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At least 415 records · Page 23

Carbon catalysis in the aqueous oxidation of SO2 by NO2 and air

Sulfur dioxide and an oxidant gas (air or NO2) were bubbled through aqueous suspensions of both washed and unwashed carbon black as well as through samples of wash water, which contained whatever soluble species were originally present on the carbon, and high-purity water. The sulfate yields obtained showed the washed and unwashed carbon to be equally catalytic for the oxidation of SO2 to sulfate by both oxidants, whereas little sulfate was generated in either the wash water or high-purity water in the absence of carbon. These results indicate that the sulfate yields produced in aqueous suspensions of the carbon studied are due to catalysis by the carbon particles rather than by soluble species dissolved from them.

Schryer, D. R.↗

Supercritical waste oxidation of aqueous wastes

For aqueous wastes containing 1 to 20 wt% organics, supercritical water oxidation is less costly than controlled incineration or activated carbon treatment and far more efficient than wet oxidation. Above the critical temperature (374 C) and pressure (218 atm) of water, organic materials and gases are completely miscible with water. In supercritical water oxidation, organics, air and water are brought together in a mixture at 250 atm and temperatures above 400 C. Organic oxidation is initiated spontaneously at these conditions. The heat of combustion is released within the fluid and results in a rise in temperature 600 to 650 C. Under these conditions, organics are destroyed rapidly with efficiencies in excess of 99.999%. Heteroatoms are oxidized to acids, which can be precipitated out as salts by adding a base to the feed. Examples are given for process configurations to treat aqueous wastes with 10 and 2 wt% organics.

Modell, M.↗

Surface tension measurements of aqueous ammonium chloride (NH4Cl) in air

Aqueous NH4Cl's solidification is often used to model metal alloy solidification processes. The present determinations of the magnitude of the variation of aqueous NH4Cl's surface tension as a function of both temperature and solutal concentration were conducted at 3, 24, and 40 C over the 72-100 wt pct water solutal range. In general, the surface tension increases 0.31 dyn/cm per percent decrease in wt pct of water, and decreases 0.13 dyn/cm for each increase in deg C. Attention is given to the experimental apparatus employed.

Lowry, S. A.↗

Aqueous alteration in the Kaba CV3 carbonaceous chondrite

Results from TEM and SEM examinations of the Kaba CV3 carbonaceous chondrite are presented, showing that the chondrules and the matrix of Kaba have undergone pervasive low-temperature aqueous alteration, resulting in the formation of Fe-bearing saponite from glass and enstatite in chondrules, and from anhydrous silicates in matrix. The alteration products in Kaba were found to resemble those in other aqueously altered carbonaceous chondrites such as the Mokoia CV3 and in Orgueil CI chondrites and Y-82162 chondrites. However, Kaba lacks the abundant high-Al phyllosilicates, reported for CAIs from Mokoia, and the serpentine and ferrihydrite, found in Orgueil.

Keller, Lindsay P.↗

Aqueous alteration in five chondritic porous interplanetary dust particles

Results are presented on AEM observations carried out on chondritic porous (CP) interplanetary dust particles (IDPs), which include data on alkali-rich layer silicates and new observations of nonstoichiometric plagioclase and alkali feldspars in individual CP IDPs. The compositional similarities found between the feldspar minerals and the layer silicates suggest that the latter have formed from these feldspars during low-temperature aqueous alterations at a stage of diagenesis in the CP IDP parent bodies. Small, but persistent, amounts of layer silicates, carbonates, and barite found in several nominally anhydrous CP IDPs support the suggestion of incipient aqueous alterations in their parent bodies, which may include short-period comet nuclei and outer-belt asteroids.

