Catalyzed Reactions on Mineral Plaster Materials Used for Indoor Air Purification

Zeolites have been used for a long time for purification and catalytical purposes. Recently, first products appeared on the market using zeolites also for improving the indoor air quality so far volatile organic compounds (VOC) are concerned. However, porous compounds like zeolites can be found also in plaster material. Therefore, it was manifest to evaluate the capability of plaster with regard to air cleaning. In this article, the contribution of plaster compounds toward adsorption and catalytical decomposition of VOCs is evaluated using α‐pinene, chlorobenzene, 2‐ethoxyethylacetate, and pentanal as target substances under standard conditions (23°C, 50% r.H.). These compounds were chosen because of their VOC typical physicochemical properties like molecular dimensions, density, boiling point, vapor pressure, and octanol–water distribution coefficient (logk_ow). Hydrated lime and metakaolin were found out to have good adsorption properties under these circumstances. Also natural zeolites showed good results especially on pentanal. By investigations in environmental chambers the reduction potential of test plasters on chlorobenzene and 2‐ethoxyethylacetate concentrations could be shown. Application of coatings had no or only temporary influence on the performance of the plaster. Additional tests in small chambers demonstrated the possibility to improve the properties of plasters with help of FAU‐ or MFI‐type zeolites but the experiments also showed that α‐pinene and pentanal undergo chemical reactions. Further effort should be made on investigations also toward other compounds, especially more volatile ones like formaldehyde. Also additional building materials like insulation material or boards should be taken into account.     

Shear velocity estimates in rough‐bed open‐channel flow

Shear velocity u_* is an important parameter in geophysical flows, in particular with respect to sediment transport dynamics. In this study, we investigate the feasibility of applying five standard methods [the logarithmic mean velocity profile, the Reynolds stress profile, the turbulent kinetic energy (TKE) profile, the wall similarity and spectral methods] that were initially developed to estimate shear velocity in smooth bed flow to turbulent flow over a loose bed of coarse gravel (D₅₀ = 1·5 cm) under sub‐threshold conditions. The analysis is based on quasi‐instantaneous three‐dimensional (3D) full depth velocity profiles with high spatial and temporal resolution that were measured with an Acoustic Doppler Velocity Profiler (ADVP) in an open channel. The results of the analysis confirm the importance of detailed velocity profile measurements for the determination of shear velocity in rough‐bed flows. Results from all methods fall into a range of ± 20% variability and no systematic trend between methods was observed. Local and temporal variation in the loose bed roughness may contribute to the variability of the logarithmic profile method results. Estimates obtained from the TKE and Reynolds stress methods reasonably agree. Most results from the wall similarity method are within 10% of those obtained by the TKE and Reynolds stress methods. The spectral method was difficult to use since the spectral energy of the vertical velocity component strongly increased with distance from the bed in the inner layer. This made the choice of the reference level problematic. Mean shear stress for all experiments follows a quadratic relationship with the mean velocity in the flow. The wall similarity method appears to be a promising tool for estimating shear velocity under rough‐bed flow conditions and in field studies where other methods may be difficult to apply. This method allows for the determination of u_* from a single point measurement at one level in the intermediate range (0·3 < h < 0·6). Copyright © 2013 John Wiley & Sons, Ltd.     

Metallogenic provinces in South America

This paper discusses the broadscale distribution of some ore deposit types in South America, trying to discern possible relations with major geotectonic features. It does not cover all ore deposits but rather a selection based on available information, genetic types, geographic distribution, and a representation of deposit types which are either abundant or very rare in South America. Included are porphyry copper, zoned copper-zinc-lead-silver, contact-metasomatic, red-bed copper-uranium-vanadium, lead-zinc (including Mississippi Valley type), mercury, tin, pegmatite, carbonatite and alkalic complex, diamond, nickelcobalt-chromite-asbestos-talc, iron, bauxite, tungsten, titanium, uranium, gold, potash and phosphate deposits. Comparisons are made with the distribution of these deposit types in other continents, especially in North America and Africa. This leads to some speculations bearing on theories of ore genesis. The evidence suggests that upper crustal processes predominate in the formation of the majority of ore deposits considered (excepting carbonatites, alkalic complexes and diamond pipes). Also, the relative level of an orogenic belt exposed by erosion seems to be an important factor bearing on the presently known distribution of many ore deposit types. Furthermore, the fact that ore deposits of given types tend to be aligned along the Cordillera in more or less defined belts with changing chemical composition accross the Andes, which partake in all its inflections, and in patterns which are similar in North and South America, indicates that they are either dependent on the distribution of eugeosynclinal vs miogeosynclinal sediments in the original geosynclinal prism, or that their character is related to distance from the major batholitic masses or to shallow stocks and volcanic activity. The indicated correlation with sediment character and evaporites speaks in favor of modem concepts viewing hydrothermal fluids as mainly meteoric but heated and circulated largely by igneous activity. This study raises more questions than it can answer and calls attention to a number of problems requiring further research. From a practical point of view, this investigation reveals several possibilities for future exploration, as well as opportunities for further development of mineral resources in South America. Several countries could probably improve or diversify their mineral production significantly, thus raising the standard of living of their increasing population. Whereas in North America both Canada and the U.S.A. span from east to west the whole range of geological environments, from cratonic to geosynclinal and orogenic, in South America the distribución of countries is essentially either along the Cordillera or over shield areas, a fact of obvious geopolitical implications with regard to mineral resources.     

