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NASA NTRS1974

New reactions of paraformaldehyde and formaldehyde with inorganic compounds

Both paraformaldehyde and formaldehyde undergo reactions in the presence of several inorganic compounds to generate a variety of interesting organic products that can be important in chemical evolutionary processes. Some examples are acrolein, acetaldehyde, methyl formate, methanol, glycolaldehyde and formic acid. The organic compounds are produced at temperatures as low as 56 C and in high yield (up to 75%). The quantity produced depends principally on the nature of the inorganic compound, the ratio of the inorganic compound to paraformaldehyde, temperature and reaction time. The percent distribution of product depends on some of the foregoing factors.

Becker, R. S.↗
NASA NTRS2001

Inorganic Chlorine Partitioning in the Summer Lower Stratosphere: Modeled and Measured [ClONO2/HCl] During POLARIS

We examine inorganic chlorine (Cly) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO2]/[HCl] by approximately 55-60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cly partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO2 measurement (too low). The high precision of our simulation (+/-15% 1-sigma for [ClONO2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models.

Voss, P. B.↗
NASA NTRS2000

An Examination of the Inorganic Chlorine Budget in the Lower Stratosphere

We use the first simultaneous in situ measurements of ClONO2, ClO, and HCl acquired using the NASA ER-2 aircraft during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission to test whether these three compounds quantitatively account for total inorganic chlorine (Cly) in the lower stratosphere in 1997. We find (ClO + ClONO2 + HCl)/Cly = 0.92 +/- 0.10, where Cly is inferred from in situ measurements of organic chlorine source gases. These observations are consistent with our current understanding of the budget and partitioning of Cly in the lower stratosphere. We find no evidence in support of missing inorganic chlorine species that compose a significant fraction of Cly. We apply the analysis to earlier ER-2 observations dating from 1991 to investigate possible causes of previously observed discrepancies in the inorganic chlorine budget. Using space shuttle, satellite, balloon, and aircraft measurements in combination with ER-2 data, we find that the discrepancy is unlikely to have been caused by missing chlorine species or an error in the photolysis rate of chlorine nitrate. We also find that HCl/Cly is not significantly controlled by aerosol surface area density in the lower stratosphere.

Bonne, G. P.↗
NASA NTRS1996

Recycle of Inorganic Nutrients for Hydroponic Crop Production Following Incineration of Inedible Biomass

Recovery of resources from waste streams is essential for future implementation and reliance on a regenerative life support system. The major waste streams of concern are from human activities and plant wastes. Carbon, water and inorganics are the primary desired raw materials of interest. The goal of resource recovery is maintenance of product quality to insure support of reliable and predictable levels of life support function performance by the crop plant component. Further, these systems must be maintained over extended periods of time, requiring maintenance of nutrient solutions to avoid toxicity and deficiencies. Today, reagent grade nutrients are used to make nutrient solutions for hydroponic culture and these solutions are frequently changed during the life cycle or sometimes managed for only one crop life cycle. The focus of this study was to determine the suitability of the ash product following incineration of inedible biomass as a source of inorganic nutrients for hydroponic crop production. Inedible wheat biomass was incinerated and ash quality characterized. The incinerator ash was dissolved in adequate nitric acid to establish a consistent nitrogen concentration in all nutrient solution treatments. Four experimental nutrient treatments were included: control, ash only, ash supplemented to match control, and ash only quality formulated with reagent grade chemicals. When nutrient solutions are formulated using only ash following-incineration of inedible biomass, a balance in solution is established representing elemental retention following incineration and nutrient proportions present in the original biomass. The resulting solution is not identical to the control. This imbalance resulted in suppression of crop growth. When the ash is supplemented with nutrients to establish the same balance as in the control, growth is identical to the control. The ash appears to carry no phytotoxic materials. Growth in solution formulated with reagent grade chemicals but matching the quality of the ash only treatment resulted in growth similar to that of the ash only treatment. The ash product resulting from incineration of inedible biomass appears to be a suitable form for recycle of inorganic nutrients to crop production.

