CHARACTERIZATION OF THE EFFECT OF PEAK SHIFTS ON THE PERFORMANCE OF THE KALMAN FILTER IN MULTICOMPONENT ANALYSES

The effect of peak shifts on the performance of a Kalman filter multicomponent analysis algorithm hasbeen investigated.A series of Gaussian test systems were employed to characterize the concentrationestimation errors and the morphology of the on-line residuals(the innovations sequence).Both forwardand reverse filters were used in the generation of the innovations sequences.It was found that thedifference between the forward and reverse innovations sequences gave an accurate indication of thedirection and magnitude of the peak shift.A series of overlapped two-component systems were alsoinvestigated.Again,a correlation between the difference innovations and the degree of the responseshift was observed.The behavior of the Katman filter in fitting the shifted fluorescence emissionspectrum of benzo[a]pyrene was also examined.The response for henzo[a]pyrene in cyclohexanesolution was compared to that obtained on the surface of a reversed phase thin layer chromatographyplate.A red shift of 4 nm was detected for the surface spectrum by observing the difference innovationssequence.This approach holds promise for correction of response shifts in multicomponent systems.     

The marine transgression in the Middle Carboniferous of Brøggerhalvøya (Svalbard)

The change from continental to marine conditions in the Middle Carboniferous on Brøggerhalvøya started at the end of the Bashkirian with short-term transgressive events at the top of the Brøggertinden Formation. Local basin subsidence was responsible for the pulsatory nature of the transgression. The establishment of a shallow marine carbonate-dominated environment is represented by the Moscovian Scheteligfjellet Member which overlies the post-Caledonian red beds of the Brøggertinden Formation. The Scheteligfjellet Member is the lowermost member of the Nordenskioldbreen Formation and shows distinct lateral facies variations. Three facies associations can be distinguished: lagoonal facies, shoal facies and open marine facies. The succeeding two members were deposited in subtidal areas of the carbonate platform. A basin subsidence event at the Carboniferous/Permian boundary was responsible for a short shift into deeper depositional environments during a time of worldwide regression. After this a continuous regression led to supratidal conditions at the top of the Nordenskioldbreen Formation.     

Syros Metasomatic Tourmaline: Evidence for Very High-{delta}11B Fluids in Subduction Zones

High-pressure (HP) metamorphic blocks enclosed in a mafic toultramafic matrix from a mélange on the island of Syrosare rimmed by tourmaline-bearing reaction zones (blackwalls).The B isotopic composition of dravitic tourmaline within theseblackwalls was investigated in situ by secondary ion mass spectrometry.Boron in these tourmalines is unusually heavy, with ¹¹B valuesexceeding +18 in all investigated samples and reaching an extremevalue of +28·4 in one sample. Blackwalls formed duringexhumation of the HP mélange at a depth of 20–25km at temperatures of 400–430°C, by influx of externalhydrous fluids. The compositions of the fluids are estimatedto be in the range of 100–300 µg/g B with ¹¹B valuesof +18 to +28. The high ¹¹B values cannot be explained by tourmalineformation from unmodified slab-derived fluids. However, suchfluids could interact with the material in the exhumation channelon their way from the dehydrating slab to the site of tourmalineformation in the blackwalls. This could produce exceptionallyhigh ¹¹B values in the fluids, a case that is modelled in thisstudy. The model demonstrates that subduction fluids may beeffectively modified in both trace element and isotopic compositionduring their migration through the material overlying the subductingslab. Blackwall tourmaline from Syros has a large grain size(several centimetres), high abundance, and an exceptionallyhigh ¹¹B value. The formation of tourmaline at the contact betweenmafic or felsic HP blocks and their ultramafic matrix involvedfluids released during dehydration reactions in the subductingslab. It forms a heavy-boron reservoir in hybrid rocks overlyingthe subducting slab, and may, thus, have a significant impacton the geochemical cycle of B and its isotopes in subductionzones. KEY WORDS: boron isotopes; tourmaline; subduction zone; fluid, high pressure     

Tufa as a record of perennial fresh water in a semi-arid rift basin, Kapthurin Formation, Kenya

