Infrared studies at the ice laboratory of Alcoy

At present, there are few laboratory spectra of analogs of astrophysical interest in the far-infrared range (FIR). Laboratory infrared (IR) spectra of simple ices and its mixtures obtained at low temperature and pressure are found mainly up to 25 μm, and few up to 200 μm. On the other hand, there are some spectra for carbonaceous material and silicates up to 2000 μm. Our laboratory is equipped with an IR spectrometer that integrates a Michelson interferometer with a resolution better than 0.25 cm⁻¹ and that operates under vacuum conditions of 10⁻¹ mbar. There is also a silicon bolometer, a very high-sensitivity detector in comparison with the standard deuterated triglycine sulfate (DTGS) detectors. The use of the bolometer and the possibility of working under vacuum conditions inside the optics and the sample compartment of the spectrometer allow obtaining high-sensitivity spectra free from H₂O vapor and CO₂ gas bands. Those conditions are necessary to obtain high-quality spectra in the FIR where absorption bands are much less intense than those in the mid-IR region. In our laboratory there is also a high-vacuum chamber that allows different studies on ices deposited onto a cold finger. We have already carried out experiments on the study of ice density as a function of temperature, UV irradiation of ices, temperature-programmed desorption (TPD) and UV-vis reflectance. In this work, we present the design of the experimental setup we are building to carry out different experiments simultaneously on the same ice sample, including spectra measurements in the mid-IR range (MIR) and the FIR. This design integrates jointly the IR spectrometer, the high-vacuum chamber and the silicon bolometer. Lastly, we show a spectrum we have obtained of a solid of astrophysical interest such as crystalline forsterite grains by using the polyethylene pellet technique.     

The coating hypothesis for ammonia ice particles in Jupiter: Laboratory experiments and optical modeling

We report laboratory experiments and modeling calculations investigating the effect of a hydrocarbon coating on ammonia ice spectral signatures. Observational evidence and thermochemical models indicate an abundance of ammonia ice clouds in Jupiter's atmosphere. However, spectrally identifiable ammonia ice clouds are found covering less than 1% of Jupiter's atmosphere, notably in areas of strong vertical transport, indicating a short lifetime for the signature of ammonia absorption on condensed ammonia particles [Baines, K.H., Carlson, R.W., Kamp, L.W., 2002. Icarus 159, 74-94]. Current literature has suggested coating of ammonia ice particles by a hydrocarbon haze as a possible explanation for this paradox. The work presented here supports the inference of a coating effect that can alter or suppress ammonia absorption features. In the experiments, thin films of ammonia ices are deposited in a cryogenic apparatus, coated with hydrocarbons, and characterized by reflection-absorption infrared spectroscopy. We have observed the effects on the ammonia ice absorption features near 3 and 9 μm with coverage by thin layers of hydrocarbons. Modeling calculations of these multilayer thin films assist in the interpretation of the experimental results and reveal the important role of optical interference in altering the aforementioned ammonia spectral features. Mie and T-matrix scattering calculations demonstrate analogous effects for ammonia ice particles and investigate the relative effects of ammonia ice particle size, shape, and coating layer thickness on the ice particle spectral signatures.     

Optical constants of amorphous and crystalline H2O-ice in the near infrared from 1.1 to 2.6 μm

Using new laboratory spectra, we have calculated the real and imaginary parts of the index of refraction of amorphous and crystalline H₂O-ice from 20 to 150 K in the frequency range 9000-3800 cm⁻¹ (1.1-2.6 μm) at a spectral resolution of 1 cm⁻¹. These optical constants can be used to create model spectra for comparison to spectra from Solar System objects. We also analyzed the differences between the amorphous and crystalline H₂O-ice spectra, including weakening of bands and shifting of bands to shorter wavelength in amorphous H₂O-ice spectra. We have also observed two spectrally distinct phases of amorphous H₂O-ice.     

