The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.     

Zur genetischen Unterscheidung von gemeinen Klüften und Verschiebungen

Zusammenfassung Oft wird zwischen Klüften und Verschiebungen ein genetischer Zusammenhang gesehen. Neuere Untersuchungen lassen einen grundsätzlichen Unterschied erkennen: Die gemeinen Klüfte entstehen durch spröden Bruch im Anschluß an eine elastische Deformation; Verschiebungen und ihnen zugeordnete Klüfte gehen zumeist aus einer plastischen Deformation hervor. Auch sind Verschiebungen an begrenzte Zonen gebunden und meist gefügefremd, obwohl sie sich bestehenden Kluftsystemen anpassen können. Die Systeme der gemeinen Klüfte sind dagegen fast gleichmäßig auf weite Bereiche verteilt und passen sich dem bestehenden Gesteinsgefüge an. Zur Deutung der Bruchtektonik sollten deshalb klufttektonische Analysen nur mit äußerster Vorsicht herangezogen werden.

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Joints and faults are commonly regarded as genetically related. Recent investigations, however, tend to bring out a fundamental genetic distinction: Common joints form by brittle fracture following elastic deformation; faults result from ductile fracture. Moreover, faults and related joints are restricted to narrow zones and rarely conform with preexisting fabric, while common joints are regionally pervasive and are fabric controlled. When evaluating fracture analyses, therefore, the genetic distinction between common joints and faults must be borne in mind.

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Résumé On croit souvent devoir mettre en relation génétique joints et failles. Des études récentes permettent d'y voir une distinction. Les joints banaux proviennent d'une rupture cassante, à la suite d'une déformation élastique. Les failles suivent une rupture plastique. En plus, les failles et les joints qui leur sont apparentés sont restreints à des zones plus ou moins étroites et se conforment rarement à la structure interne de la roche, trandis que les joints banaux ont une distribution régionale, et sont liés à la structure interne. L'analyse des ruptures géologiques doit, par conséquent, tenir compte d'une distinction fondamentale entre joints banaux, et joints apparentés aux failles.

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Two-feldspar geothermometry in granulite facies metamorphic rocks

A geothermometric technique based on equilibria between coexisting plagioclase and alkali feldspar was applied to quartzo-feldspathic granulites from Salvador, BA, Brazil. The conditions of metamorphism were determined to be in the range 750 ° C–800 ° C, 4–8 Kb, by comparison with experimental data on the stabilities of sapphirine, phlogopite and other minerals occurring in the associated rocks. Selected feldspar data gives temperatures near, but slightly below, this range. Several variants of the Wood and Banno model, as well as an empirical two-pyroxene geothermometer, were also tested and found to give temperatures which were apparently 50 °–100 ° high. The solubility of Al₂O₃ in orthopyroxene indicates temperatures which are about 200 ° to high, suggesting that Fe in the natural assemblages significantly changes relationships observed experimentally in MgO-Al₂O₃-SiO₂ systems.     

A tertiary lamprophyre dike with high pressure xenoliths and megacrysts from Wiedemanns Fjord,East Greenland

Lamprophyric dikes, mainly of camptonite/monchiquite affinities occur in the Wiedemanns Fjord area. One example contains a complex assemblage of olivine-orthopyroxene-chrome spinel nodules, megacrysts of kaersutite, diopside, strongly reverse-zoned green salite and various spinel phases. Microprobe analyses are presented for all these phases and for the lilac-coloured titansalites and strongly-coloured kaersutites of the groundmass. It is concluded that these minerals record evolution under various P, T and oxidation regimes during the formation of a lamprophyric parent magma. The nodules provide evidence for deep fractures in this area supposedly associated with early rifting in the North Atlantic.     

Karroo basalts from western Zambia and geochemical provinces in central and southern Africa

New chemical analyses of Mesozoic basalts from Zambia show that low K₂O tholeiites are present in central as well as southern Africa. The distribution of geochemical provinces thus recognised supports the view that the Karroo Volcanic Cycle was initiated by the convective uprise of mantle material beneath the Nuanetsi area of Zimbabwe.

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Zusammenfassung Neue chemische Analysen mesozoischer Basalte von Zambia zeigen, da\ Tholeiite mit niedrigen Gehalten an K₂O sowohl in Zentralals auch in Südafrika vorkommen. Die auf diese Weise ermittelte Verbreitung geochemischer Provinzen unterstützt die Ansicht, da\ der Vulkanische Zyklus von Karroo durch den konvektiven Aufstieg von Mantelmaterial unter dem Gebiet von Nuanetsi Zimbabwes ausgelöst wurde.

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Résumé De nouvelles analyses chimiques de basaltes mésozoÎques de Zambie indiquent que des tholéiites à teneur basse en K₂O se présentent dans le centre aussi bien que dans le sud de l'Afrique. La distribution des provinces géochimiques ainsi reconnue confirme la théorie que »La Période Volcanique de Karoo« débuta par le soulèvement convectif du matériau du manteau sous la région de Nuanetsi en Zimbabwe.

