Thermodynamics of Al/Al avoidance in the ordering of Al/Si tetrahedral framework structures

The main driving force behind Al/Si ordering in tetrahedral framework aluminosilicates is nearest-neighbour Al/Al avoidance. Computer simulation is used to explore the direct consequences of such Al/Al avoidance. The main result is that the order-disorder transition temperature T _c falls dramatically as the concentration x of Al in the structure is reduced, and if the only interactions are those associated with nearest-neighbour Al/Al avoidance, T _c becomes zero for x less than some critical value x _c , where x _c =0.31 for the feldspar framework and x _c =0.34 for cordierite. Also a large degree of short range order is found above T _c . Both results differ radically from the standard Bragg-Williams model. Plots of entropy and enthalpy of ordering are given as functions of x and T, which may be used to interpret experimental data or for extrapolation into ranges of x and T inaccessible to experiment. Received: 14 May 1997 / Revised, accepted: 2 June 1997     

Nitrogen Mass Fraction and Stable Isotope Ratios for Fourteen Geological Reference Materials: Evaluating the Applicability of Elemental Analyser Versus Sealed Tube Combustion Methods

Thirteen commercially available silicate reference materials (RM) and one in‐house reference material, eleven of which have no previously published values, were analysed for nitrogen mass fraction and isotopic ratios with an Elemental Analyser (EA), and a Sealed Tube Combustion line, coupled to a continuous flow isotope ratio mass spectrometer (IRMS). These materials ranged from < 10 μg g^?1 to 1% m/m nitrogen mass fractions and δ¹⁵N of ?0.5 to +19.8‰. Existing nitrogen RM BHVO‐2, MS#5 and SGR‐1b were used to assess the accuracy of the data from the sealed tube combustion line, which was found to be in good agreement with existing published values. In contrast, the EA‐IRMS failed to fully liberate nitrogen from all silicate rocks and minerals (achieving a mean of 44 ± 10% nitrogen yield) resulting in kinetic fractionation of isotope values by ?1.4‰ on average. Therefore, sealed tube combustion is better suited for analyses of silicate‐bound nitrogen. The EA worked reliably for organic samples, but care should be taken when using the EA for silicate nitrogen research. Moving forward, it is recommended that BHVO‐2, Biotite‐Fe, FK‐N and UB‐N be used as quality control materials as they appear to be most reproducible in terms of nitrogen mass fraction (relative error < 10%, 1s), and isotopic composition (< 0.6‰, 1s).     

Flow cytometry and conventional enumeration of microorganisms in ships' ballast water and marine samples

Conventional methods for bacteriological testing of water quality take long periods of time to complete. This makes them inappropriate for a shipping industry that is attempting to comply with the International Maritime Organization's anticipated regulations for ballast water discharge. Flow cytometry for the analysis of marine and ship's ballast water is a comparatively fast and accurate method. Compared to a 5% standard error for flow cytometry analysis the standard methods of culturing and epifluorescence analysis have errors of 2-58% and 10-30%, respectively. Also, unlike culturing methods, flow cytometry is capable of detecting both non-viable and viable but non-culturable microorganisms which can still pose health risks. The great variability in both cell concentrations and microbial content for the samples tested is an indication of the difficulties facing microbial monitoring programmes. The concentration of microorganisms in the ballast tank was generally lower than in local seawater. The proportion of aerobic, microaerophilic, and facultative anaerobic microorganisms present appeared to be influenced by conditions in the ballast tank. The gradual creation of anaerobic conditions in a ballast tank could lead to the accumulation of facultative anaerobic microorganisms, which might represent a potential source of pathogenic species.     

Climatic and oceanographic changes in the Northeast Atlantic reflected by magnetic properties of sediments deposited on the Portuguese Margin during the last 340 ka

Rock magnetic parameters measured along two giant piston cores MD95-2040 (40°34′N, 9°51′W) and MD95-2042 (37°47′N, 10°09′W) collected off the Portuguese Margin, related to other proxy-climatic data, have been used to reconstruct magnetic mineralogical changes of, in relation to environmental and climatic conditions over the North Atlantic, Western Europe and Northwest Africa during the last three climatic cycles (since isotope stage 10). Thin discrete layers containing coarse grains of titano-magnetite are associated with events of iceberg discharge during Heinrich events 1-6 [Heinrich, Quat. Res. 29 (1988) 142] that have equivalent events in isotope stages 5-8. Concentrations of fine-grained (Ti-) magnetite and hematite/goethite, varying in phase opposition, are directly linked with alternations of cold and warm climatic periods. Spectral analyses of the rock magnetic signals reveal Milankovitch periods at 100 and 41 ka, confirming the relationship with long-term climatic changes at high latitudes. The nature (Ti-magnetite) and size range of the finest ferrimagnetic fraction as well as its variation, suggest a control by deep currents carrying a colloidal/clayey fraction from remote sources (Iceland, Faeroes, mid-Atlantic Ridge). Variation of hematite/goethite contents is linked with transport by rivers and winds from the neighbouring continent. A tight correlation with the D-O cycles in Greenland ice records confirms that North Atlantic oceanic regimes and continental wind regimes were strongly influenced by millennial scale climatic changes throughout the last 350 ka.     

