Stable carbon isotope fractionation in the search for life on early Mars.

Isotopic measurements and, more specifically, ratios of 13C to 12C in organic relative to inorganic deposits, are useful in reconstructing past biological activity on Earth. Organic matter has a lower ratio of 13C to 12C due largely to the preferential fixation of 12C over the heavier isotope by the major carbon-fixation enzyme, ribulose-1,5-bisphosphate carboxylase/oxygenase, although other factors (e.g., availability of source carbon, fixation by other carboxylating enzymes and diagenesis of organic material) also contribute to fractionation. Would carbon isotope discrepancies between inorganic and organic carbon indicate past biological activity on Mars? In order to answer this question, we analyse what is known about terrestrial biologic and abiologic carbon fixation and its preservation in the fossil record, and suggest what the isotope discrimination during possible biologic and abiologic carbon fixation on Mars might have been like. Primarily because isotopic signatures of abiotically fixed carbon overlap with those of biotic fixation, but also because heterotrophy does not significantly alter the isotopic signature of ingested carbon, fractionation alone would not be definitive evidence for life. However, a narrow range of fractionation, including no fractionation, would suggest biotic processes. Never-the-less, isotopic ratios in organic deposits on Mars would be extremely useful in analysing prebiotic, if not biotic, carbon transformations on Mars.     

Biogeochemical evidence of microbial activity on Mars.

We suggest a new interpretation of the data on so-called SNC meteorites and delta 13C values of the calcium carbonate minerals and organic matter discovered in them. The delta 13C value of calcite (up to 15 ppt) is accounted for by the microbial reaction CO2 + H2 ---> CH4 + H2O. Methane-forming bacteria also synthesize organic carbon (in the form of biomass) from CO2, and this process is accompanied by 12C fractionation. Therefore, the organic carbon of SNC meteorites is enriched with 12C (delta 13C as low as -35 ppt). The environmental conditions under which the calcite of SNC meteorites was formed were favorable for the activity of methanogens.     

The initiation of biological processes on Earth: summary of empirical evidence.

With the currently available geological record at band, the existence of life on this planet as from at least 3.8 Gyr ago seems so firmly established as to be virtually unassailable. Specifically, various disparate lines of evidence have merged to indicate (1) that the surface of the Archaean Earth had hosted prolific microbial ecosystems as is testified by a quasi-continuous record of microbialites ("stromatolites") and associated microfossils of prokaryotic affinity over 3.5, if not 3.8 Gyr of geological history, and (2) that the sedimentary carbon record has preserved the isotopic signature of autotrophic (notably photosynthetic) carbon fixation over the same time span. With the observed enrichment of isotopically light carbon in sedimentary organic matter largely consonant with the bias in favor of 12C during photosynthesis, the mainstream of the carbon isotope record can be best explained as geochemical manifestation of the isotope discriminating properties of the ribulose-1,5-bisphosphate (RuBP) carboxylase reaction of the Calvin cycle suggesting an extreme degree of evolutionary conservatism in the biochemistry of autotrophic carbon fixation. As a consequence, partial biological control of the geochemical carbon cycle was established already during Early Archaean times and fully operative by the time of formation of the Earth's earliest sediments.     

Isotope fractionations in the terrestrial carbon cycle: a brief overview.

The bias in favour of isotopically light carbon inherent in biological carbon fixation has brought about an isotopic disproportionation of primordial (mantle-derived) carbon on a global scale, causing an enrichment of 12C in reduced (biogenic) carbon and a concomitant accumulation of the heavy complement (13C) in the residual oxidized (inorganic) carbon pool. As a result, the terrestrial carbon cycle has gone bipartite, comprising an organic branch of isotopically light carbon, and an inorganic branch made up of 13C-enriched carbon (mostly in the form of carbonate). The isotopic disparity between the two principal terrestrial carbon species can be traced back over 3.8 Gyr of Earth history, attesting to a biological modulation of the carbon cycle since the time of formation of the oldest sediments.     

Polycyclic aromatic hydrocarbon ions and the diffuse interstellar bands.

