Ammonia measurements at Niwot Ridge,Colorado and point arena,California using the tungsten oxide denuder tube technique

The applicability of the tungsten oxide denuder tube technique for the measurement of ammonia in the rural troposphere was investigated. The technique is based on selective chemisorption of NH₃ from a gas stream, thermal desorption, conversion to NO, and analysis by NO–O₃ chemiluminescence. Nitric acid, which is also collected and desorbed as NO, was distinguished from NH₃ by differences in desorption temperature. Substituted amines were also collected, but desorbed at a slightly lower temperature than NH₃ in dry air. At high relative humidities, alkylamines may be hydrolyzed to NH₃ on the denuder surface and hence detected as NH₃. Overheating of the denuder tube during the temperature-programmed desorption was found to cause significant irreversible degradation of system performance.The technique was used to measure NH₃ mixing ratios at two rural locations in the United States. At a mountain site in Colorado during the winter of 1984, the average NH₃ mixing ratio was 0.20 ppbv (=0.08 ppbv). At an isolated coastal site in northern California during the spring of 1985, the average NH₃ mixing ratio was 0.36 ppbv (=0.17 ppbv). Correlations of the latter measurements with wind direction and NO _x level suggest that the NH₃ mixing ratio in Pacific marine air at 40°N is <-0.25 ppbv.     

Estimating monthly streamflow values by cokriging

Cokriging is applied to estimation of missing monthly streamflow values in three records from gaging stations in west central Virginia. Missing values are estimated from optimal consideration of the pattern of auto- and cross-correlation among standardized residual log-flow records. Investigation of the sensitivity of estimation to data configuration showed that when observations are available within two months of a missing value, estimation is improved by accounting for correlation. Concurrent and lag-one observations tend to screen the influence of other available observations. Three models of covariance structure in residual log-flow records are compared using cross-validation. Models differ in how much monthly variation they allow in covariance. Precision of estimation, reflected in mean squared error (MSE), proved to be insensitive to this choice. Cross-validation is suggested as a tool for choosing an inverse transformation when an initial nonlinear transformation is applied to flow values.     

High-pressure crystal chemistry of phenakite (Be2SiO4) and bertrandite (Be4Si2O7(OH)2)

Compressibilities and high-pressure crystal structures have been determined by X-ray methods at several pressures for phenakite and bertrandite. Phenakite (hexagonal, space group R \(\bar 3\) ) has nearly isotropic compressibility with β=1.60±0.03×10^?4 kbar^?1 and β=1.45±0.07×10^?4 kbar^?1. The bulk modulus and its pressure derivative, based on a second-order Birch-Murnaghan equation of state, are 2.01±0.08 Mbar and 2±4, respectively. Bertrandite (orthorhombic, space group Cmc2₁) has anisotropic compression, with β _a =3.61±0.08, β _b =5.78±0.13 and β _c =3.19±0.01 (all ×10^?4 kbar^?1). The bulk modulus and its pressure derivative are calculated to be 0.70±0.03 Mbar and 5.3±1.5, respectively. Both minerals are composed of frameworks of beryllium and silicon tetrahedra, all of which have tetrahedral bulk moduli of approximately 2 Mbar. The significant differences in linear compressibilities of the two structures are a consequence of different degrees of T-O-T bending.     

Thick- and thin-skinned tectonics in the Pyrenees

A comparison is made between the Gavarnie thrust and the Mérens Fault in the Axial zone of the Pyrenees. The former has a gentle dip and quite a large displacement (at least 12 km) but does not cut through either Hercynian or Alpine isograds. The latter has a smaller displacement (~ 5 km) but dips steeply and cuts through both Hercynian and Alpine isograds at a high angle. On this basis and on the basis of shear zone geometries immediately north of it, it is proposed that the Mérens Fault nucleated as a steeply (65°–80°) dipping structure, while the Gavarnie thrust nucleated with a shallow attitude. The Mérens Fault is not a backward-rotated thrust fault, nor is it the root zone for any major nappe structure. Similar steep ductile structures occur within the Gavarnie nappe and may reflect considerable internal strain in basement lithologies.The relationship between steep and shallow structures is not yet clear; the shear zones may pre-date the thrusting in which case they may be thick-skinned structures affecting the whole lithosphere, or they may be contemporary with thrusting reflecting only local thickening above a décollement.Rheological models can be used to test proposed geometrical and kinematic models for the lithosphere-scale evolution of the Pyrenees. Suggested models are dominated by a cool, rigid, high-level mantle wedge beneath the North Pyrenean zone which probably controlled the location of north-dipping thrust faults. Thick-skinned shortening is possible in thick crust in the Axial zone but is very unlikely in the North Pyrenean zone where steeply rooted structures would have to cut through the strongest part of the lithosphere.     

A model of the redistribution of disaggregated soil particles by rainsplash

A model of the dispersion of splash droplets from a single raindrop impact on a sloping soil surface is combined with a theory of the entrainment of mineral particles from a disaggregated mixture in splash droplets to obtain a model of the dispersion of such particles by a raindrop impact. Stochastic modelling techniques extend this further to a model of the spatial redistribution of soil on a plot after a period of rainfall. Since the model is probabilistic and physically based it enables the incorporation of further advances in the understanding of splash erosion at all stages and can simulate the effect of the stochastic nature of rainfall and soil properties on the process. Several different situations are simulated. These include the movement of marked soil particles from point sources and the spatial patterns of erosion on a sloping plot. The model can also simulate the differential erosion of different soil particle size fractions.     

