Characterisation of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

Tobelite (NH₄) Al₂ [AlSi₃O₁₀] (OH)₂, the ammonium analogue of muscovite, and its deuterated form ND₄-tobelite (ND₄) Al₂ [AlSi₃O₁₀] (OD)₂ have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO₂-Al₂O₃ oxide mix with Al₂O₃ in excess of 5 mol% and a 25% NH₃ solution whose relative abundance was such that the amount of NH₄ ⁺ stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND₄-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K⁺ in muscovite, the NH₄ ⁺ or ND₄ ⁺ molecule occupies the interlayer site. IR absorption bands caused by NH₄ ⁺ and ND₄ ⁺ can be explained, to a very good approximation, on the basis of T_d symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal T_d symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K⁺ by NH₄ ⁺ has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND₄-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M ₁ (C2/c) and 2M ₂ (C2/c). Tobelite and ND₄-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND₄-tobelite synthesised at 200 Mpa, is 2M ₂. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH₄ ⁺ or ND₄ ⁺ compared to K⁺ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND₄-tobelite.     

IR-spektroskopische und weitere Untersuchungen an neuen Weichspüler-Wirkstoffen

IR Spectroscopy and Further Analyses of New Fabric Rinse Agents Distearyldimethylammoniumchloride (DSDMAC) that dominated the fabric softener market in Germany in the past is now substituted by three new types of ester-based agents, i.e. imidazoline ester, ester quats, and diester quats what poses new challenges to surface water analytics. The IR spectra and the chromatographic behaviour of these three agents are more or less similar to those of naturally occuring fatty esters. The paper reports about the use of IR spectroscopy, its benefit in the sense of fingerprinting principle, the identification of substances by functional groups, and the analytical tracing of transformation products. The latter relates to the formation of salts with anions that are easily detectable, the clean up, and the final spectroscopic determination. While in 1994 DSDMAC was still determinable in concentrations of 10…20 mg/kg in suspended solids from the Middle Rhine River, the concentration of the substitutes was below the detection limit of 2 mg/kg and 1…2 μg/L in 1995.     

Crystal chemistry of tremolite–tschermakite solid solutions

Tremolite–tschermakite solid solutions have been synthesized between 700 and 850 °C and 200 and 2000 MPa. The starting materials were oxide–hydroxide mixtures and an additional 0.1–1.8 molal CaBr₂ solution. The run products were characterized using SEM, HRTEM, EMP, XRD and FTIR. The synthesized Al tremolites formed needles and lath-shaped crystals of up to 300 × 20 μm. HRTEM investigations showed that the majority of the amphiboles were well ordered. The EMP analysis revealed that the Al tremolites were solid solutions in the ternary tremolite–tschermakite–cummingtonite. The highest observed Al content was close to the composition of magnesiohornblende (X_ts=0.54). Different cummingtonite concentrations (X_cum=0.00–0.18) were observed, which generally increased with Al content. Rietveld refinements of the lattice constants showed a linear decrease of the cell parameters a and b with increasing Al content, whereas c and β increased. Small deviations from the linear behaviour were caused by variable amounts of the cummingtonite component. For pure tschermakite lattice parameters of a=9.7438(11) Å, b=17.936(14) Å, c=5.2995(3) Å, β=105.68(9)° and V=891.7 ± 1.4 ų were extrapolated by least-squares regression. Using the a and β lattice parameters for tremolite, tschermakite and cummingtonite, it was possible to derive amphibole compositions using powder XRD. IR spectra of the Al tremolites showed a total of 12 individual bands. The FWHMs of all bands increased with increasing Al content. According to their FWHMs, these bands were grouped into three band systems at 3664–3676 cm^?1 (I), 3633–3664 cm^?1 (II) and 3526–3633 cm^?1 (III). Assuming ^[6]Al substitution at M2 and/or M3 and ^[4]Al at T1, three principal different configurational groups could be assigned as local environments for the proton. I: only Si⁴⁺ at T1 and one or two Al³⁺ at M2 and/or M3_far, II: one Al³⁺ at T1 and one to three Al³⁺ at M2 and/or at M3_far, III: either Al³⁺ on M3_near and/or two Al³⁺ on T1 and additional one to four Al³⁺ at M2. It is assumed that these three configurational groups correspond to the three groups of observed bands. This was quantitativly supported by Monte-Carlo simulations. A model with random distribution at M2 and M3 including Al avoidance at tetrahedral and octahedral sites yielded the best agreement with the spectroscopical results.     

