A Comparison of In Situ Analytical Methods for Trace Element Measurement in Gold Samples from Various South African Gold Deposits

Trace element concentrations in gold grains from various geological units in South Africa were measured in situ by field emission‐electron probe microanalysis (FE‐EPMA), laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and synchrotron micro X‐ray fluorescence spectroscopy (SR‐μ‐XRF). This study assesses the accuracy, precision and detection limits of these mostly non‐destructive analytical methods using certified reference materials and discusses their application in natural sample measurement. FE‐EPMA point analyses yielded reproducible and discernible concentrations for Au and trace concentrations of S, Cu, Ti, Hg, Fe and Ni, with detection limits well below the actual concentrations in the gold. LA‐ICP‐MS analyses required larger gold particles (> 60 μm) to avoid contamination during measurement. Elements that measured above detection limits included Ag, Cu, Ti, Fe, Pt, Pd, Mn, Cr, Ni, Sn, Hg, Pb, As and Te, which can be used for geochemical characterisation and gold fingerprinting. Although LA‐ICP‐MS measurements had lower detection limits, precision was lower than FE‐EPMA and SR‐μ‐XRF. The higher variability in absolute values measured by LA‐ICP‐MS, possibly due to micro‐inclusions, had to be critically assessed. Non‐destructive point analyses of gold alloys by SR‐μ‐XRF revealed Ag, Fe, Cu, Ni, Pb, Ti, Sb, U, Cr, Co, As, Y and Zr in the various gold samples. Detection limits were mostly lower than those for elements measured by FE‐EPMA, but higher than those for elements measured by LA‐ICP‐MS.     

An integrated zircon geochronological and geochemical investigation into the Miocene plutonic evolution of the Cyclades, Aegean Sea, Greece: Part 1: Geochronology

We use 369 individual U–Pb zircon ages from 14 granitoid samples collected on five islands in the Cyclades in the Aegean Sea, Greece, for constraining the crystallisation history of I- and S-type plutons above the retreating Hellenic subduction zone. Miocene magmatism in the Cyclades extended over a time span from 17 to 11 Ma. The ages for S-type granites are systematically ~2 million years older than those for I-type granites. Considering plutons individually, the zircon data define age spectra ranging from simple and unimodal to complex and multimodal. Seven of the 14 investigated samples yield more than one distinct zircon crystallisation age, with one I-type granodiorite sample from Mykonos Island representing the most complex case with three resolvable age peaks. Two samples from S-type granites on Ikaria appear to have crystallised zircon over 2–3 million years, whereas for the majority of individual samples with multiple zircon age populations the calculated ages deviate by 1–1.5 million years. We interpret our age data to reflect a protracted history involving initial partial melting at deeper lithospheric levels, followed by crystallisation and cooling at shallower crustal levels. Our study corroborates published research arguing that pluton construction is due to incremental emplacement of multiple magma pulses over a few million years. Assuming that multiple age peaks of our 14 samples can indeed serve to quantify time spans for magmatic emplacement, our data suggest that Aegean plutons were constructed over a few million years. Our tectonic interpretation of the U–Pb ages is that the S-type granites resulted from partial melting and migmatisation of the lower crust, possibly starting at ~23 Ma. The I-type granites and associated mafic melts are interpreted to reflect the magmatic arc stage in the Cyclades starting at ~15 Ma.     

The Sabzevar blueschists of the North-Central Iranian micro-continent as remnants of the Neotethys-related oceanic crust subduction

The Sabzevar ophiolites mark the Neotethys suture in east-north-central Iran. The Sabzevar metamorphic rocks, as part of the Cretaceous Sabzevar ophiolitic complex, consist of blueschist, amphibolite and greenschist. The Sabzevar blueschists contain sodic amphibole, epidote, phengite, calcite ± omphacite ± quartz. The epidote amphibolite is composed of sodic-calcic amphibole, epidote, albite, phengite, quartz ± omphacite, ilmenite and titanite. The greenschist contains chlorite, plagioclase and pyrite, as main minerals. Thermobarometry of a blueschist yields a pressure of 13–15.5 kbar at temperatures of 420–500 °C. Peak metamorphic temperature/depth ratios were low (~12 °C/km), consistent with metamorphism in a subduction zone. The presence of epidote in the blueschist shows that the rocks were metamorphosed entirely within the epidote stability field. Amphibole schist samples experienced pressures of 5–7 kbar and temperatures between 450 and 550 °C. The presence of chlorite, actinolite, biotite and titanite indicate greenschist facies metamorphism. Chlorite, albite and biotite replacing garnet or glaucophane suggests temperatures of >300 °C for greenschist facies. The formation of high-pressure metamorphic rocks is related to north-east-dipping subduction of the Neotethys oceanic crust and subsequent closure during lower Eocene between the Central Iranian Micro-continent and Eurasia (North Iran).     