Bubenheim, David L.↗
NASA NTRS1989

Distribution of inorganic species in two Antarctic cryptoendolithic microbial communities

Chemical differences were noted between two Antarctic cryptoendolithic (hidden within rock) microenvironments colonized by different microbial communities. Microenvironments dominated by cyanobacteria (BPC) had a higher pH (pH 7-8) than those dominated by lichen (LTL) (pH 4.5-5.5). In order to understand the interactions between the microbiota and the inorganic environment, the inorganic environment was characterized. Water-soluble, carbonate-bound, metal-oxide, organically bound, and residual inorganic species were sequentially extracted from rock samples by chemical means. Each fraction was then quantified using inductively coupled plasma atomic emission spectrometry. BPC contained much more water-soluble and carbonate-bound Ca and Mg than LTL. Metal-oxide species of Al, Fe, and Mn were more abundant in LTL than BPC. Metal oxides appeared to be mobilized (in the order Mn > Fe > Al) from the LTL lichen zone but remained immobile in BPC sandstone. The distribution of K and P bound to metal oxide reflected the distribution of iron oxide in LTL, an indication of the importance of iron in controlling the availability of nutrients in this ecosystem. Metal oxides in turn were likely controlled or influenced by organic matter associated with the lichen community. Despite overall depletion of Fe, Al, and K in the lichen zone, SEM X-ray analysis showed that they were enriched in fungal hyphae. Water-soluble P was present despite the presence of metal oxides, which sequester phosphate. This has biological relevance since P is an essential nutrient.

NASA Program Exobiology↗
NASA NTRS1990

Effect of ammonium sulfate, ammonium chloride and root-zone acidity on inorganic ion content of tobacco

Tobacco plants (Nicotiana tabacum L. cv NC82) were supplied with (NH4)2SO4 or NH4Cl at root-zone pH of 6.0 and 4.5 in hydroponic culture for 28 days. Dry matter accumulation, total N and C content, and leaf area and number were not affected by the NH4+ source or root-zone pH. Plants supplied with NH4Cl accumulated up to 1.2 mM Cl g DW-1, but accumulated 37% less inorganic H2PO4- and 47% less SO4(2-) than plants supplied with (NH4)2SO4. The large Cl- accumulation resulted in NH4Cl- supplied plants having a 31% higher inorganic anion (NO3-, H2, PO4-, SO4(2-), and Cl-) charge. This higher inorganic anion charge in the NH4Cl-supplied plants was balanced by a similar increase in K+ charge. Plants supplied with NH4Cl accumulated greater concentrations of Cl- in leaves (up to 5.1% of DW) than plants supplied with (NH4)2SO4 (less than -% DW). Despite the high Cl- concentration of leaves in NH4Cl supplied plants, these plants showed no symptoms of Cl- toxicity. This demonstrates that toxicity symptoms are not due solely to an interaction between high Cl- concentration in tissue and NH4+ nutrition. The increase in root-zone acidity to pH 4.5 from 6.0 did not induce toxicity symptoms.

NASA Program CELSS↗
NASA NTRS2006

Formation of "Chemically Pure" Magnetite from Mg-Fe-Carbonates Implications for the Exclusively Inorganic Origin of Magnetite and Sulfides in Martian Meteorite ALH84001

Magnetite and sulfides in the black rims of carbonate globules in Martian meteorite ALH84001 have been studied extensively because of the claim by McKay et al. that they are biogenic in origin. However, exclusively inorganic (abiotic) processes are able to account for the occurrence of carbonate-sulfide-magnetite assemblages in the meteorite. We have previously precipitated chemically zoned and sulfide-bearing carbonate globules analogous to those in ALH84001 (at less than or equal to 150 C) from multiple fluxes of variable-composition Ca-Mg-Fe-CO2-S-H2O solutions. Brief heating of precipitated globules to approx. 470 C produced magnetite and pyrrhotite within the globules by thermal decomposition of siderite and pyrite, respectively. We have also shown that morphology of magnetite formed by inorganic thermal decomposition of Fe-rich carbonate is similar to the morphology of so-called biogenic magnetite in the carbonate globules of ALH84001. Magnetite crystals in the rims of carbonate globules in ALH84001 are chemically pure [Note: "Chemically pure" is defined here as magnetite with Mg at levels comparable or lower than Mg detected by [8] in ALH84001 magnetite]. A debate continues on whether or not chemically pure magnetite can form by the thermal decomposition of mixed Mg-Fe-carbonates that have formed under abiotic conditions. Thomas-Keprta et al. argue that it is not possible to form Mg-free magnetite from Mg-Fe-carbonate based on thermodynamic data. We previously suggested that chemically pure magnetite could form by the thermal decomposition of relatively pure siderite in the outer rims of the globules. Mg-Fe-carbonates may also thermally decompose under conditions conducive for formation of chemically pure magnetite. In this paper we show through laboratory experiments that chemically pure magnetite can form by an inorganic process from mixed Mg-Fe-carbonates.

