¹³C of CO₂ in cordierite lies near –7, that of the calcite is slightly lighter than about –9. Thus, at least for the CO₂ in cordierite, a deep-seated origin may be possible.Based on the geologic occurrence it is speculated that the cordierite-bearing reaction rock could perhaps represent an annealed channel of late degassing in the granulitic lower crust.     

Emissions of Volatile Organic Compounds from Sunflower and Beech: Dependence on Temperature and Light Intensity

Emissions of volatile organic compounds (VOCs) from sunflower (Helianthus annuus L. cv. giganteus) were measured in a continuously stirred tank reactor. The compounds predominantly emitted from sunflower were: isoprene, the monoterpenes -pinene, -pinene, sabinene, 3-carene and limonene, an oxygenated terpene, not positively identified so far and the sesquiterpene -caryophyllene. Emission rates ranged from 0.8 x 10^–16 to 4.3 x 10 ^–15 mol cm^–2 s^–1 at a temperature of 25°C and at a light intensity of 820 µEm^–2 s^–1. A dependence of the emission rates on temperature as well as on light intensity was observed. The emission rates of -pinene, sabinene and thujene from beech (Fagus sylvatica L.) were also affected by temperature as well as by light intensity. Our results suggest that an emission algorithm for all compounds emitted from sunflower and beech has to consider temperature and light intensity simultaneously. The observations strongly indicate that the emissions of VOCs from sunflower and beech are in part closely coupled to the rate of biosynthesis and in part originate from diffusion out of pools. The emission rates can be described by an algorithm that combines the model given by Tingey and coworkers with the algorithm given by Guenther and coworkers after slight modification.     

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.     

A laser-photolysis fragment-fluorescence (LPFF) method for the detection of gaseous nitric acid in ambient air

The development and first tests of a novel method for the direct, sensitive, selective, and fast detection of gaseous nitric acid in air are described. The detection method is based on the laser-photolysis fragment-fluorescence (LPFF) method using 193 nm (ArF) laser light. The photolysis process yielding OH fluorescence has been thoroughly investigated. Up to now, the method has been found to be practically free of interferences. The mixing ratio for nitric acid is measured on-line with a detection limit of about 0.1 ppbv for an accumulation time of the signal of 10–15 min. A number of tests and field measurements were performed to demonstrate the feasibility and limits of the described detection method.     

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.