Laser induced breakdown spectroscopy of soils, rocks and ice at subzero temperatures in simulated martian conditions

We applied Laser Induced Breakdown Spectroscopy (LIBS) on moist soil/rock samples in simulated Martian conditions. The signal behavior as a function of the surface temperature in the range from + 25 °C to − 60 °C was studied at pressure of 7 mbar. We observed the strong signal oscillations below 0 °C with different negative peaks, whose position, width and magnitude depend on the surface roughness. In some cases, the signal was reduced for one order of magnitude with consequences for the LIBS analytical capability. We attribute such a signal behavior to the presence of supercooled water inside the surface pores, which freezing point depends on the pore size. On a same rock samples with different grades of the surface polishing, the signal has different temperature dependence. Its decrease was always registered close to 0 °C, corresponding to the freezing/melting of normal disordered ice, which can be present inside larger pores and scratching. An amount of the signal reduction at the phase transition temperatures does not seem to change with the laser energy density in the examined range. Comparative measurements were performed on a frozen water solution. A large depression, for two orders of magnitude, of the LIBS intensity was observed close to − 50 °C. The same negative peak, but with a smaller magnitude, was also registered on some rock/soil samples. Ablation rates and plasma parameters as a function of the sample temperature are also discussed, and their consequences for in-situ analyses.     

Thermodynamics of solute transfer between chloroform and water

The apparent enthalpies, free energies and entropies of transfer from water saturated chloroform to chloroform saturated aqueous buffer (pH 7) were determined for five primary alcohols and six other organic nonelectrolytes using an isoperibol flow microcalorimeter. A linear relationship between the enthalpies and free energies of transfer is found for the homologous series of alcohols indicating that the occurrence of enthalpy-entropy compensation in solute transfer is not restricted to solvent systems of low mutual solubility. The apparent thermodynamics of transfer from chloroform to aqueous buffer were compared with those from 2,2,4-trimethylpentane to aqueous buffer and were rationalized in terms of solvation interactions.     

Thermodynamics of non-electrolyte transfer between octanol and water

The apparent enthalpy, free energy and entropy of transfer from aqueous buffer (pH 7) to water-saturated octanol were determined for the aliphatic alcohols methanol to octanol using an isoperibol flow-calorimeter. For the higher homologues, a linear relationship between enthalpy and free energy change is found indicating an enthalpy-entropy compensation effect. The thermodynamics of transfer were rationalized in terms of the thermodynamics of solvation in the separate phases, including water itself as a solute. The role of water as a cosolvent in the octanol phase is discussed.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.     

Thermodynamics and digital simulation of intercalation processes

The insertion of guest particles into insertion and intercalation compounds is reconsidered from the viewpoint of reversible thermodynamics. A correlation between enthalpy of formation and volume changes is described, the latter being accessible from X-ray data. The phase changes caused by guest insertion are emphasized. Tungsten bronzes are used as model data. Electronic Publication     

Inorganic adsorbent containing polymeric membrane reservoir for the recovery of lithium from seawater

Polymeric membrane reservoir system which contains inorganic ion-exchange adsorbent inside is suggested for the recovery of lithium from natural seawater. Manganese oxide particles having high selectivity toward lithium adsorption was used as inorganic ion-exchange adsorbent. Polymeric membrane reservoir was prepared from non-woven fabric, polysulfone (PSf) membrane, PSf/non-woven fabric composite membrane, and Kimtex^®. Leakage of the inorganic particles and morphology of the membrane were investigated and availability as membrane reservoir for the lithium recovery was evaluated by the lithium desorption from Li_1.33Mn_1.67O₄ in the membrane reservoir. From this study, ease of water diffusion to the reservoir was the most important factor for the reservoir system to be applied to lithium recovery from seawater and membrane reservoir prepared by Kimtex^® showed the best result. The proposed system has the advantage of direct application in the sea without using pressurized flow system.     

Vibrational frequencies of (H2O) n and (D2O) n clusters for n = 2 and 8: possible relevance to inelastic neutron scattering of ice

Hartree-Fock plus MP2 corrections are reported for the vibrational frequencies in (H₂O)₂ and (D₂O)₂ and in the cubic octamers (H₂O)₈ and (D₂O)₈. The motivation was the inelastic incoherent neutron scattering of ice as studied experimentally by Li et al. (J.-C. Li, D. Londono, D.K. Ross, J.L. Finney, S.M. Bennington and A.D. Taylor (1992). J. Phys. Cond. Matter, 4, 2109). Some contact is made between our results and these experiments, and also with earlier infrared and Raman studies of Bertie and coworkers.     

