Major and Trace Element Analysis of Silicate Rocks by XRF and Laser Ablation ICP-MS Using Lithium Borate Fused Glasses: Matrix Effects, Instrument Response and Results for International Reference Materials

Major and trace element compositions of fifteen silicate rock reference materials have been determined by a combined XRF and laser ablation ICP‐MS (LA‐ICP‐MS) technique on glasses prepared by fusing the sample with a lithium borate flux (sample:flux = 1:3). Advantages of this technique include the ability to measure major and trace element abundances on a single sample using a quick and simple preparation that attacks resistant phases such as zircon without the need for acid dissolution. The method is suitable for a wide variety of bulk compositions including mafic, intermediate and silicic rocks. Abundance‐normalized mass response patterns (the ratio of signal intensity to element concentration) of the LA‐ICP‐MS analyses vary systematically with major element composition, demonstrating the presence of a matrix effect that cannot be compensated by normalisation to a single internal standard element. Increasing the sampling distance between the ICP‐MS cone and the torch reduces the magnitude of this effect, suggesting that a mechanism related to residence time of ablated particles in the plasma may be at least partially responsible for the observed variations in mass response patterns. When using a matrix‐matched calibration, agreement of the LA‐ICP‐MS results with published reference values or those obtained by solution ICP‐MS is 10% relative. Analytical precision based on replicate analyses is typically 5% RSD. Procedural detection limits that include contributions from gas background and flux are 0.01‐0.1 μg g‐¹ for the heavy mass trace elements (Rb‐U). Major element analyses by XRF show excellent agreement with results obtained using a conventional heavy element absorbing flux. High quality major and trace element data for silicate rocks can be achieved by a combined XRF and LA‐ICP‐MS analysis of Li₂B₄O₇/LiBO₂ fused glasses provided an appropriate matrix‐matched calibration is adopted.     

Quaternary stresses revealed by calcite twinning inversion: insights from observations in the Savonnières underground quarry (eastern France)

Calcite samples were extracted both from the rock matrix and the superficial coating of a karstified fault plane of an underground quarry, located in the eastern border of the Paris basin. The karstification is dated as Quaternary. Analysis of mechanical calcite twinning reveals that only the calcite matrix has also undergone a compression trending WNW that can be attributed to the Mio-Pliocene alpine collision. Both coating and matrix have undergone a strike-slip regime with σ₁ roughly trending north–south, that could correspond to the regional present-day state of stress, a strike-slip compression rather trending NNW, modified by local phenomena. To cite this article: M. Rocher et al., C. R. Geoscience 335 (2003).     

A Comparison of an Ecological Model and GIS Spatial Analysis to Describe Niche Partitioning Amongst Carrion Beetles in Nebraska

Carrion beetles depend on vertebrate carcasses to rear their young. Carcasses are a limited resource with patchy distribution, and there is an intense competition among many species for these carcasses. This situation is expected to lead to niche partitioning, such that different beetle species use different resources and thus escape direct competition. Our project used a geographic information system (GIS) and pitfall sampling to characterize carrion beetle preferences for soil texture and land use in Kearney County, Nebraska. The GIS was used to select sites where sampling was conducted using pitfall traps baited with rat carcasses. Attracted beetles were counted, identified to species, and released. The resulting data were used to construct occurrence maps of eleven species of carrion beetles by overlaying soil texture and land use. We then compared the results of EcoSim (an ecological simulation model of niche overlap) with GIS–generated maps of probability of carrion beetle occurrence. Our results are consistent with landscape–level niche partitioning by seven of the eleven examined species. Our application of GIS to the spatial analysis of carrion beetle distributions demonstrates how this technology can be used to test ecological and evolutionary hypotheses, predict habitat associations, and examine the effects of land use on a community of insects. This work could easily be extended to study the habitat preferences of the federally endangered American burying beetle, Nicrophorus americanus .     

Oxygen isotopes in single micrometer-sized quartz grains: tracing the source of Saharan dust over long-distance atmospheric transport