Neutral naphthalene (C10H8), phenanthrene (C14H10), and pyrene (C16H10) absorb strongly in the ultraviolet and may contribute to the extinction curve. High abundances are required to produce detectable structures. The cations of these PAHs absorb in the visible. C10H8+ has 12 discrete absorption bands which fall between 6800 and 5000 angstroms. The strongest band at 6741 angstroms falls close to the weak 6742 angstroms diffuse interstellar band (DIB). Five other weaker bands also match DIBs. The possibility that C10H8+ is responsible for some of the DIBs can be tested by searching for new DIBs at 6520, 6151, and 5965 angstroms, other moderately strong naphthalene cation band positions. If C10H8+ is indeed responsible for the 6742 angstroms feature, it accounts for 0.3% of the cosmic carbon. The spectrum of C16H10+ is dominated by a strong band at 4435 angstroms in an Ar matrix and 4395 angstroms in a Ne matrix, a position which falls very close to the strongest DIB, that at 4430 angstroms. If C16H10+, or a closely related pyrene-like ion is indeed responsible for the 4430 angstroms feature, it accounts for 0.2% of the cosmic carbon. We also report an intense, very broad UV-to-visible continuum which is associated with both ions and could explain how PAHs convert interstellar UV and visible radiation into IR.     

Biological modulation of the terrestrial carbon cycle: Isotope clues to early organic evolution

The characteristic difference of some 20 to 30 ‰ in the ¹³C/¹²C rations of reduced (organic) and oxidized (carbonate) carbon as observed in the contemporary environment can be traced back over 3.5 (if not 3.8) Ga of recorded Earth history. There is little doubt that the enrichment of isotopically light carbon in fossil organic matter ultimately derives from the bias in favor of ¹²C during photosynthetic carbon fixation (notably the RuBP carboxylase reaction of the Calvin cycle). Accordingly, the mainstream of the sedimentary δ ¹³C_org record can be most reasonably explained as geochemical evidence of the isotope-discriminating properties of the principal CO₂-fixing enzymatic reaction of the assimilatory pathway, thus giving eloquent testimony to an extreme degree of evolutionary conservatism in the biochemistry of autotrophic carbon fixation.     

Utilization of white potatoes in CELSS.

Potatoes (Solanum tuberosum) have a strong potential as a useful crop species in a functioning CELSS. The cultivar Denali has produced 37.5 g m-2 d-1 when grown for 132 days with the first 40 days under a 12-h photoperiod and a light:dark temperature cycle of 20 degrees C:16 degrees C, and then 92 days under continuous irradiance and a temperature of 16 degrees C. Irradiance was at 725 micromoles m-2 s-1 PPF and carbon dioxide at 1000 micromoles mol-1. The dried tubers had 82% carbohydrates, 9% protein and 0.6% fat. Other studies have shown that carbon dioxide supplementation (1000 micromoles mol-1) is of significant benefit under 12-h irradiance but less benefit under 24 h irradiance. Irradiance cycles of 60 minutes light and 30 minutes dark caused a reduction of more than 50% in tuber weight compared to cycles of 16 h light and 8 h dark. A diurnal temperature change of 22 degrees C for the 12-h light period to 14 degrees C during the 12-h dark period gave increased yields of 30% and 10% for two separate cultivars, compared with plants grown under a constant 18 degrees C temperature. Cultivar screening under continuous irradiance and elevated temperatures (28 degrees C) for 8 weeks of growth indicated that the cvs Haig, Denali, Atlantic, Desiree and Rutt had the best potential for tolerance to these conditions. Harvesting of tubers from plants at weekly intervals, beginning at 8 weeks after planting, did not increase yield over a single final harvest. Spacing of plants on 0.055 centers produced greater yield per m2 than spacing at 0.11 or 0.22 m2. Plants maintained 0.33 meters apart (0.111 m2 per plant) in beds produced the same yields when separated by dividers in the root matrix as when no separation was made.     

The origin of organic matter in the Martian meteorite ALH84001.

Stable carbon isotope measurements of the organic matter associated with the carbonate globules and the bulk matrix material in the ALH84001 Martian meteorite indicate that two distinct sources are present in the sample. The delta 13C values for the organic matter associated with the carbonate globules averaged -26% and is attributed to terrestrial contamination. In contrast, the delta 13C values for the organic matter associated with the bulk matrix material yielded a value of -15%. The only common carbon sources on the Earth that yield similar delta 13C values, other then some diagenetically altered marine carbonates, are C4 plants. A delta 13C value of -15%, on the other hand, is consistent with a kerogen-like component, the most ubiquitous form of organic matter found in carbonaceous chondrites such as the Murchison meteorite. Examination of the carbonate globules and bulk matrix material using laser desorption mass spectrometry (LDMS) indicates the presence of a high molecular weight organic component which appears to be extraterrestrial in origin, possibly derived from the exogenous delivery of meteoritic or cometary debris to the surface of Mars.     

The implantation of life on Mars: feasibility and motivation.