Liquid Structure and Thermodynamics of Alkane Mixtures

Spectroscopic investigations and light scattering experiments with saturated, liquid hydrocarbons and their mixtures indicate a specific and distinct influence of the constitution, conformation, and flexibility of the molecule on the structure and macroscopic behavior of such liquids. Orientational order present in pure liquid n-alkanes, for example, characteristically affects the thermodynamic mixing properties, such as the enthalpy of mixing ΔH_M and the entropy of mixing ΔS_M , when these liquids are mixed with each other, or with other liquids. Nowadays it is possible to determine thermodynamic mixing properties experimentally with such precision that systematic investigations of these properties allow the behavior of liquids to be studied qualitatively and–with molecular theories of liquids–to some extent also quantitatively. The latest results in this respect, exemplified by mixtures of alkanes, are discussed. These results not only demonstrate the progress made in understanding the relations between molecular (microscopic) and macroscopic properties, but are also of importance for industrial applications (e.g. separation processes) in which mixtures of hydrocarbons are involved.     

Thermodynamics of ionization of water over wide ranges of temperature and pressure

We have summarized results of many experimental investigations of the thermodynamics of ionization of H₂O(liq.) from 0–300°C and from 1.0 atm to nearly 8000 atm. Results of these investigations (equilibrium constants, enthalpies of ionization, heat capacities, partial molal volumes, and compressibilities) have been used for a number of thermodynamic calculations. It is particularly noteworthy that it is possible to use thermal data from 0–145°C with an equilibrium constant for 25°C in calculating reasonably accurate equilibrium constants for temperatures as high as 300°C. Similarly, it is possible to use volumetric data that refer to 1.0 atm in calculating useful equilibrium constants that apply for pressures as high as 2000 atm.Much of the work reported here was done while the author was on leave at the University of Lethbridge.     

海水中甲基,丁基锡的形态分析

对海水中甲基、丁基锡的氢化反应与捕集、色谱分离及其原子化等进行了条件实验和最佳化。采用１５ｃｍＣｈｒｏｍｏｓｏｒｂＧＡＷ—ＤＭＣＳ载体和ＯＶ—３固定液，色谱分离锡的无机、一甲、二甲、三甲、一丁、二丁、三丁基化合物的保留时间分别为４０、１００、１２５、１３９、１６０、１９１、２２８ｓ；在０．２００ｄｍ３水样中直接测定海水中各形态锡的检出限分别为１．９、１．６、１．８、３．０、１．３、１．４、２２．４、ｎｇＳｎ·ｄｍ－３；其相应的测量精密度在１０％左右。     

Quantification of nitrite and nitrate in seawater by triethyloxonium tetrafluoroborate derivatization-headspace SPME GC-MS

Triethyloxonium tetrafluoroborate derivatization combined with direct headspace (HS) or SPME-gas chromatography-mass spectrometry (GC-MS) is proposed here for the simultaneous determination of nitrite and nitrate in seawater at micromolar level after conversion to their corresponding volatile ethyl-esters (EtO-NO and EtO-NO₂). Isotopically enriched nitrite [¹⁵N] and nitrate [¹⁵N] are employed as internal standards and for quantification purposes. HS-GC-MS provided instrumental detection limits of 0.07 μM NO₂⁻ and 2 μM NO₃⁻. Validation of the methodology was achieved by determination of nitrite and nitrate in MOOS-1 (Seawater Certified Reference Material for Nutrients, NRC Canada), yielding results in excellent agreement with certified values. All critical aspects connected with the potential inter-conversion between nitrite and nitrate (less than 10%) were evaluated and corrected for by the use of the isotopically enriched internal standard.     

Inorganic arsenic speciation in water and seawater by anodic stripping voltammetry with a gold microelectrode

The determination of arsenic in sea and freshwater by anodic stripping voltammetry (ASV) was revisited because of problems related to unstable peaks and inconveniently strong acidic conditions used by existing methods. Contrary to previous work it was found, that As(III) can be determined by ASV using a gold microwire electrode at any pH including the neutral pH typical for natural waters. As(V) on the other hand, requires acidification to pH 1, but this is still a much milder condition than used previously. This is the basis of a new method for the chemical speciation of arsenic in natural waters. The limits of detection are 0.2 nM As(III) at pH 8 and 0.3 nM combined arsenic (III + V) at pH 1 with a 30 s deposition time. These limits are lowered by extending the deposition time. The detection step at pH 8 was stripping chronopotentiometry (SC) as this was found to give a lower detection limit than ASV. Copper is co-determined simultaneously with arsenic. The method was applied successfully to the determination of arsenic as well as copper in samples from the Irish Sea, mineral water and tap water.     