Oxygen isotope compositions were measured by ion microprobe in individual micrometer-sized quartz grains extracted from one aerosol sample collected on the Cape Verde Islands and from four surface samples (three soils and one sediment) representing potential source regions of aerosols in Western and Central Africa (Morocco, Algeria, Niger, and Chad). A large range of δ¹⁸O values, from +6.2‰ to +39.3‰ is present within the aerosol quartz grains. The different size fractions of the quartz grains from the surface samples overlap nearly entirely this range but show significant differences in their δ¹⁸O distributions for the different size fractions of the grains (i.e., different modes, different proportions of grains with low or high δ¹⁸O, ...). These differences in δ¹⁸O distributions can be related to different geological formations (i.e., mantle-derived magmatic rocks, crustal magmatic rocks, or sedimentary rocks) outcropping in each region, thus giving a fingerprint of the source region. Quartz grains with unusually high δ¹⁸O values between +30‰ and +40‰ were attributed to lacustrine cherts formed in evaporitic environments (Chad basin).The existence of distinct δ¹⁸O distributions for the surface samples, which reflect regional geology but indicate some transport of the grains, enables the characterization of mixing processes during dust emission in the atmosphere. Particles are mixed at a regional scale in the dust reservoir, but injection of fine particles into the high troposphere occurs as a discrete and localized event with no mixing during the subsequent long-range transport by the easterlies. The comparison of the δ¹⁸O distribution of the quartz from the aerosol sample with the equivalent size fractions in surface samples shows that the Niger area is the more probable source region for the aerosol although the Moroccan source cannot be excluded. This method gives a valuable tool to trace the source region of dust into the atmosphere or into sediment samples, allowing the reconstruction of air mass circulations.     

Volcanisme de l'ı̂le aux Pingouins,archipel Crozet,témoin de l'hétérogénéité du manteau fertile au sud de l'océan IndienPenguins Island,Crozet archipelago,volcanic evidence for a heterogeneous mantle in the southern Indian Ocean

Despite its small area (5.6 km²), the Penguins Island brings magmatic information concerning mantle geochemical heterogeneities in southwestern Indian Ocean. The volcanism that built the island was firstly associated with marine deposits, and secondly with aerial, giving then abundant volcanic breccias and lava flows. The rocks are weakly differentiated and result of magmatic fractionation from picritic to tephritic types. KAr ages are near 1.1 Ma. The magmatic source may be related to a HIMU reservoir or to EMI ± EMII ones, depending on the geochemical evidences that are taken into account. However, comparisons with the Marion Island, on the same oceanic plateau and far to the west, as well as with Kerguelen Islands, far to the east, suggest a very heterogeneous mantle source. To cite this article: A. Giret et al., C. R. Geoscience 334 (2002) 481–488.     

Accreted fragments of the Late Cretaceous Caribbean–Colombian Plateau in Ecuador

The eastern part of the Western Cordillera of Ecuador includes fragments of an Early Cretaceous (≈123 Ma) oceanic plateau accreted around 85–80 Ma (San Juan–unit). West of this unit and in fault contact with it, another oceanic plateau sequence (Guaranda unit) is marked by the occurrence of picrites, ankaramites, basalts, dolerites and shallow level gabbros. A comparable unit is also exposed in northwestern coastal Ecuador (Pedernales unit).

Picrites have LREE-depleted patterns, high Nd_i and very low Pb isotopic ratios, suggesting that they were derived from an extremely depleted source. In contrast, the ankaramites and Mg-rich basalts are LREE-enriched and have radiogenic Pb isotopic compositions similar to the Galápagos HIMU component; their Nd_i are slightly lower than those of the picrites. Basalts, dolerites and gabbros differ from the picrites and ankaramites by flat rare earth element (REE) patterns and lower Nd; their Pb isotopic compositions are intermediate between those of the picrites and ankaramites. The ankaramites, Mg-rich basalts, and picrites differ from the lavas from the San Juan–Multitud Unit by higher Pb ratios and lower Nd_i.

The Ecuadorian and Gorgona 88–86 Ma picrites are geochemically similar. The Ecuadorian ankaramites and Mg-rich basalts share with the 92–86 Ma Mg-rich basalts of the Caribbean–Colombian Oceanic Plateau (CCOP) similar trace element and Nd and Pb isotopic chemistry. This suggests that the Pedernales and Guaranda units belong to the Late Cretaceous CCOP. The geochemical diversity of the Guaranda and Pedernales rocks illustrates the heterogeneity of the CCOP plume source and suggests a multi-stage model for the emplacement of these rocks. Stratigraphic and geological relations strongly suggest that the Guaranda unit was accreted in the late Maastrichtian (≈68–65 Ma).     

Temperature distribution in karst systems: the role of air and water fluxes

A better understanding of heat fluxes and temperature distribution in continental rocks is of great importance for many engineering aspects (tunnelling, mining, geothermal research, etc.). This paper aims at providing a conceptual model of temperature distribution in karst environments which display thermal ‘anomalies’ as compared with other rocks. In temperate regions, water circulation is usually high enough to ‘drain‐out’ completely the geothermal heat flux at the bottom of karst systems (phreatic zone). A theoretical approach based on temperature measurements carried out in deep caves and boreholes demonstrates, however, that air circulation can largely dominate water infiltration in the karst vadose zone, which can be as thick as 2000 m. Consequently, temperature gradients within this zone are similar to the lapse rate of humid air (～0.5 °C 100 m^?1). Yet, this value depends on the regional climatic context and might present some significant variations.     