Lithological and biological features of a fossiliferous tufa in the Kapthurin Formation, Baringo, Kenya, reveal the presence of a lush wetland in a semi-arid environment during the Middle Pleistocene ( ca 500 ka) in this portion of the East African Rift Valley. Four geological sections, each between 3 m and 8 m in thickness, exposed over a distance of 0·5 km, reveal a 1 to 2 m thick paludal tufa which is composed of three carbonate beds, two dark grey silty claystones and a reddish-brown silty palaeosol. High resolution stratigraphic analysis, carbonate petrography, stable isotope and elemental geochemistry, clay mineralogy and fossil remains (molluscs, ostracods, diatoms and charophytes) reveal a ground water-fed system that fluctuated in depth and periodically disappeared altogether. Oxygen isotope ratios (δ¹⁸O) of tufa matrix range from −4·5‰ to −8·0‰ (Vienna Pee Dee Belemnite) and become more positive up section, indicating the decreasing influence of fault-related fluids and increasing residence time or freshness of wetland water, rather than evaporative enrichment. This spring was situated on a lake margin during low lake levels, thrived during periods of increased ground water input and was ultimately replaced by an alkaline lake. The wetland would appear to have existed during a cool interval within the generally warm Marine Isotope Stage 13 or perhaps during the warm second half of Marine Isotope Stage 13. The ground water source of this wetland arose through a fault system. Thus, the position of the tufa deposit is controlled structurally but the timing and duration of the wetland system may have been influenced by both climatic and tectonic factors.     

Deposition of climbing-ripple beds: a flume simulation

Thirteen runs were made in a small recirculating flume to simulate the deposition of the climbing-ripple sequences commonly present in fine-grained facies of fluvial and deltaic deposits. These sequences consist of intergradational climbing-ripple cross laminae and draped laminae. The experiments were based on the assumption that stratification type depends mainly on near-bottom flow structure and uniform sediment fallout from an overloaded flow. Various combinations of curves of velocity versus time and of sediment feed versus time in runs lasting from 45 to 840 min were used in an exploratory program; conditions for each run were selected on the basis of experience in previous runs. The runs verified that Type A (erosional-stoss) climbing ripples are produced by aggradation rates that are small relative to ripple migration rate, and Type B (depositional-stoss) climbing ripples are produced by aggradation rates that are large relative to ripple migration rate. Draped lamination results from continued fallout of sediment from suspension after ripple migration ceases or almost ceases. Comparison of geometric details of the ripple stratification produced in the flume runs with that in natural sequences, supplemented by considerations on maximum and minimum migration rates of ripples, suggests times of no more than a few tens of hours for the deposition of the climbing-ripple portions of sequences 10-20 cm thick. Runs in which deposition of a 20 cm sequence took more than 10 h produced such atypical features of ripple geometry as sharp crests, planar lee-side laminae, and angular toeset-foreset contacts.     

Ten things higher education needs to know about GIS in primary and secondary education

This paper examines the status of efforts to implement GIS in Kindergarten to Grade 12 (K-12) education in the United States. Factors promoting and impeding the growth and diffusion of GIS are identified and suggestions for action on the part of higher education GIS specialists are made. In the United States more science teachers have adopted GIS geography/social studies teachers for several reasons. These include science teacher preservice preparation and the essentially different natures of the respective disciplines. Preservice education and teachers' perceptions of geography emerge as key factors influencing the diffusion of GIS in K-12 classrooms. The need for on cognition and GIS before effective curricula and instruction can be developed is emphasized. Three strategies directed at higher education GIS specialists may help implement this eduational innovation. They are: (1) modelling GIS instruction in content classes; (2) including GIS in preservice preparation classes; and (3) outreach to professors who tach educational technology to educate than regarding GIS. The addendum by Paul Heinrich which follows this paper compares US and UK experiences in the diffusion of GIS in elementary and secondary schools.     

Physical and Chemical Models of Zoned Silicic Magmas: The Loma Seca Tuff and Calabozos Caldera, Southern Andes