Starch-iodine films respond to water vapor

Starch-iodine indicator films were found to have useful spectroscopic properties for the detection of water vapor. The large colorimetric response of these easily prepared films was easily detected by the absorption of 632.8 nm HeNe laser light, using a planar integrated optical waveguide (IOW) platform. The detection limit of a prototype sensor was found to be below 5% relative humidity (RH), with response times of the order of seconds.     

Contribution to vapor generation-inductively coupled plasma spectrometric techniques for determination of sulfide in water samples

Vapor generation-inductively coupled plasma-optical emission spectrometry was used for the determination of sulfide in water samples preserved by the addition of a zinc acetate and sodium hydroxide solution. Hydrogen sulfide and acid-volatile sulfides were transformed, by acidification, to a gaseous phase in a vapor generator and subsequently detected by inductively coupled plasma optical emission spectrometry. Compounds interfering with iodometric titration and spectrophotometric determination were examined as potential chemical interferents. The proposed method provides results comparable to iodometric titration in the tested concentration range 0.06-22.0 mg L⁻¹. Limit of detection for the determination of hydrogen sulfide by this method is 0.03 mg L⁻¹.     

Thermodynamics of solution of proto- and mezoporphyrins in N,N-dimethylformamide

This paper describes the results of thermodynamic study of dissolution of proto- and mesoporphyrins in liquid N,N-dimethylformamide (DMF) at different temperatures. Enthalpies of solution and solubility of protoporphyrin dimethylester (PDE) and mesoporphyrin dimethylester (MDE) in DMF have been obtained from T = (298 to 318) K. Free energies, enthalpies, entropies and heat capacities of solution have been computed from the combination of enthalpic and solubility data via the Gibbs–Helmholtz equation. We have shown that for all blood porphyrins this approach reproduces both free energies of solution and solubility values for the physiological temperature range.     

Determination of copper, cadmium and lead in seawater and mineral water by flame atomic absorption spectrometry after coprecipitation with aluminum hydroxide

An aluminum hydroxide coprecipitation method for the determination of cadmium, copper and lead by flame atomic absorption spectrometry in aqueous solutions, seawater and mineral water samples has been investigated. The coprecipitation conditions, such as the effect of the pH, the amount of carrier element, the effect of possible matrix ions and the time were examined in detail for the studied elements. It was found that cadmium, copper and lead are co-precipitated quantitatively (≥95%) with aluminum hydroxide at pH 7 with low R.S.D. values of around 2 to 3%. Detection limits (38) were 6 ng ml⁻¹ for Cd, 3 ng ml⁻¹ for Cu and 16 ng ml⁻¹ for Pb. The method proposed was validated by the analysis of HPS 312205 seawater standard reference material and spiked mineral water samples.     

Thermodynamics of reactions of iron with oxygen in the presence of water vapor

Changes in the standard Gibbs energies of the reactions of iron and iron oxides with pure oxygen and oxygen saturated with water vapor were calculated.     

VCSEL based detection of water vapor near 940nm

A vertical-cavity surface-emitting laser (VCSEL) was used to study the absorption spectrum of water vapor in the 940nm region. Measurements were performed in ambient air at room temperature and in a hydrogen-oxygen flame over the temperature range of 1500-1800K. Several rotational absorption lines within the 2v1 + v3 vibrational band were measured. The absorption spectra were well resolved, which demonstrates the feasibility of VCSEL-based spectroscopic measurements of water vapor at room and high-temperature in this spectral region. The results were in good agreement with the values obtained from the HITRAN-96 database.     

Free volume and water vapor permeability of dense segmented polyurethane membrane

This paper presented micro-structure, free volume and water vapor permeability of dense segmented polyurethane (SPU) membrane. Wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) techniques were employed to investigate the micro-structure. Free volume was measured by positron annihilation life spectroscopy (PALS). WAXD and DSC results indicated microcrystalline structure presents in the polymer membrane. Percent crystallinity of SPU would depend on the types of polyol used. The microphase-separated structure of copolymers was observed by transmission electron microscopy. Extent of phase separation was depended on the type and composition of polyol used. Free volume hole sizes are different for SPU samples due to the interaction between the polymer chains and packing of polymer chains due to the different compositions. The influences of temperature and chemical compositions on the free volume and water vapor permeability have been discussed. Experimental results revealed that the water vapor permeability can be controlled by free volume, which would depend on the chemical composition of SPU, and hydrophilicity of membranes.