Urban and rural limestone weathering; the contribution of dust to black crust formation

A novel approach of studying dust, black crust and host limestones by using various techniques is presented in this paper. Samples were collected from limestone monuments located in rural, urban and industrial areas in Germany and Hungary. The paper focuses on differences in the mineralogical composition, major and trace element distribution of materials and their total polyaromatic hydrocarbons (PAH) concentration having different exposure to air pollutants. High concentration of gypsum was found in laminar and dendritic black crusts and even in the dust of both urban and rural areas, despite the low concentration of SO₂ in rural atmospheric environments. The black crusts show a typical microfabric with distinct layers of various gypsum–calcite mineral associations, silt-sized mineral fragments and black particle content. In dust, newly formed gypsum crystals were found along with mineral fragments, and siliceous and, less frequently, carbonaceous fly ash particles. High concentration of lead was found both in the samples of urban and rural areas of Germany and Hungary. Lead mostly accumulates in dust and also in the black crust. Highest lead concentrations were found not on the surface of the black crust, but close to the crust/limestone boundary according to LA-ICPMS analyses. It indicates that despite the ban of leaded petrol, lead is still present in the dust and the in the soiled zones of the built environment. Similarly to lead, no significant difference in the total PAH content of dust and crust samples were found in the two countries. Dusts are equally enriched in PAH in both countries, whereas black crusts contain fewer amounts. Most of the aqueous extracts of the samples were saturated with respect to sulphate, which also indicate the presence of gypsum, whilst in some German samples unsaturated conditions were detected. In summary, by using a combination of these analytical techniques, it was possible to distinguish rural and urban samples and to outline the role of dust in bringing pollutants to the stone surface. It is suggested that the analysed dust and stone samples indicate not only present, but also the past, pollution fluxes and as a consequence stones similar to sediments or surface waters can be used as environment indicators.     

Polarized electronic absorption spectra of colourless chalcocyanite,CuSO4, with a survey on crystal fields in Cu2+ minerals

Polarized electronic absorption spectra of colourless chalcocyanite, CuSO₄, have been measured using microscope-spectrometric techniques. The spectra are characterized by a structured and clearly polarized band system in the near-infrared spectral range with components centred at 11,720, 10,545, 9,100, and 7,320 cm^?1, which have been assigned to crystal field d–d transitions of Cu²⁺ cations in pseudo-tetragonally elongated CuO₆ polyhedra with point symmetry C _i ( \(\bar{1}\) ). The polarization behaviour is interpreted based on a D ₂(C ₂″) pseudo-symmetry. Crystal field calculations were performed for the actual triclinic point symmetry by applying the Superposition Model of crystal fields, as well as in terms of a ‘classic’ pseudo-tetragonal crystal field approach yielding the parameters Dq _(eq) = 910, Dt = 395, and Ds = 1,336 cm^?1, corresponding to a cubically averaged Dq _cub = 679 cm^?1. A comparative survey on crystal fields in Cu²⁺ minerals shows that the low overall crystal field strength in chalcocyanite, combined with a comparatively weak pseudo-tetragonal splitting of energy levels, is responsible for its unique colourless appearance among oxygen-based Cu²⁺ minerals. The weak crystal field in CuSO₄ can be related to the lower position of the SO₄ ^2? anion compared to, e.g. the H₂O molecule in the spectrochemical series of ligands.     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

Increase of the mean Sun–Earth distance caused by a secular mass accumulation

Based on many planetary observations between the years 1971 and 2003, Krasinsky and Brumberg (Celest. Mech. Dyn. Astron. 90:267–288, 2004) have estimated a rate of increase in the mean Sun-Earth distance of (15±4) m per century. Together with other anomalous observations in the solar system, this increase appears to be unexplained (Lämmerzahl et al. in Astrophys. Space Sci. Lib., vol. 349, pp. 75–101, 2008). We explain these findings by invoking a recently proposed gravitational impact model (Wilhelm et al. in Astrophys. Space Sci. 343:135–144, 2013) that implies a secular mass increase of all massive bodies. This allows us to formulate a quantitative understanding of the effect within the parameter range of the model with a mass accumulation rate of the Sun of (6.4±1.7)×10¹⁰ kg?s^?1.     

