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Low-level doped solid metal/liquid metal experiments analyzed by laser ablation ICP-MS allow Henry's Law to be tested. The results indicate Henry's Law is obeyed and the experimental partition coefficients can be applied to iron meteorites. Additional information is contained in the original extended abstract.
Various investigators propose the lunar surface contains widely distributed volatiles, especially water- like species, i.e. OH and H2O. Surface volatiles are theorized to exist as a hydrated regolith layer, concentrated in extremely cold polar permanently shadowed regions (PSR), and/or solar wind implantation reservoirs in lunar glasses. The proposed sources of lunar surface volatiles range from cometary impacts, solar wind, or a supply present during moon formation. Future Artemis missions aim to collect and return the samples containing volatiles collected near lunar polar craters or PSRs. We, as advanced curation scientists, are responsible for developing techniques and methodologies for preserving returned sample integrity as much as possible. Pristine volatile-bearing samples are invaluable to the scientific community seeking to unravel the history of the solar system. Realistically, a sample will experience alteration during collection, transportation back to earth, and storage. The Planetary Exploration and Astromaterials Research Lab (PEARL) seeks to understand temperature and pressure effects on high-fidelity volatile-containing regolith simulants, the foundation for the future of cold curation. This abstract outlines the separation, identification, and quantification of headspace gases over volatile ice feed stock material using gas chromatography/mass spectrometry (GC/MS). Preliminary objectives concentrated on sample handling, reproducibility, and understanding the elution characteristics for each analyte. Initial GC/MS method development experiments utilized diluted static headspace sample preparation. Diluted samples were used because sampling headspace gases directly from a vial containing liquid analyte resulted in overloading of the column and detector. Overloading is evident based on chromatogram peak shapes and instrument contamination, or carry over, between experiments. A mixture of three alcohols were used for a majority of the sample handling and reproducibility studies. Reproducibility was tested via multiple users, calibration curves, and check standards. Stock solutions of condensed lunar volatile analytes included methanol, ammonia in methanol, hydrogen sulfide in water, and an equal volume mixture of methanol, ethanol, and isopropanol. Current samples use room air as the headspace sample matrix, however future experiments will incorporate an inert purge gas, such as argon or nitrogen. Three mL of each analyte solution were capped in separate 20 mL crimp top GC vials. Dilutions were carried out by removing an aliquot of headspace gases with a calibrated 1 mL gastight syringe and immediately transferring to a 20 mL capped crimp top vial. The GC/MS is a Thermo Fisher Trace 1310/ISQ 7000 with a TriPlus RSH autosampler and split/splitless injector module. The experiments outlined in this abstract use the following hardware: a 2.5 mL gastight headspace syringe tool, 1 mm ID x 78.5 mm length ultra-inert straight injection liner, and a TG-BondQ 30 m × 0.32 mm × 10 μm column. Various parameters, such as hardware selection and the temperature, pressure, and split ratio set points, continue to evolve as the overall experiment is refined. Diluted headspace chromatograms were collected for the individual stock solutions. Retention times, peak shapes, and mass spectra were evaluated and added to the data processing method for each molecule of interest. Figure 1 shows the total ion chromatograms for the three major lunar volatile simulant stock solutions: methanol, 7 N ammonia in methanol, and 0.4% hydrogen sulfide in water. Tailing peak shapes for ammonia (2.98 min rt) and water (4.06 min rt) indicate the molecules are not properly eluting from the selected column with the current separation method. Additionally, hydrogen sulfide and ammonia have overlapping peak windows, which could impact quantification. Ongoing experiments aim to address the peak shape and overlapping via the separation method and hardware selection. Sample preparation reproducibility experiments used stock solution containing equal volumes of a non- interactive mixture of methanol, ethanol, and isopropanol. Mass spectrum ion traces were used to identify and quantify all three alcohols. Peaks were automatically detected, identified, and integrated through the mass spectra detection and processing parameters. Calibration response curves and check standards were used to evaluate the validity of the sample preparation procedure. Figure 2 shows the methanol chromatogram peak area versus total headspace dilution volume transferred from the alcohol mixture vial. The calibration response curves and check standards validate sample preparation procedure. Continuing data analysis efforts are working towards correlating the peak area and instrument response factor to the headspace analyte concentration and condensed phase composition. Static headspace gas chromatography theory relies on Dalton’s law, Raoult’s law, Henry’s Law, and the Kolb and Ettre equation to associate peak area to the analyte composition in a non-ideal solution. Equation 1 is a simplified expression derived from the aforementioned theories. Future experiments involve liquid injections of the individual stock solutions, liquid and headspace analysis of various stock solution combinations, and the addition of regolith simulants to the mixtures. Temperature is another variable expected to affect reaction rates and will be explored.