Assessing climate persistence from climatic ‘noise’

Changes in climate are generally defined as differences between means. The autocorrelation usually encountered in geophysical series and the implied persistence, or reduced number of independent observations, tend to render significance tests of mean differences inconclusive until a considerable amount of data has accumulated, by which time a climatic change could be well under way. A more efficient alternative approach is provided by small-sample variances. Under slightly idealized conditions their frequency distribution is of the chi-square type with a number of degrees of freedom that measures the persistence in the series and can be monitored on a short time scale with a sequential sampling procedure.Also at homein CIRES, Campus Box 449, University of Colorado, Boulder, CO 80309, U.S.A.     

The internal structure of the Arosa Zone (Swiss-Austrian Alps)

The Arosa Zone, part of the main Alpine suture zone between the Austroalpine and the Penninic realms, forms a heterogeneous unit composed of rocks of oceanic and continental origin. It exhibits mélange character due to minor sedimentary mixing and local penetrative tectonic deformation during Cretaceous and Early Tertiary imbrication. Competent blocks of both Austroalpine and Penninic origin, covering up to 2.5 km², are embedded in incompetent serpentinitic or shaly-calcareous matrix. On a mesoscale, disrupted strata occur in and adjacent to thrust and shear zones. Contrasting competence between blocks and matrix partitioned deformation into brittle and ductile processes. Extension veins and shear fractures affected the competent strata whereas the matrix developed a penetrative foliation during ductile flow and accommodated high strain. Flow was mainly non-coaxial in the matrix, and coaxial extension prevailed in the blocks.In a regional tectonic setting, we define the Arosa Zone as the tectonostratigraphic unit sandwiched between the Austroalpine and Penninic units. It forms a narrow and highly imbricated zone containing both South Penninic ophiolitic and sedimentary rocks as well as blocks and slices of Austroalpine origin.

---

Zusammenfassung Die Arosa Zone ist Teil der Alpinen Suturzone zwischen Ostalpin und Pennimkum und bildet eine lithologisch heterogene Einheit aus kontinentalen und ozeanischen Gesteinen. Sie zeigt den Charakter einer Melange, die aus, untergeordnet, sedimentärer Durchmischung und lokaler, aber penetrativer tektonischer Deformation während kretazisch und alttertiärer Tektonik resultiert. Kompetente Blöcke ostalpiner und penninischer Herkunft, die bis zu 3 km im Streichen verfolgbar sind, schwimmen in einer inkompetenten serpentinitischen oder tonig-karbonatischen Matrix. Im Mesobereich treten zerbrochene Gesteinsabfolgen in oder direkt an Überschiebungs- und Scherzonen auf. Unterschiedliche Kompetenz zwischen Blöcken und Matrix teilt die Deformation in spröde und duktile Prozesse auf. Die kompetenten Gesteine zeigen Extensionsspalten und Scherbrüche, in der Matrix entwickelte sich durch duktiles Fließen eine penetrative Schieferung bei hoher Strainintensität. Die Deformation in der Matrix war hauptsächlich nicht-koaxial, koaxiale Extension herrschte in den Blöcken.Im regionalen tektonischen Rahmen definieren wir die Arosa Zone als tektonostratigraphische Einheit zwischen Ostalpin und Penninikum. Sie bildet eine schmale, stark imbrikierte Zone die, aus südpenninischen ophiolithischen und sedimentären Gesteinen, sowie aus Blöcken und Spänen ostalpiner Herkunft aufgebaut wird.