New evidence for persistent impact‐generated hydrothermal activity in the Miocene Ries impact structure,Germany

The extent of impact‐generated hydrothermal activity in the 24 km sized Ries impact structure has been controversially discussed. To date, mineralogical and isotopic investigations point to a restriction of hydrothermal activity to the impact‐melt bearing breccias, specifically the crater‐fill suevite. Here, we present new petrographic, geochemical, and isotopic data of postimpact carbonate deposits, which indicate a hydrothermal activity more extended than previously assumed. Specifically, carbonates of the Erbisberg, a spring mound located upon the inner crystalline ring of the crater, show travertine facies types not seen in any of the previously investigated sublacustrine soda lake spring mounds of the Ries basin. In particular, the streamer carbonates, which result from the encrustation of microbial filaments in subaerial spring effluents between 60 and 70 °C, are characteristic of a hydrothermal origin. While much of the primary geochemical and isotopic signatures in the mound carbonates have been obliterated by diagenesis, a postimpact calcite vein from brecciated gneiss of the subsurface crater floor revealed a flat rare earth element pattern with a clear positive Eu anomaly, indicating a hydrothermal fluid convection in the crater basement. Finally, the strontium isotope stratigraphic correlation of the travertine mound with the crater basin succession suggests a hydrothermal activity for about 250,000 yr after the impact, which would be much longer than previously assumed.     

Plagioclase‐rich chondrules in the reduced CV chondrites: Evidence for complex formation history and genetic links between calcium‐aluminum‐rich inclusions and ferromagnesian chondrules

Abstract— Plagioclase‐rich chondrules (PRCs) in the reduced CV chondrites Efremovka, Leoville, Vigarano and Grosvenor Mountains (GRO) 94329 consist of magnesian low‐Ca pyroxene, Al‐Ti‐Cr‐rich pigeonite and augite, forsterite, anorthitic plagioclase, FeNi‐metal‐sulfide nodules, and crystalline mesostasis composed of silica, anorthitic plagioclase and Al‐Ti‐Cr‐rich augite. The silica grains in the mesostases of the CV PRCs are typically replaced by hedenbergitic pyroxenes, whereas anorthitic plagioclase is replaced by feldspathoids (nepheline and minor sodalite). Some of the PRCs contain regions that are texturally and mineralogically similar to type I chondrules and consist of forsterite, low‐Ca pyroxene and abundant FeNi‐metal nodules. Several PRCs are surrounded by igneous rims or form independent compound objects. Twelve PRCs contain relic calcium‐aluminum‐rich inclusions (CAIs) composed of anorthite, spinel, high‐Ca pyroxene, ± forsterite, and ± Al‐rich low‐Ca pyroxene. Anorthite of these CAIs is generally more heavily replaced by feldspathoids than anorthitic plagioclase of the host chondrules. This suggests that either the alteration predated formation of the PRCs or that anorthite of the relic CAIs was more susceptible to the alteration than anorthitic plagioclase of the host chondrules. These observations and the presence of igneous rims around PRCs and independent compound PRCs suggest that the CV PRCs may have had a complex, multistage formation history compared to a more simple formation history of the CR PRCs. Relatively high abundances of moderately‐volatile elements such as Cr, Mn and Si in the PRCs suggests that these chondrules could not have been produced by volatilization of ferromagnesian chondrule precursors or by melting of refractory materials only. We infer instead that PRCs in carbonaceous chondrites formed by melting of the reduced chondrule precursors (magnesian olivine and pyroxene, FeNi‐metal) mixed with refractory materials (relic CAIs) composed of anorthite, spinel, high‐Ca pyroxene, and forsterite. The mineralogical, chemical and textural similarities of the PRCs in several carbonaceous chondrite groups (CV, CO, CH, CR) and common presence of relic CAIs in these chondrules suggest that PRCs may have formed in the region(s) intermediate between the regions where CAIs and ferromagnesian chondrules originated.     

Doppler Imaging of Rapidly-Rotating M Stars

With the advent of 8–12m-class telescopes and powerful new spectrographs, we can now extend the Doppler-imaging technique to the cool (and faint) end of the main sequence. At a spectral type of approximately M2, stars are thought to become fully convective and cannot possess an overshoot layer between a radiative core and a convective envelope which, as in the case of the Sun and similar stars, likely harbors the dynamo. Therefore, one could expect a fundamentally different magnetic-field topology than on the Sun and thus a qualitatively different surface temperature distribution with new, hitherto unknown, magnetic activity phenomena. Unfortunately, most single M stars do not rotate sufficiently fast for Doppler imaging and one has to “use” binaries or pre-main-sequence stars in which M stars appear spun up or, in binaries, synchronized to the orbital motion.