Golden, D. C.↗
NASA NTRS2017

BrO and Inferred Bry Profiles over the Western Pacific: Relevance of Inorganic Bromine Sources and a Bry Minimum in the Aged Tropical Tropopause Layer

We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box model to infer total gas-phase inorganic bromine (Br(sub y)) over the tropical western Pacific Ocean (tWPO) during the CONTRAST field campaign (January-February 2014). The observed BrO and inferred Bry profiles peak in the marine boundary layer (MBL), suggesting the need for a bromine source from sea-salt aerosol (SSA), in addition to organic bromine (CBry ). Both profiles are found to be C-shaped with local maxima in the upper free troposphere (FT). The median tropospheric BrO vertical column density (VCD) was measured as 1.6 x 10(exp 13) molec cm(exp -2), compared to model predictions of 0.9 x 10(exp 13) molec cm(exp -2) in GEOS-Chem (CBr(sub y) but no SSA source), 0.4 x 10(exp 13) molec cm(exp -2) in CAM-Chem (CBr(sub y) and SSA), and 2.1 x 10(exp 13) molec cm(exp -2) in GEOS-Chem (CBry and SSA). Neither global model fully captures the Cshape of the Br(sun y) profile. A local Br(sub y) maximum of 3.6 ppt (2.9-4.4 ppt; 95% confidence interval, CI) is inferred between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective tropical tropopause layer (TTL) to the aged TTL, gas-phase Br(sub y) decreases from the convective TTL to the aged TTL. Analysis of gas-phase Br(sub y) against multiple tracers (CFC-11, H2O/O3 ratio, and potential temperature) reveals a Br(sub y) minimum of 2.7 ppt (2.3-3.1 ppt; 95% CI) in the aged TTL, which agrees closely with a stratospheric injection of 2.6 +/- 0.6 ppt of inorganic Br(sub y) (estimated from CFC-11 correlations), and is remarkably insensitive to assumptions about heterogeneous chemistry. Bry increases to 6.3 ppt (5.6-7.0 ppt; 95% CI) in the stratospheric "middleworld" and 6.9 ppt (6.5-7.3 ppt; 95% CI) in the stratospheric "overworld". The local Br(sub y) minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-Chem, and suggests a more complex partitioning of gas-phase and aerosol Br(sub y) species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA-derived gas-phase Br(sub y) ) are needed to explain the gas-phase Br(sub y) budget in the upper free troposphere and TTL. They are also consistent with observations of significant bromide in Upper Troposphere-Lower Stratosphere aerosols. The total Br(sub y) budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas-phase Br(sub y) species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. Such simultaneous measurements are needed to (1) quantify SSA-derived Br(sub y) in the upper FT, (2) test Br(sub y) partitioning, and possibly explain the gas-phase Br(sub y) minimum in the aged TTL, (3) constrain heterogeneous reaction rates of bromine, and (4) account for all of the sources of Br(sub y) to the lower stratosphere.

Atmospheric Chemistry; bromine; troposphere; CONTR↗
NASA NTRS1974

Structure and function of an inorganic-organic separator for electrochemical cells: Preliminary study

The structure of a new separator material for electrochemical cells has been investigated. Investigation into details of the separator structure showed it to be multilayered and to consist mainly of a quasi-impervious organic skin, a porous region of mixed organic and inorganic material, and an area of nonuniformly treated substrate. The essential feature of the coating (slurry) is believed to be interconnected pores which allow ionic conductivity. The interconnected pores are believed to be formed by the interaction of the plasticizer and inorganic fibers. The major failure mode of silver zinc cells using such a separator (zinc nodules shorting adjacent plates) was investigated.