Luminescence investigation of loess and tephra from Halfway House section, Central Alaska

Infrared stimulated luminescence (IRSL) properties of the Old Crow tephra and bracketing loess from the Halfway House site in Central Alaska are investigated in order to test newly developed techniques, including SAR and recently proposed fading corrections. Loess samples investigated show a standard growth of luminescence with regenerative dose while the tephra sample is less sensitive by an order of magnitude and saturates at lower dose. The growth curves obtained using multiple-aliquots regeneration (MAR) saturate at a higher value than those with the single-aliquot regeneration (SAR) protocol. Fading rate determinations for these samples are shown to be imprecise and no noticeable difference was observed between loess and tephra materials. Anomalous fading corrections using an average g value of 5% are applied to the natural test dose signal intensity using the dose rate correction (DRC) method. IRSL ages obtained for loess are in agreement with the expected age while the tephra age is lower than expected, suggesting the measured fading rate is underestimated for this material.     

Refractive index measurements of ammonia and hydrocarbon ices at 632.8 nm

Optical constants in a broad temperature and wavelength range are important input parameters in radiative transfer models used in studies of planetary atmospheres. In the laboratory, the refractive index values of ices at the HeNe laser wavelength (632.8 nm) are often used to monitor the growth rate and thickness of ice films. In this report we present laboratory measurements determining the refractive index at 632.8 nm of ammonia and hydrocarbon ices in the temperature range 80-100 K. Thin ice films are vapor-deposited on a cryogenically cooled mirror located inside a high-vacuum apparatus. The real component of the refractive index of these ice films is determined by a two-angle interferometric technique. Optical modeling calculations of the transmittance and reflectance through the thin ice films assist in the interpretation of the experimental results. We discuss our results and compare them with other measurements available in the literature. The results reported here are relevant to the spectroscopy of icy objects in the solar system; they are needed to perform laboratory characterization of ices, derive optical constants, and model spectra.     

The formation and stability of carbonic acid on outer Solar System bodies

The radiation chemistry, thermal stability, and vapor pressure of solid-phase carbonic acid (H₂CO₃) have been studied with mid-infrared spectroscopy. A new procedure for measuring this molecule’s radiation stability has been used to obtain intrinsic IR band strengths and half-lives for radiolytic destruction. We report, for the first time, measurements of carbonic acid’s vapor pressure (0.290-2.33 × 10⁻¹¹ bar for 240-255 K) and its enthalpy of sublimation (71 ± 9 kJ mol⁻¹). We also report the first observation of a chemical reaction involving solid-phase carbonic acid. Possible applications of these findings are discussed, with an emphasis on the outer Solar System icy surfaces.     

一种配合物键合异构体的制备及红外光谱测定

制备了配合物键合异构体[Co(NH3)5NO2]Cl2和[Co(NH3)5ONO]Cl2,并用红外光谱测定了它们的结构.     

