Argon isotope fractionation induced by stepwise heating

Noble gas isotopes are widely used to elucidate the history of the rocks in which they have been trapped, either from distinct reservoirs or by accumulation following radioactive decay. To extract noble gases from their host rocks, stepwise heating is the most commonly used technique to deconvolve isotopically different components, e.g., atmospheric, in situ radiogenic, or excess radiogenic from mantle or crustal reservoirs. The accurate determination of the isotopic composition of these different components is of crucial importance, e.g., for ages obtained by ⁴⁰Ar-³⁹Ar stepheating plateaus. However, diffusion theory-based model calculations predict that the stepwise thermal extraction process from mineral phases induces isotope fractionation and, hence, adulterates the original composition. Such effects are largely unconsidered, as they are small and a compelling experimental observation is lacking. We report the first unequivocal evidence for significant mass fractionation of argon isotopes during thermal extraction, observed on shungite, a carbon-rich Precambrian sedimentary rock. The degree of fractionation, as monitored by ³⁸Ar/³⁶Ar and ⁴⁰Ar/³⁶Ar ratios, very well agrees with theoretical predictions assuming an inverse square root dependence of diffusion coefficient and atomic mass, resulting in easier extraction of lighter isotopes. Hence, subatmospheric ⁴⁰Ar/³⁶Ar ratios obtained for argon extracted at low temperatures may not represent paleoatmospheric argon. Shungite argon resembles modern atmospheric composition, but constraints on the timing of trapping appear difficult to obtain, as shungites are multicomponent systems.In ⁴⁰Ar-³⁹Ar stepwise heating, the isotope fractionation effect could cause systematic underestimations of plateau ages, between 0.15 and 0.4% depending on age, or considerably higher if samples contain appreciable atmospheric Ar. The magnitude of this effect is similar to the presently achieved uncertainties of this increasingly precise dating technique. Our results also indicate the importance of thermally activated diffusion as a possible fractionation mechanism, e.g., for hydrothermal gas exhalations, or for carbonaceous carrier phases such as “Q” in meteorites that have been suggested as carriers of highly fractionated noble gas residues from the early solar nebula.     

The Late Precambrian Timna igneous complex, Southern Israel: Evidence for comagmatic-type sanukitoid monzodiorite and alkali granite magma

New data from a geochemical, geochronological and isotopic study of the Late Precambrian Timna igneous complex suggest the formation of alkali granites from a LIL-enriched, mantle derived, sanukitoid-type monzodiorite (a silica oversaturated rock with Mg# >60). These data also provide new insights into the petrology, timing and regional tectonic control of the transition from the calc-alkaline to the alkaline magmatic activity in the northern Arabian-Nubian Shield (ANS) during the Late Precambrian.

The Timna alkali granite was formed by fractional crystallization from the monzodioritic magma in a quasi-stratified magmatic cell which formed 610 Ma ago in the 625 Ma old calc-alkaline, porphyritic granite crust. These monzodiorites are mantle-derived, as demonstrated by their high Mg# (63), Cr (230 ppm), and Ni (120 ppm). They are characterized by initial ⁸⁷Sr/⁸⁶Sr of 0.7034, ε-Nd (610 Ma) = +3.4, and are enriched in K₂O (2.9%), Sr (840 ppm), Ba (1290 ppm) and LREE [(La/Lu)_n= 10–25]. The chemical characteristics and REE patterns of the monzodiorites and andesitic dykes of Timna are very similar to Dokhan andesites from northeastern Egypt and the Archean sanukitoids from Canada. The isotopic, geochemical and geochronologic data all indicate that Timna monzodiorites are comagmatic with the alkali granite. The alkali granite is a typical post-orogenic, borderline A-type granite. It is enriched in potassium (K₂O=4.68–6.64%), has a negative europium anomaly (Eu/Eu^*=0.058–0.38) and ε-Nd (610 Ma) of +3.9. The calc-alkaline granite is a typical I-type granite with a small positive europium anomaly (Eu/Eu^*=1.02–1.16). Its age and the Sr, Nd and Pb isotopic characteristics with ε-Nd (625 Ma) of +5.6 to +5.9 are significantly different from these of the alkali granite and monzodiorites, and indicate little interaction with the monzodiorite during the formation of the alkali granite.