An experimental investigation of Ce, Sm and Tm rare earth element (REE) partition coefficients between coexisting garnets (both natural and synthetic) and hydrous liquids shows that Henry's Law may not be obeyed over a range of REE concentrations of geological relevance. Systematic differences between the three REE and the two garnet compositions may be explained in terms of the differences between REE ionic radii and those of the dodecahedral site into which they substitute, substantiating the Harrison and Wood (1980) model of altervalent substitution. Model calculations demonstrate that significant variation can occur in the rare earth contents of melts produced from a garnet lherzolite, if Henry's Law partition coefficients do not apply for the garnet phase.
Distilled water and several waters of varying salinity were subjected, over a 0-32 C temperature range, to measurements for Henry's law constants for dimethylsulfide. Values for distilled water and seawater of the solubility parameters A and C are obtained which support the concept that the concentration of dimethylsulfide in the atmosphere is far from equilibrium with seawater.
The uptake of nitric acid by sulfuric acid solutions representative of stratospheric particulate at low temperatures was measured to determine the solubility of nitric acid in sulfuric acid solutions as a function of H2SO4 concentration and solution temperature. Solubilities are reported for sulfuric acid solutions ranging from 58 to 87 wt pct H2SO4 over a temperature range from 188 to 240 K, showing that, in general, the solubility of nitric acid increases with decreasing sulfuric acid concentration and with decreasing temperature. The measured solubilities indicate that nitric acid in the global stratosphere will be found predominantly in the gas phase.
The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.
Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.
A thermodynamic model is presented for vapor-liquid equilibrium in the N2 + CH4 system, which is implicated in calculations of the Titan tropospheric clouds' vapor-liquid equilibrium thermodynamics. This model imposes constraints on the consistency of experimental equilibrium data, and embodies temperature effects by encompassing enthalpy data; it readily calculates the saturation criteria, condensate composition, and latent heat for a given pressure-temperature profile of the Titan atmosphere. The N2 content of condensate is about half of that computed from Raoult's law, and about 30 percent greater than that computed from Henry's law.
A method that uses a mass spectrometer as a manometer is employed in the measurement of Xe and Kr adsorption parameters on shales and related samples, where gas partial pressures were lower than 10 to the -11th atm, corresponding adsorption coverages are only small fractions of a monolayer, and Henry's Law behavior is expected and observed. Results show heats of adsorption in the 2-7 kcal/mol range, and Henry constants at 0-25 C of 1 cu cm STP/g per atmosphere are extrapolated. Although the adsorption properties obtained are variable by sample, the range obtained suggests that shales may be capable of an equilibrium adsorption with modern air high enough to account for a significant fraction of the atmospheric inventory of Xe, and perhaps even of Kr. This effect will nevertheless not account for the factor-of-25 defficiency of atmospheric Xe, in comparison with the planetary gas patterns observed in meteorites.
