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.     

Chemical and biological features of the saline Lake Krasnovishnevoye (Baraba,Russia) in comparison with Lake Malinovoe (Kulunda,Russia): a reconnaissance study

The Baraba and Kulunda steppes are located in southwestern Siberia in an area with an arid continental climate. This paper presents results of the first study of the hypersaline Lake Krasnovishnevoye(Baraba steppe, TDS(total dissolved solids)=297 g/L, pH 7.88). The major chemical, mineralogical and biological features of the lake were studied and compared to those of Lake Malinovoe, a typical saline neutral lake of Kulunda steppe(TDS=396 g/L, pH 7.63). The phytoplankton composition and the culturable diversity of anoxygenic phototrophic bacteria from Lake Krasnovishnevoye correspond to the ones in the Kulunda lakes. Nevertheless, the peculiarities of water composition and regime of Lake Krasnovishnevoye reduce the biodiversity to prokaryotes and unicellular algae.     

An applied model for the height of the daytime mixed layer and the entrainment zone

A model is presented for the height of the mixed layer and the depth of the entrainment zone under near-neutral and unstable atmospheric conditions. It is based on the zero-order mixed-layer height model of Batchvarova and Gryning (1991) and the parameterization of the entrainment zone depth proposed by Gryning and Batchvarova (1994). However, most zero-order slab type models of mixed-layer height may be applied. The use of the model requires only information on those meteorological parameters that are needed in operational applications of ordinary zero-order slab type models of mixed-layer height: friction velocity, kinematic heat flux near the ground and potential temperature gradient in the free atmosphere above the entrainment zone. When information is available on the horizontal divergence of the large-scale flow field, the model also takes into account the effect of subsidence, although this is usually neglected in operational models of mixed-layer height owing to lack of data. Model performance is tested using data from the CIRCE experiment.     

X-ray single-crystal and Raman study of knorringite,Mg3(Cr1.58Mg0.21Si0.21)Si3O12, synthesized at 16 GPa and 1,600 °C

The crystal structure of a knorringite-type compound, Mg₃(Cr_1.58Mg_0.21Si_0.21)Si₃O₁₂, synthesized in a multi-anvil press at P = 16 GPa and T = 1,600 °C, was refined from single-crystal X-ray diffraction data up to R = 2.36 % for 314 independent reflections. Garnet was found to be cubic and have space group Ia $\overline{3}$ d, with the unit cell parameters a = 11.5718 (1) Å, V = 1,549.54 (2) Å³. The knorringite crystal studied contains 21 mol% of majorite end-member. The structural characterization of knorringitic garnet is important because the study of its thermodynamic constants provides new constraints on thermobarometry of peridotitic garnet assemblages of the lowermost upper mantle. The Raman spectra of synthetic knorringite have been obtained for the first time.     

Satellite-based analysis of the spatial patterns of fire- and storm-related forest disturbances in the Ural region,Russia

Natural Hazards - Large-scale wildfires and windstorms are the most important disturbance agents for the Russian boreal forests. The paper presents an assessment of fire-related and wind-induced...     

Wind-driven diversion of summer river runoff preconditions the Laptev Sea coastal polynya hydrography: Evidence from summer-to-winter hydrographic records of 2007–2009

This paper examines the role of atmospheric forcing in modifying the pathways of riverine water on the Laptev Sea shelf, using summer-to-winter hydrographic surveys from 2007 to 2009. Over the two consecutive winter seasons of 2007–2008 and 2008–2009 in the area of the winter coastal polynya, our data clearly link winter surface salinity fields to the previous summer conditions, with substantially different winter salinity patterns preconditioned by summer atmospheric forcing. In the summer of 2007, dominant along-shore westerly winds in the cyclonic regime force the Lena River runoff to flow eastward. In contrast, in the summer of 2008, dominant along-shore easterly winds over the East Siberian Sea and on-shore northerly winds over the Laptev Sea in the anticyclonic regime lock the riverine water in the vicinity of the Lena Delta. Over the coastal polynya area in the southeastern Laptev Sea these patterns precondition a surface salinity difference of 8–16 psu between the winters of 2008 and 2009. Overall, this indicates a residence time of at least half a year for riverine water on the Laptev Sea shelf. Future climate change associated with an enhanced summer cyclonicity over the eastern Arctic may turn more riverine water eastward along the eastern Siberian coast, resulting in weaker vertical density stratification over the Laptev Sea shelf, with possible impact on the efficiency of vertical mixing and polynya dense water production.     

Chromium solubility in MgSiO3 ilmenite at high pressure

The crystal structure and chemical composition of crystals of (Mg_1?x Cr _x )(Si_1?x Cr _x )O₃ ilmenite (with x = 0.015, 0.023 and 0.038) synthesized in the model system Mg₃Cr₂Si₃O₁₂–Mg₄Si₄O₁₂ at 18–19 GPa and 1,600 °C have been investigated. Chromium was found as substitute for both Mg at the octahedral X site and Si at the octahedral Y site, according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a shortening of the <X–O> and a lengthening of the <Y–O> distances with respect to the values typically observed for pure MgSiO₃ ilmenite and eskolaite Cr₂O₃. Although no high Cr contents are considered in the pyrolite model, Cr-bearing ilmenite may be the host for chromium in the Earth’s transition zone. The successful synthesis of ilmenite with high Cr contents and its structural characterization are of key importance because the study of its thermodynamic constants combined with the data on phase relations in the lower-mantle systems can help in the understanding of the seismic velocity and density profiles of the transition zone and the constraining composition and mineralogy of pyrolite in this area of the Earth.     

