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.     

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.     

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.     

Energy Balance Of A Sparse Coniferous High-Latitude Forest Under Winter Conditions

Measurements carried out in Northern Finland on radiation and turbulent fluxes over a sparse, sub-arctic boreal forest with snow covered ground were analysed. The measurements represent late winter conditions characterised by low solar elevation angles. During the experiment (12–24 March 1997) day and night were about equally long. At low solar elevation angles the forest shades most of the snow surface. Therefore an important part of the radiation never reaches the snow surface but is absorbed by the forest. The sensible heat flux above the forest was fairly large, reaching more than 100 W m^-2. The measurements of sensible heat flux within and above the forest revealed that the sensible heat flux from the snow surface is negligible and the sensible heat flux above the forest stems from warming of the trees. A simple model for the surface energy balance of a sparse forest is presented. The model treats the diffuse and direct shortwave (solar) radiation separately. It introduces a factor that accounts for the shading of the ground at low solar elevation angles, and a parameter that deals with the partial transparency of the forest.Input to the model are the direct and diffuse incoming shortwave radiation.Measurements of the global radiation (direct plus diffuse incoming shortwaveradiation) above the forest revealed a considerable attenuation of the globalradiation at low solar elevation. A relation for the atmospheric turbidity asfunction of the solar elevation angle is suggested. The global radiation wassimulated for a three month period. For conditions with a cloud cover of lessthan 7 oktas good agreement between model predictions and measurementswere found. For cloud cover 7 and 8 oktas a considerable spread can beobserved. To apply the proposed energy balance model, the global radiationmust be separated into its diffuse and direct components. We propose a simpleempirical relationship between diffuse shortwave and global radiation asfunction of cloud cover.     

Campanian Climatic Change: Isotopic Evidence from Far East, North America, North Atlantic and Western Europe

Paleoclimatic settings have been reconstructed for the Campanian using original oxygen-isotopic analyses of well-preserved molluskan and foraminifera shells from Russian Far East, Hokkaido, USA, Belgium and some DSDP holes (95, 98, 102, 390A, and 392A) in North Atlantic. Early Early Campanian climatic optimum has been recognized from data on high bottom shelf water paleotemperatures in middle latitudes of both the western circum-Pacific (to 24.2°C) and the eastern circum-Pacific (to 26.4°C) areas and high bottom shallow water paleotemperatures in high latitudes of the Koryak Upland (22.4–25.5°C), which agrees with the data on the Campanian Barykovskaya flora in high latitudes (Golovneva and Herman, 1998) and Jonker flora and its equivalents in middle latitudes. Judging from the data on comparatively high bottom shallow water paleotemperature values in high latitudes, South Alaska (19.4°C) and the Koryak Upland (22.4–25.5°C), we also expect Latest Campanian temperature maximum, which has not been confirmed, however, for low and middle latitudes by neither of isotopic nor paleobotanic data now. Main climatic tendency during the Campanian (with the exception of Latest Campanian) has been learned from isotopic composition of Campanian aragonitic ammonoid shells from the Hokkaido-South Sakhalin (Krilyon) marine basin. In contrary to Huber’s et al. (2002) assumption, we expect warm greenhouse conditions during the most part of the Campanian.     

Galactic Cosmic Ray Intensity in the Upcoming Minimum of the Solar Activity Cycle

During the prolonged and deep minimum of solar activity between cycles 23 and 24, an unusual behavior of the heliospheric characteristics and increased intensity of galactic cosmic rays (GCRs) near the Earth’s orbit were observed. The maximum of the current solar cycle 24 is lower than the previous one, and the decline in solar and, therefore, heliospheric activity is expected to continue in the next cycle. In these conditions, it is important for an understanding of the process of GCR modulation in the heliosphere, as well as for applied purposes (evaluation of the radiation safety of planned space flights, etc.), to estimate quantitatively the possible GCR characteristics near the Earth in the upcoming solar minimum (~2019–2020). Our estimation is based on the prediction of the heliospheric characteristics that are important for cosmic ray modulation, as well as on numeric calculations of GCR intensity. Additionally, we consider the distribution of the intensity and other GCR characteristics in the heliosphere and discuss the intercycle variations in the GCR characteristics that are integral for the whole heliosphere (total energy, mean energy, and charge).     

Characteristic Features of Solar Cosmic Rays in the 21st–24th Solar-Activity Cycles According to Data from Catalogs of Solar Proton Events

Geomagnetism and Aeronomy - Homogeneous series of solar cosmic-ray events for four solar-activity cycles against the background of decreased activity in cycles 23 and 24 are considered. The number...     

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...     

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.