Trapping and adsorption of CO2 in amorphous ice: A FTIR study

The interaction of carbon dioxide and amorphous water ice at 95 K is studied using transmission infrared spectroscopy. Samples are prepared in two ways: co-deposition of the gases admitted simultaneously or sequential deposition, in which amorphous water ice (ASW) is grown first and CO₂ vapor is added subsequently. In either case, a fraction of the CO₂ molecules is found to interact with water in a way that gives rise to shifts and splittings in the infrared bands with respect to those of a pure CO₂ solid. In co-deposition experiments, a larger amount of carbon dioxide is trapped within the amorphous water than in sequential deposition samples, where a substantial proportion of molecules appears to be trapped in macropores of the ASW. The specific surface area of sequential samples is evaluated and compared to previous literature results. When the sequential samples are heated to 140 K, beyond the onset temperature at which water ice undergoes a phase transition, the CO₂ molecules at the pores relocate inside the bulk in a structure similar to that found in co-deposited samples, as deduced by changes in the shape of the CO₂ infrared bands.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

Two‐dimensional speckle spectroscopy of Hα features

In May 2002, the solar chromosphere was observed with a two‐dimensional spectrometer which is mounted in the German Vacuum Tower Telescope (VTT) at the Observatorio del Teide/Tenerife. The aim of this observation was to investigate the fine structure of the solar chromosphere seen in Hα. We took narrow‐band filtergrams (Δλ ≈ 72 mÅ) by scanning through this line. Broad‐band images taken strictly simultaneously with the narrow‐band filtergrams were restored by speckle methods. The instantaneous optical transfer function from this restoration procedure was used for the reconstruction of the narrow‐band images. Some results of this high spatial resolution observation are presented below.     

E3D,the Euro3D visualization tool I: Description of the program and its capabilities

We present the first version of E3D, the Euro3D visualization tool for data from integral field spectroscopy. We describe its major characteristics, based on the proposed requirements, the current state of the project, and some planned future upgrades. We show examples of its use and capabilities. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Euro3D data format: A common FITS data format for integral field spectrographs

As integral field spectrographs have become more common around the world and in Europe in particular, the need for a common data format has been recognized. Here, we present the Euro3D format that is adapted as a post‐instrumentalsignature‐removal format for all instruments within the Euro3D network. It follows the FITS standard, and includes several extensions, all of them being binary FITS tables. This article is intended to give a comprehensive overview, but does not attempt to serve as a full definition document. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Intercalation of kaolinite with acetamide

Upon intercalation of both ordered (low defect) and disordered (high defect) kaolinites with acetamide, two types of interaction are observed. Firstly, hydrogen bonding between the NH₂ groups of the acetamide with the siloxane oxygens is formed, as evidenced by the formation of two new bands at 3400 and 3509 cm^–1. Secondly, the appearance of additional bands at ∼3600 cm^–1 in both the infrared and Raman spectra of the acetamide intercalates is attributed to a second type of hydrogen bonding by the interaction of the C=O group and the inner surface hydroxyls. Changes in the intensity of the hydroxyl deformation modes in the 895 to 940 cm^–1 region are attributed to the changes in the hydrogen bonding of the kaolinite surfaces. It is proposed that the hydrogen bonding between the adjacent kaolinite layers is replaced with hydrogen bonding between both kaolinite surfaces and the acetamide molecule. Changes in the molecular structure of acetamide are observed upon intercalation. The amide 1 band is lost and replaced with a well-defined NH₂ deformation vibration. The loss of the amide 1 band is attributed the hydrogen bond formation between the amide hydrogens and the siloxane surface. The bands of the C=O group at 1680 and 1740 cm^–1 become a single band at 1680 cm^–1. The amide 2 band remains unchanged. The lack of intensity of the 1740 cm^–1 band is attributed to the formation of hydrogen bonding between the inner surface hydroxyl groups and the carbonyl group. Received: 4 February 1998/ Revised, accepted: 30 June 1998     

Mössbauer effect study of anapaite, Ca2Fe2+(PO4)2 · 4H2O, and of its oxidation products

Mössbauer spectra (MS) of anapaite (Ca₂ Fe²⁺(PO₄)₂?·?4H₂O) and of a sample after being immersed in a 4% H₂O₂ solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420?K and 11 to 300?K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe²⁺ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370?K?±?25?K and 340?K?±?25?K, and the intrinsic isomer shifts as 1.427?±?0.005?mm/s and 1.418?±?0.005?mm/s respectively. From the external-field (60?kOe) MS recorded at 4.2 and 189?K for the non-treated sample, the principal component V _zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η?≈?0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE _Q(T), cannot be interpreted on the basis of the thermal population of the ⁵ D electronic levels resulting from the tetragonal compression of the O₆ co-ordination. The low-temperature linear behaviour of ΔE _Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2?K produces magnetic hyperfine splitting with effective hyperfine fields of ?136, ?254 and ?171?kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H₂O₂ concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe²⁺ (～6.5%) is converted into Fe³⁺.