Modelling of the vertical fluxes of nitric acid,ammonia, and ammonium nitrate

Results from numerical investigations regarding the exchange of HNO₃, NH₃, and NH₄NO₃ between the atmosphere and the biosphere are presented. The investigations were performed with a modified inferential method which is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these nitrogen compounds. This modified inferential method calculates the micrometeorological quantities (such as the friction velocity and the fluxes of sensible and latent heat), the height-invariant fluxes of the composed chemically conservative trace species with group concentrationsc ₁=[HNO₃]+[NH₄NO₃] (total nitrate),c ₂=[NH₃]+[NH₄NO₃] (total ammonia), andc ₃=[HNO₃]-[NH₃] as well as the fluxes of the individual nitrogen compounds. The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The modified inferential method requires only the data of wind velocity, temperature, humidity and concentrations (HNO₃, NH₃, and NH₄NO₃) measured at a reference height by stations of a monitoring network.     

Chloritoid stability in manganese rich low-grade metamorphic rocks,Venn-Stavelot Massif,Ardennes

The Southern Venn-Stavelot Massif is characterized by Ordovician and Devonian rocks very rich in manganese and aluminum, which are attacked by a low grade regional metamorphism. The assemblages 1 (phengite, paragonite, chlorite, chloritoid, garnet, quartz, hematite, rutile) and 2 (phengite, paragonite, chlorite, kaolinite (andalusite, pyrophyllite), garnet, quartz, hematite, rutile) are of basic interest for the formation of chloritoid. As the two rock types are isofaciell and quasi-identical in chemistry except for the iron oxides, there is clear evidence for the influence of on the chloritoid formation at its lower p-T stability limit. This can be shown by a discussion of the phase relations of chloritoid, garnet, kaolinite, chlorite and phengite in respect to the oxidation ratio mol 2 Fe₂O₃x 100/2 Fe₂O₃+ FeO of the host rocks. Especially chloritoid and chlorite change their chemistry in a characteristic way with rising oxidation ratio in getting richer and richer in manganese and magnesium (chloritoid) and magnesium (chlorite). A simultaneous increase in trivalent iron in these phases is supposed. At an oxidation ratio of 85–90 the stability limit of chloritoid is reached. The increasing substitution of manganese and magnesium up to this limit should have a stabilizing effect. In a rough estimate the oxygen partial pressure is supposed to be in the order of 10⁻¹⁰ atm at the stability limit of chloritoid assuming a temperature of metamorphism between 360–400° C. Rocks with oxidation ratios between 90 and 100 are characterized by the presence of kaolinite. If the oxidation ratio is still higher (all iron as Fe³⁺, parts of the manganese in the trivalent state), the rocks belong to assemblage 3 (phengite, paragonite, chlorite, viridine, (kaolinite), (garnet), quartz, hematite, braunite, rutile). Dedicated to Prof. Dr. K. Jasmund at his 60. birthday.     

Stabilization of extracellular polymeric substances (Bacillus subtilis) by adsorption to and coprecipitation with Al forms