In order to verify the air content in hydraulic fluid, an instrument was needed to measure the dissolved air content before the fluid was loaded into the system. The instrument also needed to measure the dissolved air content in situ and in real time during the de-aeration process. The current methods used to measure the dissolved air content require the fluid to be drawn from the hydraulic system, and additional offline laboratory processing time is involved. During laboratory processing, there is a potential for contamination to occur, especially when subsaturated fluid is to be analyzed. A new method measures the amount of dissolved air in hydraulic fluid through the use of a dissolved oxygen meter. The device measures the dissolved air content through an in situ, real-time process that requires no additional offline laboratory processing time. The method utilizes an instrument that measures the partial pressure of oxygen in the hydraulic fluid. By using a standardized calculation procedure that relates the oxygen partial pressure to the volume of dissolved air in solution, the dissolved air content is estimated. The technique employs luminescent quenching technology to determine the partial pressure of oxygen in the hydraulic fluid. An estimated Henry s law coefficient for oxygen and nitrogen in hydraulic fluid is calculated using a standard method to estimate the solubility of gases in lubricants. The amount of dissolved oxygen in the hydraulic fluid is estimated using the Henry s solubility coefficient and the measured partial pressure of oxygen in solution. The amount of dissolved nitrogen that is in solution is estimated by assuming that the ratio of dissolved nitrogen to dissolved oxygen is equal to the ratio of the gas solubility of nitrogen to oxygen at atmospheric pressure and temperature. The technique was performed at atmospheric pressure and room temperature. The technique could be theoretically carried out at higher pressures and elevated temperatures.
Solubilities of noble gases in magnetite were determined by growing magnetite in a noble-gas atmosphere between 450 and 700 K. Henry's law is obeyed at pressures up to .01 atm for He, Ne, Ar and up to .00001 atm for Kr, Xe, with the following distribution coefficients at 500 K: He 0.042, Ne 0.016, Ar 3.6, Kr 1.3, Xe 0.88, some 100 to 100,000 times higher than previous determinations on silicate and fluoride melts. Apparent heats of solution are in sharp contrast with earlier determinations on melts which were small and positive, but are comparable to the values for clathrates. Presumably the gases are held in anion vacancies.
Distribution coefficients have been found for the partitioning of Ni, Co, and Mn between calcium-rich clinopyroxenes and coexisting silicate liquids. Values are found for the 1110-1360 C temperature range. The breakdown of Henry's Law was not observed. The measured clinopyroxene/liquid distribution coefficients ranged from 1.5-14.0 for Ni, 0.5-2.0 for Co, and 0.3-1.2 for Mn. Analyses of pyroxenes grown from charges differing in the amounts of transition metals indicate that Ni and Co occupy the M1 site of diopside and that Mn occupies the M1 and M2 sites. Equilibrium constants were found in terms of the activities of the components in the liquid and solid phases. These activities are based on the mole fractions. An activity/concentration model was used for the liquid phase in order to explain the variations in the clinopyroxene/liquid coefficients due to bulk composition.
The distribution coefficients of Zr and Nb have been found between armalcolite, ilmenite, clinopyroxene, rutile, plagioclase, and a coexisting high-Ti mare basalt melt in the 1105-1128 C temperature range. Henry's Law is not broken over the compositional range evaluated. The distribution coefficients of clinopyroxene are strongly dependent on melt and crystal compositions. The Al2O3 activity in the melt is a strong controlling parameter. It is concluded that: (1) Apollo 11 (low K) and Apollo 17 high-Ti mare basalts may have been generated by the partial melting of an ilmenite-rich cumulate, (2) Apollo 11 (high K) basalts may have been generated by a small amount of partial melting of a more fractionated ilmenite-rich cumulate, (3) KREEP magmas may have been formed as residual melts produced by fractional crystallization of the lunar magma ocean, and (4) anomalous (type II) MOR basalts may have been generated by small degrees of partial melting of a relatively undepleted mantle with clinopyroxene remaining in the residium.
Partition coefficients for Ce, Sm, and Tm between garnet, clinopyroxene, orthopyroxene, olivine, and melt are determined at 35 kbar for 2.3, 8, 20, and 37.7% melting of a garnet lherzolite nodule with chondritic REE abundances. Partition coefficients are found to increase as the degree of partial melting increases. From 2.3 to 8% melting, this increase is for the most part a consequence of non-Henry's law behavior of REE in minerals.