Association of calcium with colloidal particles and speciation of calcium in the Kalix and Amazon rivers

A considerable amount of colloidally bound Ca has been detected in water samples from Amazonian rivers and the Kalix River, a sub-arctic boreal river. Fractionation experiments using several analytical techniques and processing tools were conducted in order to elucidate the matter. Results show that on average 84% of the total Ca concentration is present as free Ca. Particulate, colloidal and complexed Ca constitute the remaining 16%, of which the colloidal fraction is significant. Ultrafiltration experiments show that the colloidal fraction in the sampled Amazonian rivers and the Kalix River range between 1% and 25%.In both the Amazonian and the Kalix rivers the technique of cross-flow ultrafiltration was used to isolate particles and colloids. The difference in concentration measured with ICP-AES and a Ca ion-selective electrode in identical samples was used to define the free Ca concentration and thus indirectly the magnitude of the particulate, colloidal and complexed fractions. Results from the Kalix and Amazonian rivers are in excellent agreement. Furthermore, the results show that the colloidal concentrations of Ca can be greatly overestimated (up to 227%) when conventional analysis and calculation of ultrafiltration data is used due to retention of free Ca ions during the ultrafiltration process. Calculation methods for colloidal matter are presented in this work, using complementary data from ISE analysis.In the Kalix River temporal changes in the fractionation of Ca were studied before, during and after a spring-flood event. Changes in the size distribution of colloidally associated Ca was studied using FlFFF (Flow Field-Flow Fractionation) coupled on-line to a HR ICP-MS. The FlFFF-HR ICP-MS fractograms clearly show the colloidal component of Ca, supporting the ultrafiltration findings. During winter conditions the size distribution of colloidally associated Ca has a concentration maximum at ∼5 to 10 nm in diameter, shifting to smaller sizes (<5 nm) during and after the spring flood. This shift in size distribution follows a change in the river during this period from ironoxyhydroxy colloids being the most important colloidal carrier phase to humic substances during and after the spring flood.WHAM and NICA-Donnan models were used to calculate the amount of colloidally bound Ca. The results similar for both models, show that on average 16% of the Ca may be associated to a colloidal phase, which is in broad agreement with the measurements.     

Geochemistry of a chert breccia

A complex history of diagenetic interactions between a siliceous sediment, seawater and fresh water is revealed by intraformational chert breccias. Chert breccias were formed in the Campanian Mishash Formation in Israel, by “practically contemporaneous” fracturing of lithified cherty layers followed by silicification and lithification of the matrix. Pairs of fragments and matrix were compared with respect to their chemical (Ca, Sr, Na, K, Mg, Li, B, SO₄, Ba) and isotopic (δ¹⁸O, δD, δ¹¹B) composition. δ¹¹B was analyzed by ion-probe and includes a profile across a fragment-matrix contact. The epicontinental cherts of the Mishash Fm. are enriched by a factor of 10 to 50 in all elements other than O and Si in comparison with Deep-Sea cherts. All results are compatible with the proposition that the lithification of the matrix occurred in contact with fresh-water, as opposed to seawater in which the fragments, as well as most of the Mishash sediments were formed. The strongest evidence for this difference is in the higher concentration of B in the fragments (27-70 ppm vs. 11-21ppm in the matrix) and higher δ¹⁸O (29 to 35‰ vs. 21 to 33‰). δD is a less efficient discriminator, though compatible with fresher water diagenesis of the matrix: −115‰ to −76‰ for hydrogen in the chert of the fragments, compared to −141 to −85‰ for the matrix. δ¹¹B in the matrix shows some of the lowest values recorded in sediments (δ¹¹B = −33‰), but varies strongly, suggesting that the source of boron in the matrix is a mixture of a freshwater and a marine component. Both seawater and the freshwater that has equilibrated with the cherts underwent varying degrees of evaporation. Ca, Sr and SO₄ are carried by apatite, trapped as detritus in the matrix. The concentration of lithium in the matrix is high (11-16 ppm), whereas in the adjacent fragments it is mostly only within 1-2 ppm. Li probably enters the matrix from the interstitial solution, during the opal → quartz transformation. The second, prolonged, transformation takes place in a (freshwater) flow-through, open system. This allows a much larger mass of Li to be scavenged by the transforming silica despite its low concentration in freshwater.