The alkali granites are correlative with the post-collisional extensional granites in Jordan and Egypt while the porphyritic granites can be correlated with the late orogenic types. Crustal thickening associated with orogenic compression resulted in crustal anatexis to form the I-type granitic rocks, whereas crustal thinning associated with extension allowed LIL-enriched mantle melts to rise very near to the surface, where space was available for these to pond and fractionate to alkali granite.     

Noble gas composition of the solar wind as collected by the Genesis mission

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^84,86Kr and ^129,132Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ³He/⁴He: (4.64 ± 0.09) × 10⁻⁴, ²⁰Ne/²²Ne: 13.78 ± 0.03, ²¹Ne/²²Ne: 0.0329 ± 0.0001, ³⁶Ar/³⁸Ar 5.47 ± 0.01. The elemental composition is: ⁴He/²⁰Ne: 656 ± 5, and ²⁰Ne/³⁶Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ⁸⁶Kr/⁸⁴Kr: 0.302 ± 0.003, ¹²⁹Xe/¹³²Xe: 1.05 ± 0.02, ³⁶Ar/⁸⁴Kr 2390 ± 150, and ⁸⁴Kr/¹³²Xe 9.5 ± 1.0. The ³He/⁴He and the ⁴He/²⁰Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (∼100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.     

Ionic conductivity in gem-quality single-crystal alkali feldspar from the Eifel: temperature,orientation and composition dependence

We measured the ion conductivity of single-crystal alkali feldspar originating from two different locations in the Eifel/Germany, named Volkesfeld and Rockeskyller sanidine and having potassium site fractions \(C_\mathrm{K}\) of 0.83 and 0.71, respectively. The dc conductivities resulting from electrochemical impedance spectroscopy over the temperature range of 300–900 \(^{\circ }\hbox {C}\) show a weak composition dependence but pronounced differences between the b-direction [\(\perp (010)\)] and \(c^{*}\)-direction [\(\perp (001)\)] of the monoclinic feldspar structure. Conductivity activation energies obtained from the observed linear Arrhenius plots are close to 1.2 eV in all cases, which is closely similar to the activation energies of the \(^{22}\mathrm{Na}\) tracer diffusivity in the same crystals. Taking into account literature data on K tracer diffusion and diffusion correlation effects, the present results point to a predominance of the interstitialcy mechanism over the vacancy mechanism in mass and charge transport on the alkali sublattice in potassium-rich alkali feldspar.     

Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

Climatology of Ozone, PAN, CO, and NMHC in the Free Troposphere Over the Southern North Atlantic

Free tropospheric measurements of ozone, peroxyacetylnitrate andprecursors (CO, NMHC) that were made within the framework of the EUROTRACsub-project TOR (Tropospheric Ozone Research) between 1990 and 1995 at theGAW station Izana, Tenerife (28°18N, 16°30W) arediscussed. The average annual cycles reveal the importance of transport fromnorthern mid-latitudes and the role of photo-chemistry. According toair-mass trajectories, which were supplied to us from AEROCE(Atmosphere/Ocean Chemistry Experiment), transport from northernmid-latitudes is associated with high precursor concentrations in winter,whereas ozone concentrations in winter are not much influenced by transportpatterns, suggesting a rather uniform distribution over the northern part ofthe Northern Hemisphere around mean value of 43 ± 5 ppb. In summer,high ozone concentrations of up to 90 ppb are often encountered duringtransport from north, while the levels of precursors are much lower than inwinter, because of photochemical destruction. Trajectories from southerlylatitudes and the Sahara usually have the lowest ozone concentrationsassociated with them.     