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Occasional paper No. 75 Geological Survey of Zambia. Published by permission of the Director.

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Publishes with the approval of the Director, Institute of Geological Sciences (N.E.R.C.). U.K.     

Obsidian hydration dating of volcanic events

Obsidian hydration dating of volcanic events had been compared with ages of the same events determined by the ¹⁴C and KAr methods at several localities. The localities, ranging in age from 1200 to over 1 million yr, include Newberry Craters, Oregon; Coso Hot Springs, California; Salton Sea, California; Yellowstone National Park, Wyoming; and Mineral Range, Utah. In most cases the agreement is quite good. A number of factors including volcanic glass composition and exposuretemperature history must be known in order to relate hydration thickness to age. The effect of composition can be determined from chemical analysis or the refractive index of the glass. Exposure-temperature history requires a number of considerations enumerated in this paper.     

Properties of sea grass and sand flat sediments from the intertidal zone of St. Andrew Bay,Florida

Organic and carbonate carbon and textural properties of the substrates underlyingHalodule wrightii andThalassia testudinum sea grass beds in the intertidal zone of St. Andrew Bay, Florida were compared to adjacent unvegetated sand flats by physiographic divisions within the bay and to the subtidal slopes of the bay. Sea grass and sand flat sediments were principally fine-grained quartz sands. The mean particle-size of the sea grass sediments were finer-grained than those of the sand flats only in the west arm and lagoon of the bay. Size-frequency distributions of the sea grass sediments were generally slightly more negatively skewed and more leptokurtic than those of the sand flats. The sea grass sediments were less well sorted than were the sand flat sediments. The average organic and carbonate carbon contents of the sea grass beds were 1.9-fold greater than that of the sand flats but much less than that of the subtidal sea grass meadows. In the areas of pollution, sea grasses were absent; near this areaHalodule wrightii was the dominant sea grass.     

The major‐ and trace‐element whole‐rock fingerprints of Egyptian basalts and the provenance of Egyptian artefacts

Discrimination diagrams have been developed that source Egyptian basaltic artefacts using whole‐rock major element geochemistry. These include K₂O versus SiO₂, TiO₂ and P₂O₅ against MgO/Fe₂O₃^t (total Fe as Fe₂O₃), and a discriminant analysis diagram using SiO₂, Fe₂O₃^t, CaO, and MnO. A complementary set of diagrams uses easily obtained trace element data (Nb/Y versus Zr/Nb; Zr [ppm] versus Rb/Sr; TiO₂ [wt % volatile free] versus V; and Cr [ppm] versus Zr/Y) to determine the bedrock sources. These diagrams have been applied to seven First Dynasty basalt vessels (Abydos), two Fourth Dynasty basalt paving stones (Khufu's funerary temple, Giza), and two Fifth Dynasty paving stones (Sahure's complex, Abu Sir). They show that the bedrock source for all the artefacts was the Haddadin flow in northern Egypt. Multidimensional scaling and cluster analysis applied to the whole‐rock data (major elements and trace elements together) and previously published mineral fingerprinting studies confirm these results. Comparing mineral versus whole‐rock fingerprinting techniques, a major advantage of the former is the small sample size required (0.001 g compared to ≥ 0.1 g). Analytical costs are similar for both methods assuming that a comparison (bedrock) database can be assembled from the literature. For most archaeological problems, a whole‐rock bedrock database is more likely to exist than a mineral database, and whole‐rock analyses on artefacts will generally be easier to obtain than mineral analyses. Whole‐rock fingerprinting may be more sensitive than mineral‐based fingerprinting. Thus, if sample quantity is not an issue, whole‐rock analysis may have a slight cost, convenience, and technical advantage over mineral‐based methods. Our results also emphasize that the Egyptians cherished their Haddadin basalt flow and used it extensively and exclusively for manufacturing basalt vessels and paving stones for at least 600 years (∼3150 B.C. to 2500 B.C., approximate ages of the vessels and Abu Sir paving stones, respectively). © 2001 John Wiley & Sons, Inc.     

Tidal intrusion fronts

A tidal intrusion front forms as a dense seawater inflow plunges (subducts) beneath ambient estuarine water during flood tide. The associated foam lines and color changes have been observed on many smaller estuaries with constricted mouths. Internal hydraulic theory and laboratory experiments are reviewed and expressions are obtained for the position of plunging and the amount of associated mixing. The existence of a tidal intrusion front and its structure are discussed in terms of densimetric Froude numbers. These fronts are particularly important in smaller estuaries in which the intrusion process may dominate wind and tidal mixing and thus determine the overall stratification of the estuary. Three classes of three-dimensional plunging flow are identified and discussed. In particular, it is suggested that the peculiar, cursive V-shape plunge line is characteristic of strongly plunging flow.     

Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.