The trapping of noble gases by chromite and carbon, two putative carriers of primordial noble gases in meteorites, was studied by synthesizing 19 samples in a Ne-Ar-Kr-Xe atmosphere at 440-720 K. Noble gas contents are found to approximately obey Henry's Law, but only slight correlations are found with composition, surface area, or adsorption temperature. Geometric mean distribution coefficients for bulk samples and HCl residues in 10 cu cm STP/g atm are: Xe 100, Kr 15, Ar 3.5, and Ne 0.62. Elemental fractionation data support the suggestion of Lewis et al. (1977) that chromite and carbon in C2 and C3 chondrites were formed by the reaction: Fe, Cr + 4CO yields (Fe, Cr)3O4 + 4C + carbides. In contrast to meteoritic minerals, the synthetic specimens show no isotopic fractionation of noble gases. In a subsequent study, attention is given to the cases of sulfides and spinels, on the way to consideration of the origin of planetary gases. Sulfides showed three distinctive trends relative to chromite or magnetite. The elemental fractionation pattern of Ar, Kr and Xe in meteorites, terrestrial rocks and planets resembles the adsorption patterns on the carbons, spinels, sulfides, and other solids studied. The high release temperature of meteoritic noble gases may be explained by transformation of the physisorbed or chemisorbed gas. The ready loss of meteoritic heavy gases on surficial oxidation is consistent with adsorption, as is the high abundance.
In order to resolve the discrepancy noted in values currently used for the first dissociation constant of SO2 in water, the pertinent literature was critically examined and a value of 0.0132 M at 25 C was recommended. An expression correlating this value as a function of temperature for zero-50 C has been developed. Attention is also given to the literature for the Henry's law constant, and a value of 1.242 M/atm at 25 C is recommended. Ionic activity corrections and speciation in more concentrated solutions are discussed, and recommendations are made for estimating the activity coefficients of the various ionic species in solutions of moderate ionic strength.
A theoretical description of the mechanisms of isotopic fractionation arising during adsorption of noble gases in a Henry's Law pressure regime is given. Experimental data on the isotopic composition of Xe adsorbed on activated charcoal in the temperature range 220 K to 350 K are presented. Both theoretical considerations and the experimental data indicate that equilibrium adsorption does not significantly alter the isotopic structure of adsorbed structure of adsorbed noble gases. Therefore, if adsorption is responsible for the elemental noble gas pattern in meteorites and the earth, the heavy noble gas isotopic fractionation between them must have been produced prior to and by a different process than equilibrium adsorption.
The observation that altitude decompression sickness (DCS) is associated with pain in the lower extremities is not new, although it is not a consistent finding. DCS in divers is generally in the upper body, an effect often attributed to non-loading of the body while immersed. In caisson workers, DCS is reported more in the lower extremities. Surprisingly, many researchers do not mention the location of DCS joint pain, apparently considering it to be random. This is not the case for the tissue ratios encountered in studying decompression associated with simulated EVA. In NASA/JSC tests, altitude DCS generally presented first in either the ankle, knee, or hip (83 percent = 73/88). There was a definite statistical relation between the maximum Spencer precordial Doppler Grade and the incidence of DCS in the extremity, although this is not meant to imply a casual relation between circulating gas bubbles and joint pain. The risk of DCS with Grade 4 was considerably higher than that of Grades 0 to 3. The DCS risk was independent of the 'tissue ratio.' There was a predominance of lower extremity DCS even when exercise was performed with the upper body. The reason for these locations we hypothesize to be attributed to the formation of tissue gas micronuclei from kinetic and tensile forces (stress-assisted nucleation) and are the result of the individuals ambulating in a 1g environment. Additionally, since these showers of Doppler bubbles can persist for hours, it is difficult to imagine that they are emanating solely from tendons and ligaments, the supposed site of joint pain. This follows from Henry's law linking the volume of joint tissue (the solvent) and the solubility coefficient of inert gas; there is volumetrically insufficient connective tissue to produce the prolonged release of gas bubbles. If gas bubbles are spawned and released from connective tissue, their volume is increased by those from muscle tissue. Therefore, the nexus between Doppler-detectable gas bubbles and joint-pain decompression sickness is essentially a statistical, rather than a direct, one.