Environmental conditions on Mars are extremely hostile, and would be destructive to any organisms which might arrive there unprotected to-day. However, it is a biocompatible planet. Its unalterable astrophysical parameters would allow the maintenance of a much thicker, warmer carbon dioxide atmosphere than that which currently exists. Though very cold (averaging about -60 degrees C), highly oxidizing and desiccated, Mars may possess substantial quantities of the materials needed to support life--in particular, water and carbon dioxide. A general scenario for implanting life on Mars would include three main phases: (1) robotic and human exploration to determine whether sufficiently large and accessible volatile inventories are available; (2) planetary engineering designed to warm the planet, release liquid water and produce a thick carbon dioxide atmosphere; and (3) if no indigenous Martian organisms emerge as liquid water becomes available, a program of biological engineering designed to construct and implant pioneering microbial communities able to proliferate in the newly clement, though still anaerobic, Martian environment. The process of establishing an ecosystem, or biosphere, on a lifeless planet is best termed 'ecopoiesis.' This new word, derived from Greek, means 'the making of an abode for life.' It is by no means clear whether ecopoiesis on Mars is scientifically possible or technologically achievable. Thus we urge that it be one of the objectives of space research during the next century to assess the feasibility of ecopoiesis on Mars.     

Subcritical and supercritical water oxidation of CELSS model wastes.

Controlled-Ecological-Life-Support-System (CELSS) model wastes were wet-oxidized at temperatures from 250 to 500 degrees C, i.e., below and above the critical point of water (374 degrees C and 218 kg/cm2 or 21.4 MPa). A solution of ammonium hydroxide and acetic acid and a slurry of human urine, feces, and wipes were used as model wastes. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 degrees C, i.e., above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. Although the extent of nitrogen oxidation to nitrous oxide (N2O) and/or nitrogen gas (N2) increased with reaction temperature, most of the nitrogen was retained in solution as ammonia near 400 degrees C. This important finding suggests that most of the nitrogen in the waste feed can be retained in solution as ammonia during oxidation at low supercritical temperatures and be subsequently used as a nitrogen source for plants in a CELSS while at the same time organic matter is almost completely oxidized to carbon dioxide and water. It was also found in this study the Hastelloy C-276 alloy reactor corroded during waste oxidation. The rate of corrosion was lower above than below the critical temperature for water.     

Cometary constraints on the planet forming environment.

Molecular elemental and isotopic abundances of comets provide sensitive diagnostics for models of the primitive solar nebula. New measurements of the N2, NH and NH2 abundances in comets together with the in situ Giotto mass spectrometer and dust analyzer data provide new constraints for models of the comet forming environment in the solar nebula. An inventory of nitrogen-containing species in comet Halley indicates that NH3 and CN are the dominant N carriers observed in the coma gas. The elemental nitrogen abundance in the gas component of the coma is found to be depleted by a factor approximately 75 relative to the solar photosphere. Combined with the Giotto dust analyzer results for the coma dust component, we find for comet Halley Ngas + dust approximately 1/6 the solar value. The measurement of the CN carbon isotope ratio from the bulk coma gas and dust in comet Halley indicates a significantly lower value, 12C/13C = 65 +/- 9 than the solar system value of 89 +/- 2. Because the dominant CN carrier species in comets remains unidentified, it is not yet possible to attribute the low isotope ratio predominantly to the bulk gas or dust components. The large chemical and isotopic inhomogeneities discovered in the Halley dust particles on 1 mu scales are indicative of preserved circumstellar grains which survived processing in the interstellar clouds, and may be related to the presolar silicon carbide, diamond and graphite grains recently discovered in carbonaceous chondrites. Less than 0.1% of the bulk mass in the primitive meteorites studied consists of these cosmically important grains. A larger mass fraction (approximately 5%) of chemically heterogeneous organic grains is found in the nucleus of comet Halley. The isotopic anomalies discovered in the PUMA 1 Giotto data in comet Halley are probably also attributable to preserved circumstellar grains. Thus the extent of grain processing in the interstellar environment is much less than predicted by interstellar grain models, and a significant fraction of comet nuclei (approximately 5%) may be in the form of preserved circumstellar matter. Comet nuclei probably formed in much more benign environments than primitive meteorites.     

Chemical evolution and the origin of life.

During the last three decades major advances have been made in our understanding of the formation of carbon compounds in the universe and of the occurence of processes of chemical evolution. 1) Carbon and other biogenic elements (C,H,N,O,S and P) are some of the most abundant in the universe. 2) The interstellar medium has been found to contain a diversity of molecules of these elements. 3) Some of these molecules have also been found in comets which are considered the most primordial bodies of the solar system. 4) The atmospheres of the outer planets and their satellites, for example, Titan, are actively involved in the formation of organic compounds which are the precursors of biochemical molecules. 5) Some of these biochemical molecules, such as amino acids, purines and pyrimidines, have been found in carbonaceous chondrites. 6) Laboratory experiments have shown that most of the monomers and oligomers necessary for life can be synthesized under hypothesized but plausible primitive Earth conditions from compounds found in the above cosmic bodies. 7) It appears that the primitive Earth had the necessary and sufficient conditions to allow the chemical synthesis of biomacromolecules and to permit the processes required for the emergence of life on our planet. 8) It is unlikely that the emergence of life occurred in any other body of the solar system, although the examination of the Jovian satellite Europa may provide important clues about the constraints of this evolutionary process. Some of the fundamental principles of chemical evolution are briefly discussed.     