Rietmeijer, Frans J. M.↗

Aqueous alteration of the Nakhla meteorite

Interior samples of three different Nakhla specimens contain an iron-rich silicate 'rust' (which includes a tentatively identified smectite), Ca-carbonate (probably calcite), Ca-sulfate (possibly gypsum or bassanite), Mg-sulfate (possibly epsomite or kieserite), and NaCl (halite); the total abundance of these phases is estimated as less than 0.01 weight percent of the bulk meteorite. Rust veins are truncated and decrepitated by fusion crust and are preserved as faulted segments in partially healed olivine crystals, indicating that the rust is preterrestrial in origin. Because Ca-carbonate and Ca-sulfate are intergrown with the rust, they are also indicated to be of preterrestrial origin. Similar textural evidence regarding origins of the NaCl and Mg-sulfate is lacking. Impure and poorly crystallized sulfates and halides on the fusion crust of the meteorite suggest leaching of interior (preterrestrial) salts from the interior after Makhla arrived on earth, but coincidental addition of these same salts by terrestrial contamination cannot be exluded. At least the clay-like silicate 'rust', Ca-carbonate, and Ca-sulfate were formed by precipitation from water-based solutions on the Nakhla parent planet, although temperature and pressure conditions of aqueous precipitation are unconstrained by currently available data. It is possible that aqueous alteration on the parent body was responsible for the previously observed disturbance of the Rb-Sr geochronometer in Nakhla at or near 1.3 Ga.

Gooding, James L.↗

Aqueous alteration on the parent bodies of carbonaceous chondrites: Computer simulations of late-stage oxidation

CI carbonaceous chondrites may be products of hydrous alteration of CV- or anhydrous CM-type materials. The CIs typically contain veins filled with carbonates and sulfates, probably indicating a period of late stage aqueous alteration under oxidizing conditions. To test this idea, computer simulations of aqueous alteration of CV- and CM-type carbonaceous were performed. Simulations were restricted to the oxidation of hydrous mineral assemblages produced in previous simulations in order to determine whether further reaction and oxidation results in the phyllosilicate, carbonate, sulfate and oxide vein assemblages typical of CI carbonaceous chondrites. Our simulations were performed at 1, 25, 100, and 150 C (the appropriate temperature range) for the CV and CM mineral assemblages and using the computer code EQ3/6.

Bourcier, W. L.↗

Aqueous geochemistry on Mars: Possible clues from salts and clays in SNC meteorites

All subgroups of the shergottite, nakhlite, and chassignite (SNC) meteorites contain traces of water precipitated minerals that include various combinations of carbonates, sulfates, halides, ferric oxides, and aluminosilicate clays of preterrestrial origin. Oxygen three-isotope analysis of thermally extracted bulk water has confirmed that at least some of the water in SNC's is, indeed, extraterrestrial. A mixture of aqueous precipitates found in the SNC's, comprising smectite, illite, and gypsum (with minor halite +/- calcite and hematite), provides a self-consistent, though not unique, model for the bulk elemental composition of surface sediments at the Viking Lander sites. Therefore, if the salts and clays in SNC's are truly linked to aqueous alteration and soil formation on Mars, then the suite of SNC secondary minerals might provide the best currently available insight into near-surface martian chemistry.

Gooding, James L.↗

Noble gas evidence of an aqueous reservoir near the surface of Mars more recently than 1.3 Ga

Considerable evidence points to a Martian origin of the SNC meteorites. One of these meteorites, Nakhla, contains a leachable component which has an elevated Xe-129/Xe-132 ratio relative to its Kr-84/Xe-132 ratio when compared to the approximately linear array defined by Chassigny, most shergottites, and lithology C of EETA 79001. This array is thought to be a mixing line between Martian mantle and Martian atmosphere. The leachable component probably consists in part of iddingsite, an alteration product produced by interaction of olivine with aqueous fluid at temperatures lower than 150 C. The radiogenic Xe component may represent a distinct reservoir in the Martian crust or mantle. More plausibly, it is Martian atmosphere, fractionated by solution in liquid water and by interaction with sediment. The crystallization age of Nakhla is 1.3 Ga. Its low shock state suggests that it was ejected from near the surface of Mars. Liquid water is required for the formation of iddingsite. These observations provide further evidence for the near surface existence of aqueous fluids more recently than 1.3 Ga.