Molecular Gas and Dust in the Massive Star Forming Region S 233 IR

The massive star forming region S 233 IR is observed in the molecular lines CO J = 2-1, 3-2, NH3 (1,1), (2,2) and the 870#m dust continuum. Four submillimeter continuum sources, labelled SMM 1-4, are revealed in the 870μm dust emission. The main core, SMM1, is found to be associated with a deeply embedded near infrared cluster in the northeast; while the weaker source SMM2 coincides with a more evolved cluster in the southwest. The best fit spectral energy distribution of SMM1 gives an emissivity of β = 1.6, and temperatures of 32 K and 92 K for the cold- and hot-dust components. An SMM1 core mass of 246 M⊙ and a total mass of 445 M⊙ are estimated from the 870μm dust continuum emission.SMM1 is found to have a temperature gradient decreasing from inside out, indicative of the presence of interior heating sources. The total outflow gas mass as traced by the CO J = 3-2 emission is estimated to be 35 M⊙. Low velocity outflows are also found in the NH3 (1,1) emission. The non-thermal dominant NH3 line width as well as the substantial core mass suggest that the SMM1 core is a “turbulent,massive dense core”, in the process of forming a group or a cluster of stars. The much higher star formation efficiency found in the southwest cluster supports the suggestion that this cluster is more evolved than the northeast one. Large near infrared photometric variations found in the source PCS-IR93, a previously found highly polarized nebulosity, indicate an underlying star showing the FU Orionis type of behavior.     

Simulation of Titan haze formation using a photochemical flow reactor: The optical constants of the polymer

Solar UV is the principal energy source impinging the atmosphere of Titan while the energy from the electrons in Saturn's magnetosphere is less than 0.5% of the UV light. Titan haze analogs were prepared by the photolysis of a mixture of gases that simulate the composition of its atmosphere (nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene). The real (n) and imaginary (k) parts of the complex refractive index of haze analogs formed from four different gas mixtures were calculated from the spectral properties of the solid polymer in UV-visible, near infrared and infrared wavelength spectral regions. The value of n was constant at 1.6±0.1 throughout the 0.2-2.5 μm region. The variation of k with wavelength for the values derived for Titan has a lower error than the absolute values of k so the more significant comparisons are with the slopes of the k(λ) plots in the UV-VIS region. Three of the photochemical Titan haze analogs had slopes comparable to those derived for Titan from the Voyager data (Rages and Pollack, 1980, Icarus 41, 119-130; McKay and Toon, 1992, in: Proceedings of the Symposium on Titan, in: ESA SP, Vol. 338, pp. 185-190). The slopes of the k(λ) plots for haze analogs prepared by spark discharge (Khare et al., 1984, Icarus 60, 127-137) and plasma discharge (Ramirez et al., 2002, Icarus 156, 515-529) were also comparable to Titan's. These finding show that the k(λ) plots do not differentiate between different laboratory simulations of atmospheric chemistry on Titan in the UV-VIS near IR region (0.2-2.5 microns). There is a large difference between the k(λ) in the infrared between the haze analogs prepared photochemically and analogs prepared using a plasma discharges (Khare et al., 1984, Icarus 60, 127-137; Coll et al., 1999, Planet. Space Sci. 47, 1331-1340; Khare et al., 2002, Icarus 160, 172-182). The C/N ratio in the haze analog prepared by discharges is in the 2-11 range while that of the photochemical analogs is in the 18-24 range. The use of discharges and UV light for initiating the chemistry in Titan's atmosphere is discussed.     

The galactic infrared/submillimeter dust radiation

Summary The unprecedented quality of the IRAS data prompted a series of papers reinvestigating the origin of the galactic infrared/submillimeter radiation and the nature of the heating sources of the interstellar dust. The scope of this paper is to review the main results of these new studies. Sect. 1 contains a general introduction to the subject and an overview of the earlier work. In Sect. 2 and 3, we summarize our current knowledge on dust properties and on the interstellar radiation field. Then, we present the recent interpretations of the infrared emission of our Galaxy, which are based on the IRAS data: in Sect. 4 we present the results from the galactic disk; Sect. 5 covers the question of the contribution from small dust particles, and in Sect. 6 we describe the infrared radiation from the galactic center. The nature of the heating sources and the origin of the galactic infrared radiation is then discussed in Sect. 7. Finally, Sect. 8 presents a comparison of our Galaxy with external galaxies