Bozek, J. M.↗
NASA NTRS1978

Inorganic-organic separators for alkaline batteries

A flexible separator is reported for use between the electrodes of Ni-Cd and Ni-Zn batteries using alkaline electrolytes. The separator was made by coating a porous substrate with a battery separator composition. The coating material included a rubber-based resin copolymer, a plasticizer and inorganic and organic fillers which comprised 55% by volume or less of the coating as finally dried. One or more of the filler materials, whether organic or inorganic, is preferably active with the alkaline electrolyte to produce pores in the separator coating. The plasticizer was an organic material which is hydrolyzed by the alkaline electrolyte to improve conductivity of the separator coating.

Sheibley, D. W.↗
NASA NTRS1979

Control of volume resistivity in inorganic organic separators

Control of resistivity in NASA inorganic-organic separators is achieved by incorporating small percentages of high surface area, fine particle silica with other ingredients in the separator coating. The volume resistivity is predictable from the surface area of filler particles in the coating. The approach is applied to two polymer- plasticizer -filler coating systems, where the filler content of each is below the generally acknowledged critical pigment volume concentration of the coating. Application of these coating systems to 0.0254 cm thick (10-mil) fuel cell grade asbestos sheet produces inexpensive, flexible, microporous separators that perform as well as the original inorganic-organic concept, the Astropower separator.

Sheibley, D. W.↗
NASA NTRS1979

Survey of inorganic polymers

A literature search was carried out in order to identify inorganic, metallo-organic, and hybrid inorganic-organic polymers that could serve as potential matrix resins for advanced composites. The five most promising candidates were critically reviewed and recommendations were made for the achievement of their potential in terms of performance and cost. These generic polymer classes comprise: (1) Poly(arylsil sesquioxanes); (2) Poly(silyl arylene siloxanes); (3) Poly(silarylenes); (4) Poly(silicon-linked ferrocenes); and (5) Poly(organo phosphazenes). No single candidate currently possesses the necessary combination of physicomechanical properties, thermal stability, processability, and favorable economics. The first three classes exhibit the best thermal performance. On the other hand, poly (organo phosphazenes), the most extensively studied polymer class, exhibit the best combination of structure-property control, processability, and favorable economics.

Gerber, A. H.↗
NASA NTRS1979

Lunar building materials: Some considerations on the use of inorganic polymers

The use of inorganic polymer systems synthesized from the available lunar chemical elements, viz., silicon, aluminum, and oxygen to make adhesives, binders, and sealants needed in the fabrication of lunar building materials and the assembly of structures is considered. Inorganic polymer systems, their background, status, and shortcomings, and the use of network polymers as a possible approach to synthesis are examined as well as glassy metals for unusual structural strength, and the use of cold-mold materials as well as foam-sintered lunar silicates for lightweight shielding and structural building materials.

Lee, S. M.↗
NASA NTRS1980

Control of volume resistivity in inorganic-organic separators

Control of resistivity in NASA inorganic-organic separators is achieved by incorporating small percentages of high surface area, fine-particle silica with other ingredients in the separator coating. The volume resistivity appears to be predictable from coating composition, that is, from the surface area of filler particles in the coating. The approach has been applied to two polymer-'plasticizer'-filler coating systems, where the filler content of each is below the generally acknowledged critical pigment volume concentration of the coating. Application of these coating systems to 0.0254 cm thick (10 mil) fuel-cell grade asbestos sheet produces inexpensive, flexible, microporous separators that perform at least as well as the original inorganic-organic concept, the Astropower separator.

Sheibley, D. W.↗
NASA NTRS1984

Inorganic composites for space applications

The development of inorganic composite materials for space applications is reviewed. The composites do not contain any organic materials, and therefore, are not subject to degradation by ultraviolet radiation, volatilization of constituents, or embrittlement at low temperatures. The composites consist of glass, glass/ceramics or ceramic matrices, reinforced by refractory whiskers or fibers. Such composites have the low thermal expansion, refractories, chemical stability and other desirable properties usually associated with the matrix materials. The composites also have a degree of toughness which is extraordinary for refractory inorganic materials.