Drake, Michael J.↗

Regenerating using aqueous cleaners with ozone and electrolysis

A new process converts organic oil and grease contaminates in used water based cleaners into synthetic surfactants. This permits the continued use of a cleaning solution long after it would have been dumped using previously known methods. Since the organic soils are converted from contaminates to cleaning compounds the need for frequent bath dumps is totally eliminated. When cleaning solutions used in aqueous cleaning systems are exhausted and ready for disposal, they will always contain the contaminates removed from the cleaned parts and drag-in from prior cleaning steps. Even when the cleaner is biodegradable these contaminants will frequently cause the waste cleaning solution to be a hazardous waste. Chlorinated solvents are rapidly being replaced by aqueous cleaners to avoid the new ozone-depletion product-labeling-law. Many industry standard halocarbon based solvents are being completely phased out of production, and their prices have nearly tripled. Waste disposal costs and cradle-to-grave liability are also major concerns for industry today. This new process reduces the amount of water and chemicals needed to maintain the cleaning process. The cost of waste disposal is eliminated because the water and cleaning compounds are reused. Energy savings result by eliminating the need for energy currently used to produce and deliver fresh water and chemicals as well as the energy used to treat and destroy the waste from the existing cleaning processes. This process also allows the cleaning bath to be maintained at the peak performance of a new bath resulting in decreased cycle times and decreased energy consumption needed to clean the parts. This results in a more efficient and cost effective cleaning process.

Mcginness, Michael P.↗

Mars aqueous chemistry experiment

Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. The second year of the MACE project has shown significant progress in two major areas. MACE Instrument concept definition is a baseline design that has been generated for the complete MACE instrument, including definition of analysis modes, mass estimates and thermal model. The design includes multiple reagent reservoirs, 10 discrete analysis cells, sample manipulation capability, and thermal control. The MACE Measurement subsystems development progress is reported regarding measurement capabilities for aqueous ion sensing, evolved gas sensing, solution conductivity measurement, reagent addition (titration) capabilities, and optical sensing of suspended particles.

Clark, Benton C.↗

Aqueous alternatives for metal and composite cleaning

For many years the metalworking industry has cleaned metal and composite substrates with chlorinated solvents. Recently, however, health and disposal related environmental concerns have increased regarding chlorinated solvents, including 1,1,1-trichloroethane, trichloroethylene, methylene chloride, or Freon'. World leaders have instituted a production ban of certain ozone depleting chlorofluorocarbons (CFC's) by 1996. The Occupational Safety and Health Administration (OSHA) has instituted worker vapor exposure limitations for virtually all of the solvents used in solvent-based cleaners. In addition, the United States Environmental Protection Agency (EPA) has defined nearly all solvent-based cleaners as 'hazardous'. Cradle to grave waste responsibility is another reason manufacturers are trying to replace chlorinated solvents in their cleaning processes. Because of these factors, there now is a world wide effort to reduce and/or eliminate the use of chlorinated solvents for industrial cleaning. Waterbased cleaners are among the alternatives being offered to the industry. New technology alkaline cleaners are now available that can be used instead of chlorinated solvents in many cleaning processes. These waterbased cleaners reduce the release of volatile organic compounds (VOC's) by as much as 99 percent. (The definition and method of calculation of VOC's now varies from region to region.) Hazardous waste generation can also be significantly reduced or eliminated with new aqueous technology. This in turn can ease worker exposure restrictions and positively impact the environment. This paper compares the chemical and physical properties of this aqueous cleaners versus chlorinated solvents.

Quitmeyer, Joann↗

Aqueous cleaning design presentation

The phase-out of CFC's and other ozone depleting chemicals has prompted industries to re-evaluate their present methods of cleaning. It has become necessary to find effective substitutes for their processes as well as to meet the new cleaning challenges of improved levels of cleanliness and to satisfy concerns about environmental impact of any alternative selected. One of the most popular alternatives being selected is aqueous cleaning. This method offers an alternative for removal of flux, grease/oil, buffing compound, particulates and other soils while minimizing environmental impact. What I will show are methods that can be employed in an aqueous cleaning system that will make it environmentally friendly, relatively simple to maintain and capable of yielding an even higher quality of cleanliness than previously obtained. I will also explore several drying techniques available for these systems and other alternatives along with recent improvements made in this technology. When considering any type of cleaning system, a number of variables should be determined before selecting the basic configuration. Some of these variables are: (1) Soil or contaminants being removed from your parts; (2) The level of cleanliness required; (3) The environmental considerations of your area; (4) Maintenance requirements; and (5) Operating costs.

Maltby, Peter F.↗

QFD analysis of RSRM aqueous cleaners

This paper presents a Quality Function Deployment (QFD) analysis of the final down-selected aqueous cleaners to be used on the Redesigned Solid Rocket Motor (RSRM) program. The new cleaner will replace solvent vapor degreasing. The RSRM Ozone Depleting Compound Elimination program is discontinuing the methyl chloroform vapor degreasing process and replacing it with a spray-in-air aqueous cleaning process. Previously, 15 cleaners were down-selected to two candidates by passing screening tests involving toxicity, flammability, cleaning efficiency, contaminant solubility, corrosion potential, cost, and bond strength. The two down-selected cleaners were further evaluated with more intensive testing and evaluated using QFD techniques to assess suitability for cleaning RSRM case and nozzle surfaces in preparation for adhesive bonding.