---

Résumé La Zone d'Arosa, partie de la zone de suture alpine entre l'Austro-alpin et le Pennique, forme une unité hétérogène composée de roches d'origines océanique et continentale. Elle présente le caractère d'un mélange qui résulte d'un brassage sédimentaire mineur, et de déformations tectoniques, locales mais pénétratives, au cours du Crétacé et du Tertiaire ancien. Des blocs compétents de l'Austro-alpin et du Pennique qui couvrent jusqu'à 2.5 km², sont enrobés dans une matrice incompétente serpentineuse ou argilo-calcaire. A moyenne échelle, les couches disloquées se rencontrent dans les zones charriées et cisaillées, ou y sont adjacentes. La différence de compétence entre les blocs et la matrice répartit la déformation en processus cassants et ductiles. Les roches compétentes montrent des fentes d'extension et des fractures de cisaillement, alors que dans la matrice, sous l'action d'un flux ductile et d'une intensité de contrainte élevée, se développe une foliation pénétrative. La déformation fut principalement non coaxiale dans la matrice et coaxiale dans les blocs d'extension.Dans un cadre tectonique régional, nous définissons la Zone d'Arosa comme une unité tectonostratigraphique prise entre l'Austro-alpin et le Pennique. Elle constitue une zone étroite et fortement imbriquée composée aussi bien de roches ophiolitiques du Sud-Pennique et de roches sédimentaires, que de blocs et d'écaillés de l'Austro-alpin.

---

. , . - , 3 , , - . , . . , . - , - . . , - .

     

Secular variation of calcium carbonate mineralogy; an evaluation of ooid and micrite chemistries

Three ooid types are recognized from the Lower Tournaisian »Kohlenkalk« shelf facies at Velbert, Germany. Ooids from this unit have a predominantly concentric laminae fabric. Radial-concentric and small radial fibrous ooids are minor components to this oolite. The diagenetic response of Kohlenkalk ooid chemistry is significantly different from that observed in contemporaneous crinoid and brachiopod material. Fabric evidence suggests that radial-concentric and radial-fibrous ooids were probably originally aragonite/high-Mg calcite and high-Mg calcite respectively. Fabric and trace elemental chemistries of the concentric fabric ooids suggests that they were originally precipitated as aragonite and subsequently altered to low-Mg calcite.Recent papers have proposed temporal shifts in the dominant mineralogy of shallow marine non-skeletal carbonates between calcite and aragonite. Changing Phanerozoic atmospheric pCO₂ levels and oceanic Mg/Ca ratios may have been factors controlling the dominant mineralogy. The chemistries of the Kohlenkalk ooids in conjunction with other ooid and micrite data spanning the Mid-Paleozoic to Recent are evaluated in context with these temporal shifts between »calcite« and »aragonite seas«. The strontium chemistries of the ooids (¯x = 1010 ppm, range 145–3010 ppm) and micrites (¯x = 841 ppm, range 3–8800 ppm) suggests they had an aragonite precursor mineralogy. No statistical correlation was observed between ooid/micrite chemistries, their mineralogies and the proposed secular trend. Therefore, we suggest that aragonitic ooids and micrites were dominant components of shallow-marine carbonate environments throughout the Phanerozoic. The distribution and abundance of aragonitic and calcitic ooids in the geologic past was probably dependant on local hydraulic, physicochemical, and environmental conditions, areally constrained by global tectonics, eustatic, climatic and atmospheric effects, with significant diagenetic overprinting of the original geochemical and fabric information.

---

Zusammenfassung In der Kohlenkalk-Schelffazies des Untertournais bei Velbert (Bundesrepublik Deutschland) lassen sich drei Ooidtypen unterscheiden. Gemeinsam ist diesen Ooiden ein vorwiegend konzentrischer Lagenbau. Dagegen ist das Vorkommen radial-konzentrischer und radial-fibröser Ooide minimal. Die diagenetische Entwicklung der Kohlenkalkooide ist hinsichtlich ihrer chemischen Zusammensetzung deutlich von gleichalten Crinoiden- oder Brachiopodenmaterial zu unterscheiden. Strukturelle Beobachtungen lassen darauf schließen, daß radial-konzentrische und radial-fibröse Ooide ursprünglich aus Aragonit/Hoch-Mg-Calcit bzw. Hoch-Mg-Calcit bestanden. Die Zusammensetzung der Spurenelemente und die Struktur der konzentrisch aufgebauten Ooide hingegen deutet auf eine Fällung von Aragonit, der im Laufe der Diagenese zu Niedrig-Mg-Calcit umgewandelt wurde.In letzter Zeit wurde in einigen Veröffentlichungen die These vertreten, daß die Mineralogie von nicht-skelett Karbonaten zwischen Calcit und Aragonit in unbekannten Intervallen wechselt. Wechsel des atmosphärischen CO₂ Drucks und des Mg/Ca Verhältnisses in den Ozeanen während des Phanerozoikums könnten Vorgänge sein, die die vorherrschende Mineralogie dieser Karbonate beeinflussen. In dieser Arbeit wird der Chemismus der Kohlenkalkooide in Verbindung mit anderen Ooiden und Daten über Mikrite des Mittelpaläozoikums bis heute in bezug auf den Wechsel zwischen »Calcit«- und »Aragonit-Ozeanen« diskutiert. Der Strontiumgehalt der Ooide (¯x = 1010 ppm, Spannbreite: 145–3010 ppm) und der Mikrite (¯x = 841 ppm, Spannbreite: 3–8800 ppm) spricht für eine primäre Aragonitfällung. Zwischen der Ooid/Mikrit Chemie und ihrer Mineralogie gab es keine mögliche statistische Korrelation. Daraus schließen wir, daß während des ganzen Phanerozoikums aragonitische Ooide und mikrite große Bedeutung in flachmarinen Schelfregionen mit Karbonatsedimentation hatten und haben. Das Vorkommen aragonitischer und calcitischer Ooide ist wahrscheinlich an hydraulische und physiko-chemische Vorgänge gebunden, die auf globale Tektonik, eustatische-, klimatische- und atmosphärische Veränderungen zurückzuführen sind. Diese führten dazu, daß die ursprüngliche Geochemie und Struktur diagenetisch verändert wurde.