Malmendier, J. W.↗
NASA NTRS1994

Increase of carbonyl fluoride (COF2) in the stratosphere and its contribution to the 1992 budget of inorganic fluorine in the upper stratosphere

Volume mixing ratio profiles of COF2 have been derived through most of the stratosphere between 30 deg N and 54 deg S from series of 0.01-/cm resolution infrared solar spectra recorded in the occultation mode by the atmospheric trace molecule spectroscopy (ATMOS) instrument during the ATLAS 1 space shuttle mission of March-April 1992. When compared with similar results obtained from the ATMOS/Spacelab 3 mission of April-May 1985, the cumulative increase in the burden of COF2 in the middle and upper stratosphere was found to be 67% for that 7-year time interval. By combining a subset of these COF2 results with upper stratospheric concentrations of HF also derived from the ATMOS observations, it was further found that the budget of inorganic fluorine above 35 km altitude increased by (60 +/- 10)% over the 1985-1992 time interval, which corresponds to an average exponential rate of increase of (6.7 +/- 1/1)%/yr, or a linear rate of increase reference to 1985 of (8.5 +/- 1.3)%/yr at the 1 sigma confidence level. The total inorganic F atom volume mixing ratio found in the upper stratosphere for 1985 and 1992 and the increase during this perid mirror the rise in man-made fluorine-bearing compounds at the ground during the early to mid 1980s. This demonstrates the negligible impact of natural sources of fluorine, in particular volcanic activity, on the observed change in F in the upper stratosphere. Implications of the present findings and comparison with model results are discussed.

Zander, R.↗
NASA NTRS1995

Estimates of total organic and inorganic chlorine in the lower stratosphere from in situ and flask measurements during AASE 2

Aircraft sampling has provided extensive in situ and flask measurements of organic chlorine species in the lower stratosphere. The recent Airborne Arctic Stratospheric Expedition 2 (AASE 2) included two independent measurements of organic chlorine species using whole air sample and real-time techniques. From the whole air sample measurements we derive directly the burden of total organic chlorine (CCl(y)) in the lower stratosphere. From the more limited real-time measurements we estimate the CCl(y) burden using mixing ratios and growth rates of the principal CCl(y) species in the troposphere in conjunction with results from a two-dimensional photochemical model. Since stratospheric chlorine is tropospheric in origin and tropospheric mixing ratios are increasing, it is necessary to establish the average age of a stratospheric air parcel to assess its total chlorine (Cl(sub Total)) abundance. Total inorganic chlorine (Cl(y)) in the parcel is then estimated by the simple difference, Cl(y) = Cl(sub Total) - CCl(y). The consistency of the results from these two quite different techniques suggests that we can determine the CCl(y) and Cl(y) in the lower stratosphere with confidence. Such estimates of organic and inorganic chlorine are crucial in evaluating the photochemistry controlling chlorine partitioning and hence ozone loss processes in the lower stratosphere.

Woodbridge, E. L.↗
NASA NTRS1994

Increase of carbonyl fluoride (COF2) in the stratosphere and its contribution to the 1992 budget of inorganic fluorine in the upper stratosphere

Volume mixing ratio profiles of COF2 have been derived through most of the stratosphere between 30 deg N and 54 deg S from series of 0.01-cm(exp -1) resolution infrared solar spectra recorded in the occultation mode by the atmospheric trace molecule spectroscopy (ATMOS) instrument during the ATLAS 1 space shuttle mission of March-April 1992. When compared with similar results obtained from the ATMOS/Spacelab 3 mission of April-May 1985, the cumulative increase in the burden of COF2 in the middle and upper stratosphere was found to be 67% for that 7-year time interval. By combining a subset of these COF2 results with upper stratospheric concentrations of HF also derived from the ATMOS observations, it was further found that the budget of inorganic fluorine above 35 km altitude increased by (60 +/- 10) % over the 1985-1992 time interval, which corresponds to an average exponential rate of increase of(6.7 +/- 1.1) % /yr , or a linear rate of increase referenced to 1985 of (8.5 +/- 1.3) % /yr at the 1(sigma) confidence level. The total inorganic F atom volume mixing ratio found in the upper stratosphere for 1985 and 1992 and the increase during this period mirror the rise in man-made fluorine-bearing compounds at the ground during the early to mid 1980s. This demonstrates the negligible impact of natural sources of fluorine, in particular volcanic activity, on the observed change of F in the upper stratosphere. Implications of the present findings and comparison with model results are discussed.

Zander, R.↗