Intermediate-scale sea ice — Atmosphere interactions over high southern latitudes in winter

Associations between polar air cloud vortices (polar lows), as an indicator of intermediate-scale atmospheric activity, and the Antarctic sea ice, are examined for the Southern Hemisphere winter (June–September). Seven consecutive winters, spanning a period of marked interannual variability of the atmospheric circulation and sea ice (1977–83), are analyzed using sets of DMSP (Defense Meteorological Satellite Program) imagery. Relatively high frequencies of polar lows are found in ice-edge and adjacent ocean latitudes. There is some evidence for an equatorward shift in the latitude of maximum monthly polar low occurrence during the June to September period. Polar low incidence over the Southern Hemisphere on interannual time scales shows a close association with positive sea ice anomalies in the longitudes of more frequent cold air outbreaks from higher latitudes. This is particularly apparent for winters of strongly anomalous circulation, such as FGGE (1979) and the major ENSO of 1982–83. However, for individual cases on daily to weekly time scales, the feedback of cold air — sea ice advance — polar low development is not always evident, and implies that additional processes may contribute to polar air cyclogenesis in the marginal ice zone.     

Pyrolysis-GC-MS and NMR studies of dissolved seawater humic substances and isolates of a marine diatom

¹³C- and ¹H-NMR spectra were obtained for humic substances isolated from a coastal marine environment and also for the intracellular and extracellular extracts of a marine diatom. Phaeodactylum tricornutum Bohlin. Highly branched alkyl chains constitute a large proportion of the structure of the marine humic material, whereas aromatic components are less important. Carbohydrate-type materials, possibly uronic acids, are also present in appreciable amounts. Furans (derived from carbohydrates). pyrroles and nitriles (derived from proteins, nucleic acids and/or tetrapyrroles) and phenols and methylphenols (non-lignin derived) are pyrolysis products derived from pyrolysis-gas chromatography-mass spectrometry of the extracts. The results indicate the similarities in chemical structure of P. tricornutum exudate and dissolved marine humic material.     

Geochemical and mineralogical haloes about the Elura Zn-Pb-Ag orebody, western New South Wales

The Elura Zn-Pb-Ag deposit, situated 43 km NNW of Cobar, western New South Wales, is hosted by the C.S.A. Siltstone, a distal turbidite sequence. Deep weathering has given rise to a bleached quartz-muscovite-kaolinite rock to a depth of approximately 80 m. Weathered bedrock is mantled by a thin (0.3–2 m) layer of soil and transported overburden which contains thin layers of maghemite-bearing gravels. Outcrop in the area is extremely poor with the insignificant gossan subcrop covered by 0.2 m of soil. The water table is presently at a depth of about 80 m. Groundwater is saline with up to 2.5% total dissolved solids.Oxidation of the orebody has resulted in the formation of a gossan and ferruginization of wall rocks. Elements associated with ore and retained at high concentration in the gossan are Ag, As, Ba, Cu, Hg, Mo, Pb, Sb, (Se) and Sn; much of the Zn has been leached whilst Cd and Tl are below the detection limits. Silver, Cu and Hg have been partially leached and concentrated in the supergene zone. Ferruginous wall rock contains substantial amounts of Pb, As and Ba but other element contents are substantially lower than in the gossan.Secondary dispersion from the Elura orebody is largely restricted to an interpreted paleodrainage channel SW of the orebody and has occurred in two distinct periods. Mobile elements, particularly Zn, leached during gossan formation, occur in anomalous concentrations at or near the water table. More recently, the less mobile elements Pb, As, Bi, Hg and Sb have been leached from mechanically transported fragments of ferruginized wall rock and gossan by the saline groundwaters and occur as anomalies up to 150 m from the gossan in near-surface bedrock. Copper and Zn form broad low-contrast anomalies whilst Sn is retained within the gossan.Iron-rich bands, 50–1200 mm in thickness, which are common in the weathered zone about the Elura orebody, were formed by precipitation from groundwater passing along bedding planes, shears, fractures and cracks. They have higher As, Bi, Co, Cu, Mn, Ni, Zn, lower values of Ba and Sr, and similar Pb, Sb and Sn contents to the weathered siltstones. Iron may be derived from Fe-rich carbonates in the siltstones and be redeposited as goethite and minor hematite. These Fe-rich bands have trapped target and pathfinder elements which are believed to be from primary haloes rather than from the orebody or gossan.A two-stage mechanism for the formation of some secondary minerals within the weathered zone has been confirmed by stable light isotope studies. These studies have also shown that fractionation of S isotopes is minimal during gossan formation, and that a S isotopic halo in weathered bedrock may be used as an exploration tool.     

Detection of Cyclic Patterns Using Wavelets: An Example Study in the Ormskirk Sandstone, Irish Sea

This study shows how wavelet analysis can be used on well log and drill core data to identify cyclicity in sedimentary sequences. Three possible methods for determining wavelength were investigated: the Morlet wavelet, the Fourier transform, and the semivariogram. When applied to several hypothetical signals similar to those observed in petrophysical measurements in hydrocarbon reservoirs, all three methods could identify the presence of cyclicity. Only the wavelet scalogram, however, gave a clear indication of when the cyclic element was present and where frequency changes occurred in the signal. To illustrate the wavelet analysis, we processed well log and core data from a well in the Ormskirk Sandstone and determined the wavelet coefficients for each zone and the wavelengths of the strongest cyclicities. The cyclicities observed corresponded well with sedimentary features of the formation (e.g., channels and channel sets). Also, ratios of the cyclicity wavelengths corresponded with ratios of the Milankovitch precession, obliquity, and eccentricity periods. This result is in agreement with other investigators, who have proposed that Milankovitch-driven climate changes exercised an important control on Ormskirk Sandstone deposition.