Extracellular polymeric substances (EPS) are continuously produced by bacteria during their growth and metabolism. In soils, EPS are bound to cell surfaces, associated with biofilms, or released into solution where they can react with other solutes and soil particle surfaces. If such reaction results in a decrease in EPS bioaccessibility, it may contribute to stabilization of microbial-derived organic carbon (OC) in soil. Here we examined: (i) the chemical fractionation of EPS produced by a common Gram positive soil bacterial strain (Bacillus subtilis) during reaction with dissolved and colloidal Al species and (ii) the resulting stabilization against desorption and microbial decay by the respective coprecipitation (with dissolved Al) and adsorption (with Al(OH)_3(am)) processes. Coprecipitates and adsorption complexes obtained following EPS-Al reaction as a function of pH and ionic strength were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The stability of adsorbed and coprecipitated EPS against biodegradation was assessed by mineralization experiments for 1100 h. Up to 60% of the initial 100 mg/L EPS-C was adsorbed at the highest initial molar Al:C ratio (1.86), but this still resulted only in a moderate OC mass fraction in the solid phase (17 mg/g Al(OH)_3(am)). In contrast, while coprecipitation by Al was less efficient in removing EPS from solution (maximum values of 33% at molar Al:C ratios of 0.1-0.2), the OC mass fraction in the solid product was substantially larger than that in adsorption complexes. Organic P compounds were preferentially bound during both adsorption and coprecipitation. Data are consistent with strong ligand exchange of EPS phosphoryl groups during adsorption to Al(OH)_3(am), whereas for coprecipitation weaker sorption mechanisms are also involved. X-ray photoelectron analyses indicate an intimate mixing of EPS with Al in the coprecipitates, which is not observed in the case of EPS adsorption complexes. The incubation experiments showed that both processes result in overall stabilization of EPS against microbial decay. Stabilization of adsorbed or coprecipitated EPS increased with increasing molar Al:C ratio and biodegradation was correlated with EPS desorption, implying that detachment of EPS from surface sites is a prerequisite for microbial utilization. Results indicate that the mechanisms transferring EPS into Al-organic associations may significantly affect the composition and stability of biomolecular C, N and P in soils. The observed efficient stabilization of EPS might explain the strong microbial character of organic matter in subsoils.     

Episodic Cenozoic volcanism and tectonism in the Andes of Peru

Radiometric and geologic information indicate a complex history of Cenozoic volcanism and tectonism in the central Andes. K-Ar ages on silicic pyroclastic rocks demonstrate major volcanic activity in central and southern Peru, northern Chile, and adjacent areas during the Early and Middle Miocene, and provide additional evidence for volcanism during the Late Eocene. A provisional outline of tectonic and volcanic events in the Peruvian Andes during the Cenozoic includes: one or more pulses of igneous activity and intense deformation during the Paleocene and Eocene; a period of quiescence, lasting most of Oligocene time; reinception of tectonism and volcanism at the beginning of the Miocene; and a major pulse of deformation in the Middle Miocene accompanied and followed through the Pliocene by intense volcanism and plutonism. Reinception of igneous activity and tectonism at about the Oligocene-Miocene boundary, a feature recognized in other circum-Pacific regions, may reflect an increase in the rate of rotation of the Pacific plate relative to fixed or quasifixed mantle coordinates. Middle Miocene tectonism and latest Tertiary volcanism correlates with and probably is genetically related to the beginning of very rapid spreading at the East Pacific Rise.     

Boron abundances and isotopic ratios of olivine grains on Itokawa returned by the Hayabusa spacecraft

We report the B abundances and isotopic ratios of two olivine grains from the S‐type asteroid Itokawa sampled by the Hayabusa spacecraft. Olivine grains from the Dar al Gani (DaG) 989 LL6 chondrite were used as a reference. Since we analyzed polished thin sections in both cases, we expect the contribution from the solar wind B (rich in ¹⁰B) to be minimal because the solar wind was implanted only within very thin layers of the grain surface. The Itokawa and DaG 989 olivine grains have homogeneous B abundances (~400 ppb) and ¹¹B/¹⁰B ratios compatible with the terrestrial standard and bulk chondrites. The observed homogeneous B abundances and isotopic ratios of the Itokawa olivine grains are likely the result of thermal metamorphism which occurred in the parent asteroid of Itokawa, which had a similar composition as LL chondrites. The chondritic B isotopic ratios of the Itokawa samples suggest that they contain little cosmogenic B (from cosmic‐ray spallation reactions) rich in ¹⁰B. This observation is consistent with the short cosmic‐ray exposure ages of Itokawa samples inferred from the small concentrations of cosmogenic ²¹Ne. If other Itokawa samples have little cosmogenic B as well, the enrichment in ¹⁰B found previously on the surface of another Itokawa particle (as opposed to the bulk grain study here) may be attributed to implanted solar wind B.     

Tying platform drowning to perturbations of the global carbon cycle with a δ13COrg-curve from the Valanginian of DSDP Site 416

The carbonate carbon isotope record of the Phanerozoic is marked by repeated high-amplitude excursions towards more positive values. Although the interpretation of C-isotope events remains controversial, they are regarded as a proxy of the global C-cycle. Using δ¹³C_Org-measurements of samples from DSDP Site 416, it is shown that a classic example of platform drowning coincided with the onset of the mid-Valanginian carbon-cycle excursion. Widespread carbonate platform drowning would have contributed to the observed positive shift in the C-isotope record. As choking of carbonate production was compensated by increased organic production, both processes favoured a shift in marine carbon partitioning from the oxidized to the reduced carbon reservoir. This would have resulted in an increased flux of CO₂ from the atmosphere into the marine and sedimentary carbon reservoir.