Composition-Induced Variations in SIMS Instrumental Mass Fractionation during Boron Isotope Ratio Measurements of Silicate Glasses

An analytical artefact is reported here related to differences in instrumental mass fractionation between NIST SRM glasses and natural geological glasses during SIMS boron isotope determinations. The data presented demonstrated an average 3.4‰ difference between the NIST glasses and natural basaltic to rhyolitic glasses mainly in terms of their sputtering-induced fractionation of boron isotopes. As no matrix effect was found among basaltic to rhyolitic glasses, instrumental mass fractionation of most natural glass samples can be corrected by using appropriate glass reference materials. In order to confirm the existence of the compositionally induced variations in boron SIMS instrumental mass bias, the observed offset in SIMS instrumental mass bias has been independently reproduced in two laboratories and the phenomenon has been found to be stable over a period of more than one year. This study highlights the need for a close match between the chemical composition of the reference material and the samples being investigated.     

Late Quaternary megafloods from Glacial Lake Atna, Southcentral Alaska, U.S.A.

Geomorphic, stratigraphic, geotechnical, and biogeographic evidence indicate that failure of a Pleistocene ice dam between 15.5 and 26 ka generated a megaflood from Glacial Lake Atna down the Matanuska Valley. While it has long been recognized that Lake Atna occupied ≥ 9000 km² of south-central Alaska's Copper River Basin, little attention has focused on the lake's discharge locations and behaviors. Digital elevation model and geomorphic analyses suggest that progressive lowering of the lake level by decanting over spillways exposed during glacial retreat led to sequential discharges down the Matanuska, Susitna, Tok, and Copper river valleys. Lake Atna's size, ∼ 50 ka duration, and sequential connection to four major drainages likely made it a regionally important late Pleistocene freshwater refugium. We estimate a catastrophic Matanuska megaflood would have released 500–1400 km³ at a maximum rate of ≥ 3 × 10⁶ m³ s^{− 1}. Volumes for the other outlets ranged from 200 to 2600 km³ and estimated maximum discharges ranged from 0.8 to 11.3 × 10⁶ m³ s^{− 1}, making Lake Atna a serial generator of some of the largest known freshwater megafloods.     

Mineral dissolution in the Cape Cod aquifer, Massachusetts, USA: I . Reaction stoichiometry and impact of accessory feldspar and glauconite on strontium isotopes, solute concentrations, and REY distribution

To compare relative reaction rates of mineral dissolution in a mineralogically simple groundwater aquifer, we studied the controls on solute concentrations, Sr isotopes, and rare earth element and yttrium (REY) systematics in the Cape Cod aquifer. This aquifer comprises mostly carbonate-free Pleistocene sediments that are about 90% quartz with minor K-feldspar, plagioclase, glauconite, and Fe-oxides. Silica concentrations and pH in the groundwater increase systematically with increasing depth, while Sr isotopic ratios decrease. No clear relationship between ⁸⁷Sr/⁸⁶Sr and Sr concentration is observed. At all depths, the ⁸⁷Sr/⁸⁶Sr ratio of the groundwater is considerably lower than the Sr isotopic ratio of the bulk sediment or its K-feldspar component, but similar to that of a plagioclase-rich accessory separate obtained from the sediment. The Si-⁸⁷Sr/⁸⁶Sr-depth relationships are consistent with dissolution of accessory plagioclase. In addition, solutes such as Sr, Ca, and particularly K show concentration spikes superimposed on their respective general trends. The K-Sr-⁸⁷Sr/⁸⁶Sr systematics suggests that accessory glauconite is another major solute source to Cape Cod groundwater. Although the authigenic glauconite in the Cape Cod sediment is rich in Rb, it is low in in-grown radiogenic ⁸⁷Sr because of its young Pleistocene age. The low ⁸⁷Sr/⁸⁶Sr ratios are consistent with equilibration of glauconite with seawater. The impact of glauconite is inferred to vary due to its variable abundance in the sediments. In the Cape Cod groundwater, the variation of REY concentrations with sampling depth resembles that of K and Rb, but differs from that of Ca and Sr. Shale-normalized REY patterns are light REY depleted, show negative Ce anomalies and super-chondritic Y/Ho ratios, but no Eu anomalies. REY input from feldspar, therefore, is insignificant compared to input from a K-Rb-bearing phase, inferred to be glauconite. These results emphasize that interpretation of groundwater chemistry, even in relatively simple aquifers, may be complicated by solute contributions from “exotic” accessory minerals such as glauconite. To detect such peculiarities, groundwater studies should combine the study of elemental concentration and isotopic composition of several solutes that show different geochemical behavior.     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).     

U–Pb ages of Neoarchean granitoids from the Black Hills, South Dakota, USA: implications for crustal evolution in the Archean Wyoming province