Trace-element composition and zoning in clinopyroxene- and amphibole-group minerals: Implications for element partitioning and evolution of carbonatites

The present work is a first comprehensive study of the trace-element composition and zoning in clinopyroxene- and amphibole-group minerals from carbonatites, incorporating samples from 14 localities worldwide (Afrikanda, Aley, Alnö, Blue River, Eden Lake, Huayangchuan, Murun, Oka, Ozernaya Varaka, Ozernyi, Paint Lake, Pinghe, Prairie Lake, Turiy Mys). The new electron-microprobe data presented here significantly extend the known compositional range of clinopyroxenes and amphiboles from carbonatites. These data confirm that calcic and sodic clinopyroxenes from carbonatites are not separated by a compositional gap, instead forming an arcuate trend from nearly pure diopside through intermediate aegirine–augite compositions confined to a limited range of CaFeSi₂O₆ contents (15–45 mol%) to aegirine with < 25 mol% of CaMgSi₂O₆ and a negligible proportion of CaFeSi₂O₆. A large set of LA-ICPMS data shows that the clinopyroxenes of different composition are characterized by relatively low levels of Cr, Co and Ni (≤ 40 ppm) and manifold variations in the concentration of trivalent lithophile and some incompatible elements (1–150 ppm Sc, 26–6870 ppm V, 5–550 ppm Sr, 90–2360 ppm Zr, and nil to 150 ppm REE), recorded in some cases within a single crystal. The relative contribution of clinopyroxenes to the whole-rock Rb, Nb, Ta, Th and U budget is negligible. The major-element compositional range of amphiboles spans from alkali- and Al-poor members (tremolite) to Na–Al-rich Mg- or, less commonly, Fe-dominant members (magnesiohastingsite, hastingsite and pargasite), to calcic–sodic, sodic and potassic–sodic compositions intermediate between magnesio-ferrikatophorite, richterite, magnesioriebeckite, ferri-nyböite and (potassic-)magnesio-arfvedsonite. In comparison with the clinopyroxenes, the amphiboles contain similar levels of tetravalent high-field-strength elements (Ti, Zr and Hf) and compatible transition elements (Cr, Co and Ni), but are capable of incorporating much higher concentrations of Sc and incompatible elements (up to 500 ppm Sc, 43 ppm Rb, 1470 ppm Sr, 1230 ppm Ba, 80 ppm Pb, 1070 ppm REE, 140 ppm Y, and 180 ppm Nb). In some carbonatites, amphiboles contribute as much as 25% of the Zr + Hf, 15% of the Sr and 35% of the Rb + Ba whole-rock budget. Both clinopyroxenes and amphiboles may also host a significant share (~ 10%) of the bulk heavy-REE content. Our trace-element data show that the partitioning of REE between clinopyroxene (and, in some samples, amphibole) and the melt is clearly bimodal and requires a revision of the existing models assuming single-site REE partitioning. Clinopyroxenes and amphiboles from carbonatites exhibit a diversity of zoning patterns that cannot be explained exclusively on the basis of crystal chemistry and relative compatibility of different trace-element in these minerals. Paragenetic analysis indicates that in most cases, the observed zoning patterns develop in response to removal of selected trace elements by phases co-precipitating with clinopyroxene and amphibole (especially magnetite, fluorapatite, phlogopite and pyrochlore). With the exception of magnesiohastingsite–richterite sample from Afrikanda, the invariability of trace-element ratios in the majority of zoned clinopyroxene and amphibole crystals implies that fluids are not involved in the development of zoning in these minerals. The implications of the new trace-element data for mineral exploration targeting REE, Nb and other types of carbonatite-hosted rare-metal mineralization are discussed.     

Drinking water production from surface water sources in the tropics: Brasília DF,Brazil

Drinking water production at three waterworks was evaluated with respect to variable weather conditions in the Brasília Distrito Federal. Results of the investigation revealed that seasonal variations in rainfall play an important role in influencing the quality of the surface water sources used for drinking water production in the district. In most surface sources, particles and apparent colour are likely to originate from erosion during rain events. This represents the primary challenge facing waterworks, notably when the raw water qualities of the sources to be treated at one facility differ by one order of magnitude, as well significantly varying from one season to the next. Treatment efficiencies in terms of turbidity, apparent colour and dissolved organic carbon (DOC) removal were evaluated. Drinking water quality was found to be significantly influenced by raw water quality at all considered treatment plants. With regard to DOC removal, treatment was most efficient in waterworks which treated raw water with high percentages of biopolymers and humics. Most dissolved organics were removed by coagulation. Finally, conclusions are drawn on how to better cope with challenges facing drinking water production in a tropical climate. The first of these recommendations is the introduction of online turbidity and dissolved organic matter monitoring in order to optimise the coagulation process for the removal of these two parameters. A combination of different coagulants could also be considered for this process. Additional more sophisticated improvements to process stability, such as determination of floc characteristics, introduction of artificial neural networks or the eventual upgrade of the treatment train using membrane filtration, are also suggested.