The late Pleistocene Calabozos ash-flow and caldera complexlies in central Chile in a section of the Andean cordillerathat is transitional between dominantly andesitic-to-rhyoliticvolcanism to the north and mafic andesitic and high-aluminabasaltic volcanism to the south. The Calabozos rocks range incomposition from basaltic andesite to rhyodacite and definea high-K calcalkalic suite. They contain 2–25% phenocrystsof plagioclase, clinopyroxene, orthopyroxene, Fe-Ti oxides,and apatite, ? minor biotite or amphibole. More than 1000km³ of rhyodacitic to dacitic magma erupted atthe Calabozos caldera complex as three major compositionallyzoned ash-flow sheets, Unit L (0?8 Ma), Unit V (0? 30Ma), andUnit S (0?15 Ma) of the Loma Seca Tuff. Phenocryst modes, trace-elementcontents, inferred magmatic volatile contents, and oxygen fugacitiesvary systematically with major-element composition in the tuffs.In the cases of Units V and S, it is possible to reconstructcompositional, thermal, and volatile gradients that existedin density-stratified magma chambers shortly prior to theireruption. The magma graded from crystal-poor, water-rich, andbiotite-bearing rhyodacite in the upper reaches of the chamberto more crystal-rich, water-poor, and amphibole-bearing daciteat deeper levels. Fe-Ti oxide equilibration temperatures are800 to 900?C for rhyodacite and 900 to 950?C for dacite. Magmathat erupted as Unit S was slightly hotter and more oxidizedthan magma that gave rise to Unit V. More mafic magmas wereassociated with the voluminous rhyodacitic to dacitic magmareservoir, as indicated by the presence of andesite and basalticandesite lava flows and by scoria inclusions in Unit V. The compositional suite from basaltic andesite to rhyodacitecan be simulated satisfactorily by crystal-fractionation calculationsbased on major-element phenocryst and rock compositions, andis consistent with modes of the Calabozos rocks. Rhyodacitesof Units V and S, however, are enriched in elements such asRb, Ba, and Zr relative to trace-element contents predictedby crystal-fractionation models. The enrichment can be achievedby assimilation of wall rock or a partial melt of the wall rock.The latter requires that the ratio of assimilation rates tocrystallization rates be between 0?1 and 0?3. Rates of assimilationversus crystallization were greater for Unit S than for UnitV, which is consistent with the lower Fe-Ti oxide temperaturesand less oxidized state of the latter. The Loma Seca Tuff is similar in bulk composition to sanidine-bearingash-flow sheets erupted on ‘mature’ continentalcrust, but it is mineralogically akin to ash-flow tuffs eruptedon ‘immature’ crust. The difference is attributed,in part, to the effect of the density of the crust on the rateof magma ascent at shallow levels. The ascent of large bodiesof silicic magma is slower in silicic (less dense) crust thanin mafic crust, causing the magmas to be erupted at a laterpoint in the crystallization history.     

Strong Compositional Zonation in a Silicic Magmatic System: Los Humeros, Mexican Neovolcanic Belt

The Los Humeros volcanic center, located 180 km east of MexicoCity, is one of several silicic centers in the ‘back-arc’portion of the Mexican Neovolcanic Belt. Eruptive products spanthe compositional range from high-silica rhyolite to basalt.During the last 0?46 Ma, three major explosive eruptions andan extended period of lava flow emplacement periodically sampledan integrated magma reservoir that was initially zoned fromrhyolitic uppermost levels to andesitic and perhaps basalticlower levels, with compositional gaps in the ranges 63–67and 72–75 per cent SiO₂. The compositional zonation canlargely be explained by fractional crystallization, but mustbe accompanied by assimilation to explain the range of Sr andNd isotopic ratios. Higher than predicted concentrations ofNi, Cr, and strongly incompatible elements such as Rb and Bain andesites suggest continuous replenishment of a fractionatingchamber by mantle-derived basalts. The volumetric predominanceof rhyolite in the early history of the center points to a longperiod of accumulation of differentiates without eruptive withdrawal. Once volcanic activity started tapping the chamber, eruptiverates seem to have exceeded the rate of regeneration of differentiatedmagma. Although there is overlap in the compositional zonationof the products of successive eruptive events, the dominantvolume of each is always more mafic than that of the precedingeruption, indicating only limited regeneration of differentiatedmagmas during repose periods. This seems to have been a consequenceof the chamber remaining in approximate thermal balance duringthe last 0?46 Ma, as shown by similar Fe-Ti oxide temperaturesfor given magma compositions, regardless of age. Calculationssuggest that the chamber received thermal input through theinjection of basalt at an average rate of 0?1 km³ per thousandyears. Apparently this thermal input was too small to generatedifferentiated magma by partial melting of the wall rocks ofthe chamber, but large enough to offset conductive or hydrothermalcooling that would promote differentiation by extensive crystallization.