Zircons in basement rocks from the eastern Wyoming province (Black Hills, South Dakota, USA) have been analyzed by ion microprobe (SHRIMP) in order to determine precise ages of Archean tectonomagmatic events. In the northern Black Hills (NBH) near Nemo, Phanerozoic and Proterozoic (meta)sedimentary rocks are nonconformably underlain by Archean biotite–feldspar gneiss (BFG) and Little Elk gneissic granite (LEG), both of which intrude older schists. The Archean granitoid gneisses exhibit a pervasive NW–SE-trending fabric, whereas an earlier NE–SW-trending fabric occurs sporadically only in the BFG, which is intruded by the somewhat younger LEG. Zircon crystals obtained from the LEG and BFG exhibit double terminations, oscillatory zoning, and Th/U ratios of 0.6±0.3—thereby confirming a magmatic origin for both lithologies. In situ analysis of the most U–Pb concordant domains yields equivalent ²⁰⁷Pb/²⁰⁶Pb ages (upper intercept, U–Pb concordia) of 2559±6 and 2563±6 Ma (both ±2σ) for the LEG and BFG, respectively, which constrains a late Neoarchean age for sequential pulses of magmatism in the NBH. Unzoned (in BSE) patches of 2560 Ma zircon commonly truncate coeval zonation in the same crystals with no change in Th/U ratio, suggesting that deuteric, fluid-assisted recrystallization accompanied post-magmatic cooling. A xenocrystic core of magmatic zircon observed in one LEG zircon yields a concordant age of 2894±6 Ma (±2σ). This xenocryst represents the oldest crustal material reported thus far in the Black Hills. Whether this older zircon originated as unmelted residue of 2900 Ma crust that potentially underlies the Black Hills or as detritus derived from 2900 Ma crustal sources in the Wyoming province cannot be discerned. In the southern Black Hills (SBH), the peraluminous granite at Bear Mountain (BMG) of previously unknown age intrudes biotite–plagioclase schist. Zircon crystals from the BMG are highly metamict and altered, but locally preserve small domains suitable for in situ analysis. A U–Pb concordia upper intercept age of 2596±11 Ma (±2σ) obtained for zircon confirms both the late Neoarchean magmatic age of the BMG and a minimum age for the schist it intrudes. Taken together, these data indicate that the Neoarchean basement granitoids were emplaced at 2590–2600 Ma (SBH) and 2560 Ma (NBH), most likely in response to subduction associated with plate convergence (final assembly of supercontinent Kenorland?). In contrast, thin rims present on some LEG–BFG zircons exhibit strong U–Pb discordance, high common Pb, and low Th/U ratios—suggesting growth or modification under hydrothermal conditions, as previously suggested for similar zircons from SE Wyoming. The LEG–BFG zircon rims yield a nominal upper intercept date of 1940–2180 Ma, which may represent a composite of multiple rifting events known to have affected the Nemo area between 2480 and 1960 Ma. Together, these observations confirm the existence of a Paleoproterozoic rift margin along the easternmost Wyoming craton. Moreover, the 2480–1960 Ma time frame inferred for rifting in the Black Hills (Nemo area) corresponds closely to a 2450–2100 Ma time frame previously inferred for the fragmentation of supercontinent Kenorland.     

Benthic foraminifera in sandy (siliciclastic) coastal sediments of the Arabian Gulf (Saudi Arabia): a technical report

The Uromia–Dokhtar Magmatic Arc (UDMA) is a northwest–southeast trending magmatic belt which is formed due to oblique subduction of Neotethys underneath Central Iran and dominantly comprises magmatic rocks. The Jebal-e-Barez Plutonic Complex (JBPC) is located southeast of the UDMA and composed of quartz diorite, granodiorite, granite, and alkali granite. Magmatic enclaves, ranging in composition from felsic to mafic, are abundant in the studied rocks. Based on the whole rock and mineral chemistry study, the granitoids are typically medium-high K calc-alkaline and metaluminous to peraluminous that show characteristics of I-type granitoids. The high field strength (HFS) and large ionic radius lithophile (LIL) element geochemistry suggests fractional crystallization as a major process in the evolution of the JBPC. The tectonomagmatic setting of the granitoids is compatible with the arc-related granitic suite, a pre-plate collision granitic suite, and a syncollision granitic suite. Field observations and petrographic and geochemical studies suggest that the rocks in this area are I-type granitoids and continental collision granitoids (CCG), continental arc granitoids (CAG), and island arc granitoid (IAG) subsections. The geothermobarometry based on the electron probe microanalysis of amphibole, feldspars, and biotite from selected rocks of JBPC implies that the complex formed at high-level depths (i.e., 9–12 km; upper continental crust) and at temperatures ranging from 650 to 750 °C under oxidation conditions. It seems that JBPC is located within a shear zone period, and structural setting of JBPC is extensional shear fractures which are product of transpression tectonic regime. All available data suggested that these granitoids may be derived from a magmatic arc that was formed by northeastern ward subduction of the Neotethyan oceanic crust beneath the Central Iran in Paleogene and subsequent collision between the Arabian and Iranian plates in Miocene.

     

Dissolution of olivine during natural weathering

Naturally weathered olivine occurring as phenocrysts in Hawai’ian volcanic rocks from several volcanic centers and regolith/outcrop settings, and as tectonized olivines from several metadunite bodies in the southern Appalachian Blue Ridge, are all similarly corroded by natural weathering. Conical (funnel-shaped) etch pits occur as individual pits, base-to-base pairs of cone-shaped pits, or en echelon arrays. Etch-pit shapes and orientations in the smallest etch-pit arrays visible in conventional scanning electron microscopy resemble even smaller features previously reported from transmission electron microscope investigations of olivine weathering. Etch pits occur in samples with chemical and/or mineralogical evidence of weathering, and/or are associated with, or proximal or directly connected to, fractures or exposed outcrop surface, and therefore are formed by weathering and not inherited from pre-weathering aqueous alteration (e.g., serpentinization, iddingsitization) of these parent rocks. Many etch pits are devoid of weathering products. Natural weathering of olivine is surface-reaction-limited. Similarity of corrosion forms from naturally weathered olivine from multiple igneous and metamorphic parent-rock bodies suggests that olivine weathers in the same manner regardless of its specific crystallization/recrystallization history, eruption/weathering/exposure ages of the olivine’s host rock, and the local regolith history.     

Chemistry of alkali extraction of brown coals—I. Kinetics, characterisation and implications to coalification

Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state ¹³C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.