Aerosol optical thickness retrieval over the Atlantic Ocean using GOES imager data

An algorithm based on simulated satellite signal calculated by the 6S radiative transfer model has been developed in order to retrieve the aerosol optical thickness of dust over the Atlantic ocean. The algorithm is applied to the visible channel of Geostationary Operational Environmental Satellite (GOES 8) images. The inversion uses a look-up table giving the satellite signal intensity as a function of surface albedo, viewing geometry, solar illumination and the optical properties of the aerosols. The study consists of assessing the feasibility of monitoring and mapping the transport of suspended particles across the Atlantic from the Sahara to the Caribbean. The study area is between 10 and 25 N and 30 and 65 W. The optical thickness of aerosols has been calculated over a period of 11 days between 10th and 20th of June 1997 for the 14:15 UT GOES image acquisition. The calculated aerosol optical thickness ranges from 0.0 to 0.81 with an important event of dust presence occurring between 13th and 16th of June. The retrieved aerosol optical thickness is in good agreement with the values obtained between 14h UT and 15h UT from ground based sun photometer measurements on the island of Guadeloupe, and a coefficient correlation (R²) of 0.88 has been found between the data sets.     

Coupling of a Column System with ICP‐MS for the Characterisation of Colloid‐mediated Metal(loid) Transport in Porous Media

In this work a coupling method for the characterisation of colloid‐mediated transport of the metal(loid) species in porous media was developed. For this transport experiments quartz sand was used as column packing material and the synthetic three‐layer clay mineral laponite as model colloid. The determination of colloids was conducted by means of UV detection. The quantification of the metal(loid) ions was carried out in two different ways: (1) The fractions collected at the column outlet were analysed with an inductively coupled plasma mass spectrometer (ICP‐MS) (offline measurements); (2) the column system was directly coupled with ICP‐MS (online measurements). In the column experiments the influence of laponite colloids on the transport of Cu, Pb, Zn, Pt and As species was investigated. In the offline experiments as a consequence of dilution during sample preparation no metal(loid) species at the column outlet could be found. Unlike this the breakthrough of all metal(loid)s could be detected under the same experimental column conditions in the coupling experiments. This coupling technique offers the online detection of the metal species and colloidal particles with high resolution even at low concentrations and without any time‐consuming preparation. The coupling experiments have shown that the laponite particles accelerate the transport of the cationic metals. For anionic metal(loid) species no influence of laponite on their transport behaviour was found.     

Attenuation tomography of the Southern Apennines (Italy)

The aim of this study is to improve our knowledge of the attenuation structure in the Southern Apennines using a new amplitude ratio tomography method (Phillips et al., Geophys Res Lett 32(21):L21301, 2005) applied on both direct and coda envelope measurements derived from 150 events recorded by 47 stations of the Istituto Nazionale di Geofisica e Vulcanologia National Seismic Network (Rete Sismica Nazionale Centralizzata). The two-dimensional (2-D) analysis allows us to take into account lateral crustal variations and heterogeneities of this region. Using the same event and station distribution, we also applied a simple 1-D methodology, and the performance of the 1-D and 2-D path assumptions is tested by comparing the average interstation variance for the path-corrected amplitudes using coda and direct waves. In general, coda measurement results are more stable than using direct waves when the same methodology is applied. Using the 2-D approach, we observe more stable results for both waves. However, the improvement is quite small, probably because the crustal heterogeneity is weak. This means that, for this region, the 1-D path assumption is a good approximation of the attenuation characteristics of the region. A comparison between Q tomography images obtained using direct and coda amplitudes shows similar results, consistent with the geology of the region. In fact, we observe low Q along the Apennine chain toward the Tyrrhenian Sea and higher values to the east, in correspondence with the Gargano zone that is related to the Apulia Carbonate Platform. Finally, we compared our results with the coda Q values proposed by Bianco et al. (Geophys J Int 150:10–22, 2002) for the same region. The good agreement validates our results as the authors used a completely independent methodology.