---

Résumé Parmi les facies de plate-forme du Tournaisien inférieur, dans le calcaire carbonifère de Velbert (RFA), on distingue trois types d'ooïdes: les plus abondantes présentent une structure lamellaire concentrique; d'autres, en quantité subordonnée, sont radiaires-concentriques et fibro-radiées. En réponse à leur chimisme, les ooïdes du calcaire carbonifère ont connu une évolution diagénétique nettement différente de celle des sédiments à crinoïdes et à brachiopodes de même âge. L'organisation structurale des ooides radiaires-concentriques et fibro-radiées indique que'elles étaient constituées respectivement d'aragonite + calcite magnésienne et de calcite magnésienne. Par contre, la structure et le chimisme des éléments en traces des ooïdes concentriques suggèrent qu'elles ont été d'abord précipitées en aragonite et transformées ensuite en calcite pauvre en Mg.Selon certains travaux récents, la composition minéralogique des sédiments carbonatés non organo-détritiques aurait fluctué au cours du temps entre l'aragonite et la calcite. Des factures déterminants de ce processus auraient pû être les changements, au cours du Phanérozoïque, de pCO₂ dans l'atmosphère et du rapport Mg/Ca dans les océans. Le chimisme des ooïdes du calcaire carbonifère, comparé à celui de micrites et d'autres ooïdes d'âges phanérozoïque moyen à récent est examiné en relation avec ces passages de «mers à calcite» à «mer à aragonite» au cours du temps. Le chimisme du Sr des ooïdes (x = 1010 ppm; intervalle 145–3010 ppm) et des micrites (x = 841 ppm; intervalle 3–8800 ppm) suggère une précipitation primaire d'aragonite. Il n'apparaît aucune corrélation statistique entre le chimisme des ooïdes et micrites, leur minéralogie, et les fluctuations temporelles suggérées. Pour ces raisons, nous pensons que les ooïdes et micrites aragonitiques ont été les composants dominants des milieux carbonatés peu profonds pendant tout le Phanérozoïque. L'abondance et la répartition des ooïdes aragonitiques et calcitiques dans la nature ancienne ont vraisemblablement résulté de conditions locales hydrauliques, physico-chimiques et d'environnement, déterminées par la tectonique globale, et par les changements eustatiques, climatiques ou atmosphériques, qui ont surimposé leur empreinte diagénetique aux caractères structuraux et géochimiques primaires.

---

- ( ) , . . ; - - . . , - - , . , , . , . ₂ / , . , . / ¯ 1010 m; : 145–3010 m / / ¯ - 841 ; : 3–8800 m / . / . , , . , - , , . .

     

Temperature dependence of the water-ice spectrum between 1 and 4 microns: Application to Europa,Ganymede and Saturn's rings

Reflection spectra of water ice from 1 to 4 μm are presented as a function of temperature. It is found that a feature at 6056 cm^?1 changes its intensity sufficiently that it can be used as a spectroscopic measure of the ice temperature. A temperature calibration curve of this feature down to 55 K is developed and is used to determine ice temperatures for the Galilean satellites Europa (95±10 K), Ganymede (103±10 K), and the rings of Saturn (80±5 K). The ice temperatures for the Galilean satellites are lower than their measured brightness temperatures, which can be explained by a higher albedo of the ice covered regions relative to the rest of the satellite and possibly a concentration of the ice near the polar caps.