Nitrogen fixation on early Mars and other terrestrial planets: experimental demonstration of abiotic fixation reactions to nitrite and nitrate.

Understanding the abiotic fixation of nitrogen is critical to understanding planetary evolution and the potential origin of life on terrestrial planets. Nitrogen, an essential biochemical element, is certainly necessary for life as we know it to arise. The loss of atmospheric nitrogen can result in an incapacity to sustain liquid water and impact planetary habitability and hydrological processes that shape the surface. However, our current understanding of how such fixation may occur is almost entirely theoretical. This work experimentally examines the chemistry, in both gas and aqueous phases, that would occur from the formation of NO and CO by the shock heating of a model carbon dioxide/nitrogen atmosphere such as is currently thought to exist on early terrestrial planets. The results show that two pathways exist for the abiotic fixation of nitrogen from the atmosphere into the crust: one via HNO and another via NO(2). Fixation via HNO, which requires liquid water, could represent fixation on a planet with liquid water (and hence would also be a source of nitrogen for the origin of life). The pathway via NO(2) does not require liquid water and shows that fixation could occur even when liquid water has been lost from a planet's surface (for example, continuing to remove nitrogen through NO(2) reaction with ice, adsorbed water, etc.).

Functionalization of carbon nanotubes via nitrogen glow discharge.

We have exposed single-wall carbon nanotubes (SWCNTs) to microwave-generated N2 plasma with the aim to functionalize the nanotubes. The results strongly depend on the distance between the discharge source and the sample, since nitrogen atoms generated can be lost due to recombination. No functionalization was observed when this distance was 7.0 cm. At intermediate distances (2.5 cm), the incorporation of nitrogen and oxygen onto the SWCNT was observed, while, at short distances (1 cm), products containing CN were also observed.

Impact of low-temperature plasmas on Deinococcus radiodurans and biomolecules.

The effects of cold plasma on Deinococcus radiodurans, plasmid DNA, and model proteins were assessed using microbiological, spectrometric, and biochemical techniques. In low power O(2) plasma (approximately 25 W, approximately 45 mTorr, 90 min), D. radiodurans, a radiation-resistant bacterium, showed a 99.999% reduction in bioburden. In higher power O(2) plasma (100 W and 500 mTorr), the reduction rate increased about 10-fold and observation by atomic force microscopy showed significant damage to the cell. Damage to cellular lipids, proteins, and chromosome was indicated by losses of infrared spectroscopic peaks at 2930, 1651, 1538, and 1245 cm(-1), respectively. In vitro experiments show that O(2) plasmas induce DNA strand scissions and cross-linking as well as reduction of enzyme activity. The observed degradation and removal of biomolecules was power-dependent. Exposures to 200 W at 500 mTorr removed biomolecules to below detection limits in 60 s. Emission spectroscopy indicated that D. radiodurans cells were volatilized into CO(2), CO, N(2), and H(2)O, confirming that these plasmas were removing complex biological matter from surfaces. A CO(2) plasma was not as effective as the O(2) plasma, indicating the importance of plasma composition and the dominant role of chemical degradation. Together, these findings have implications for NASA planetary protection schemes and for the contamination of Mars.

Abiotic nitrogen fixation on terrestrial planets: reduction of NO to ammonia by FeS.

Understanding the abiotic fixation of nitrogen and how such fixation can be a supply of prebiotic nitrogen is critical for understanding both the planetary evolution of, and the potential origin of life on, terrestrial planets. As nitrogen is a biochemically essential element, sources of biochemically accessible nitrogen, especially reduced nitrogen, are critical to prebiotic chemistry and the origin of life. Loss of atmospheric nitrogen can result in loss of the ability to sustain liquid water on a planetary surface, which would impact planetary habitability and hydrological processes that shape the surface. It is known that NO can be photochemically converted through a chain of reactions to form nitrate and nitrite, which can be subsequently reduced to ammonia. Here, we show that NO can also be directly reduced, by FeS, to ammonia. In addition to removing nitrogen from the atmosphere, this reaction is particularly important as a source of reduced nitrogen on an early terrestrial planet. By converting NO directly to ammonia in a single step, ammonia is formed with a higher product yield (~50%) than would be possible through the formation of nitrate/nitrite and subsequent conversion to ammonia. In conjunction with the reduction of NO, there is also a catalytic disproportionation at the mineral surface that converts NO to NO2 and N2O. The NO2 is then converted to ammonia, while the N2O is released back in the gas phase, which provides an abiotic source of nitrous oxide.

Laboratory studies of butane nucleation on organic haze particles: application to Titan's clouds.

Titan, Saturn's largest satellite, has a thick nitrogen/methane atmosphere with various hydrocarbons present in minor amounts. Recent observations suggest that CH4 may condense to form clouds near the moon's tropopause. Titan's methane cloud formation is probably triggered by a sequential nucleation of hydrocarbons onto Titan's haze material as tropospheric convection occurs due to differential heating of the surface or as the haze settles through the lower stratosphere. To better constrain Titan's cloud formation mechanism, investigations of the nucleation of several hydrocarbons will be necessary. Butane was chosen for this study because it has a relatively high freezing point and is estimated to be present at 200 part per billion levels. If this amount of butane were to condense on each haze particle, a visible cloud would be observed. Laboratory measurements at T = 125 K were performed to determine the relative ease of solid butane nucleation onto laboratory-produced tholin particles having an elemental composition of C5H5N, and solid films of hexane and acetonitrile. We find that butane nucleation onto the haze particles requires a relatively high saturation ratio of S > 1.30. Because butane nucleation is difficult, it may occur on only a very small subset of the total haze particles available. Such selective nucleation of butane would lead to those particles becoming coated with significant amounts of butane. Requiring a high saturation ratio for butane nucleation will reduce the optical depth of butane clouds by a factor of 100 because the particles will be fewer in number for a given condensed mass.