Enhanced red fluorescence emission in the oxygen minimum zone of the Arabian Sea

 Depth profiles of fluorescence at several excitation and emission wavelengths were measured along with CTD data during the cruise So119 of RV Sonne in the Arabian Sea from 12 May to 10 June 1997. In addition to chlorophyll fluorescence from phytoplankton in the near-surface layer, the profiles in the oxygen minimum region well below the euphotic zone show enhanced red fluorescence. Red fluorescence intensity is inversely related to the oxygen concentration in intermediate and deep waters. A relationship to characteristic water masses of the region cannot be found in the data, and this holds also with chemical data such as DOC. Absorbance spectra of water samples taken in the oxygen minimum zone show an absorption band at 420 nm wavelength with about 50 nm bandwidth, much weaker than gelbstoff absorbance in the same wavelength range. The absorption band remains stable after sample filtration with 0.45 μm glass fibre filters. Hence, the size of the absorbing matter is in the range of dissolved molecules or particles much smaller than 1 μm. Fluorescence spectra of unfiltered samples with 420 nm excitation show a weak emission band at 600 nm and a more pronounced one at 660 nm wavelength. The trailing edge of the 660 nm band falls into the range of chlorophyll emission, thus giving rise to the observed depth profiles of red fluorescence in the oxygen minimum zone. Red fluorescence measured on samples remain stable during a few hours after sampling even in the presence of oxygen. It is not detectable after several weeks of sample storage in the dark and cannot be reproduced even after depletion of dissolved oxygen. Received: 22 May 2002 / Accepted: 18 February 2003 Responsible Editor: Andreas Oschlies Acknowledgements. This work was supported by a grant from the Federal Minister of Education and Technology, Bonn, within the frame work of the JGOFS Arabian Sea program. We are grateful to the captain and the crew of RV Sonne for their support. We are indebted to Mrs. Kirsten Neumann from the Institute of Marine Chemistry and Biogeochemistry of the University of Hamburg for providing the oxygen data, and to Mr. Nikolai Delling from the same institute for making the DOC and chlorophyll data available to us.     

Modern modes of provenance and dispersal of terrigenous sediments in the North Pacific and Bering Sea: implications and perspectives for palaeoenvironmental reconstructions

During expedition 202 aboard the RV Sonne in 2009, 39 seafloor surface sediment sites were sampled over a wide sector of the North Pacific and adjoining Bering Sea. The data served to infer land–ocean linkages of terrigenous sediment supply in terms of major sources and modes of sediment transport within an over-regional context. This is based on an integrated approach dealing with grain-size analysis, bulk mineralogy and clay mineralogy in combination with statistical data evaluation (end-member modelling of grain-size data, fuzzy cluster analysis of mineralogical data). The findings on clay mineralogy served to update those of earlier work extracted from the literature. Today, two processes of terrigenous sediment supply prevail in the study area: far-distance aeolian sediment supply to the pelagic North Pacific, and hemipelagic sediment dispersal from nearby land sources via ocean currents along the continental margins and island arcs. Aeolian particles show the finest grain sizes (clay and fine silt), whereas hemipelagic sediments have high abundances of coarse silt. Exposed sites on seamounts and the continental slope are partly swept by strong currents, leading to residual enrichment of fine sand. Four sediment sources can be distinguished on the basis of distinct index minerals revealed by statistical data analysis: dust plumes from central Asia (quartz, illite), altered materials from the volcanic regions of Kamchatka and the Aleutian Arc (smectite), detritus from the Alaskan Cordillera (chlorite, hornblende), and fluvial detritus from far-eastern Siberia and the Alaska mainland (quartz, feldspar, illite). These findings confirm those of former studies but considerably expand the geographic range of this suite of proxies as far south as 39°N in the open North Pacific. The present integrated methodological approach proved useful in identifying the major modern processes of terrigenous sediment supply to the study region. This aspect deserves attention in the selection of sediment core sites for future palaeoenvironmental reconstructions related to aeolian and glacial dynamics, as well as the recognition of palaeo-ocean circulation patterns in general.