Marrs, Roy D.↗

Evidence for organic synthesis in high temperature aqueous media - facts and prognosis

Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to greater than 400 C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. The reactivity of organic compounds in hot water (200-350 C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to greater than 400 C.

Simoneit, Bernd R. T.↗

Mars Aqueous Chemistry Experiment (MACE)

The concept of an aqueous-based chemical analyzer for Martian surface materials has been demonstrated to be feasible. During the processes of analysis, design, breadboarding, and most importantly, testing, it has become quite apparent that there are many challenges in implementing such a system. Nonetheless, excellent progress has been made and a number of problems which arose have been solved. The ability to conduct this work under a development environment which is separate and which precedes the project-level development has allowed us to find solutions to these implementation realities at low cost. If the instrument had been selected for a mission without this laboratory pre-project work, the costs of implementation would be much higher. In the four areas covered in Sections D, E, F, and G of this Final Report, outstanding progress has been made. There still remains the task of flight-qualifying certain of the components. This is traditionally done under the aegis of a Flight Project, but just as the concept development can be done at much lower cost when kept small and focused, so could the qualification program of critical parts benefit. We recommend, therefore, that NASA consider means of such qualifications and brass-boarding, in advance of final flight development. This is a generic recommendation, but hardware such as the Mars aqueous chemistry experiment (MACE) and other similarly-new concepts are particularly applicable. MACE now has wide versatility, in being able to reliably dispense both liquids and solids as chemical reagents to an entire suite of samples. The hardware and the experiment is much simpler than was developed for the Viking Biology instrument, yet can accomplish all the inorganic chemical measurements that the Viking desing was capable of. In addition, it is much more flexible and versatile to new experiment protocols (and reagents) than the Viking design ever could have been. MACE opens up the opportunity for many different scientific disciplines to design sub- experiments and to benefit from the investigations that can be conducted. In this sense, it will have the value of a facility, although our recommendation would be that it be under the stewardship of a single lead investigator to insure that conflicting requirements not compromise the straight-forward design that have been achieved. MACE is an excellent candidate for upcoming Mars missions, including the Mars Surveyor Program (MSP) lander missions in 2001 and 2003. In addition, it could be used for any mission to the surface of any other planet or planetary body (including small bodies). An important next step is to encourage various investigators to propose specific uses for this experiment that specifically address their major scientific objectives for upcoming missions.

Benton, Clark C.↗

An Experimental Study of the Effects of A Rotating Magnetic Field on Electrically Conducting Aqueous Solutions

The use of a rotating magnetic field for stirring metallic melts has been a commonly adopted practice for a fairly long period. The elegance of the technique stems from its non-intrusive nature and the intense stirring it can produce in an electrically conducting medium. A further application of the method in recent times has been in the area of crystal growth from melts (e.g. germanium). The latter experiments have been mainly research oriented in order to understand the basic physics of the process and to establish norms for optimizing such a technique for the commercial production of crystals. When adapted for crystal growth applications, the rotating magnetic field is used to induce a slow flow or rotation in the melt which in effect significantly curtails temperature field oscillations in the melt. These oscillations are known to cause dopant striations and thereby inhomogeneities in the grown crystal that essentially degrades the crystal quality. The applied field strength is typically of the order of milli-Teslas with a frequency range between 50-400 Hz. In this investigation, we report findings from experiments that explore the feasibility of applying a rotating magnetic field to aqueous salt solutions, that are characterized by conductivities that are several orders of magnitude smaller than semi-conductor melts. The aim is to study the induced magnetic field and consequently the induced flow in such in application. Detailed flow field description obtained through non-intrusive particle displacement tracking will be reported along with an analytical assessment of the results. It is anticipated that the obtained results will facilitate in establishing a parameter range over which the technique can be applied to obtain a desired flow field distribution. This method can find applicability in the growth of crystals from aqueous solutions and give an experimenter another controllable parameter towards improving the quality of the grown crystal.

Ramachandran Narayanan↗

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

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.

Iraci, L. T.↗