Fullerenes in space.

The discovery and synthesis of fullerenes led to the hypothesis that they may be present and stable in interstellar space. Fullerenes have been reported in an impact crater on the LDEF spacecraft. Investigations of fullerenes in carbonaceous meteorites have yielded only small upper limits. Fullerene compounds and their ions could be interesting carrier molecules for some of the "diffuse interstellar bands" (DIBs), a long standing mystery in astronomy. We have detected two new diffuse bands that are consistent with laboratory measurements of the C60+, as first evidence for the largest molecule ever detected in space. Criteria for this identification are discussed. The inferred abundance (up to 0.9 % of cosmic carbon locked in C60+) suggests that fullerenes may play an important role in interstellar chemistry. We present new observations on DIB substructures consistent with fullerene compounds, and the search for neutral C60 in the diffuse medium.     

Bio-markers and the search for extinct life on Mars.

Geologic and climatologic studies suggest that conditions on early Mars were similar to early Earth. Because life on Earth is believed to have originated during this early period (3.5 billion years ago), the Martian environment could have also been conducive to the origin of life. To investigate this possibility we must first define the attributes of an early Martian biota. Then, specific geographic locations on Mars must be chosen where life may have occurred (i.e. areas which had long standing water), and within these distinct locations search for key signatures or bio-markers of a possible extinct Martian biota. Some of the key signatures or bio-markers indicative of past biological activity on Earth may be applicable to Mars including: reduced carbon and nitrogen compounds, CO3(2-), SO4(2-), NO3-, NO2- [correction of NO2(2)], Mg, Mn, Fe, and certain other metals, and the isotopic ratios of C, N and S. However, we must also be able to distinguish abiotic from biologic origins for these bio-markers. For example, abiotically fixed N2 would form deposits of NO3- and NO2-, whereas biological processes would have reduced these to ammonium containing compounds, N2O, or N2, which would then be released to the atmosphere. A fully equipped Mars Rover might be able to perform analyses to measure most of these biomarkers while on the Martian surface.     

Hot atoms in cosmic chemistry

High energy chemical reactions and atom molecule interactions might be important for cosmic chemistry with respect to the accelerated species in solar wind, cosmic rays, colliding gas and dust clouds and secondary knock-on particles in solids. “Hot” atoms with energies ranging from a few eV to some MeV can be generated via nuclear reactions and consequent recoil processes. The chemical fate of the radioactive atoms can be followed by radiochemical methods (radio GC or HPLC). Hot atom chemistry may serve for laboratory simulation of the reactions of energetic species with gaseous or solid interstellar matter. Due to the effective measurement of 10⁸–10¹⁰ atoms only it covers a low to medium dose regime and may add to the studies of ion implantation which due to the optical methods applied are necessarily in the high dose regime.

Experimental results are given for the systems: C/H₂O (gas), C/H₂O (solid, 77 K), N/CH₄ (solid, 77K) and C/NH₃ (solid, 77 K). Nuclear reactions used for the generation of 2 to 3 MeV atoms are: ¹⁴N(p, ) ¹¹C, ¹⁶O(p, pn) ¹¹C and ¹²C(d,n) ¹³N with 8 to 45 MeV protons or deuterons from a cyclotron. Typical reactions products are: CO, CO₂, CH₄, CH₂O, CH₃OH, HCOOH, NH₃, CH₃NH₂, cyanamide, formamidine, guanidine etc. Products of hot reactions in solids are more complex than in corresponding gaseous systems, which underlines the importance of solid state reactions for the build-up of precursors for biomolecules in space. As one of the major mechanisms for product formation, the simultaneous or fast consecutive reactions of a hot carbon with two target molecules (reaction complex) is discussed.     

Comparison study of ductile iron produced with Martian regolith harvested iron from ionic liquids and Bosch byproduct carbon for in-situ resource utilization versus commercially available 65-45-12 ductile iron

As researchers continue to study methods to facilitate long-term missions beyond low-Earth orbit, the ability to manufacture high-quality mechanical and structural components on the Lunar and Martian surfaces remains a crucial piece to the puzzle for a sustained presence. Due to the immense cost of sending supplies to extraterrestrial bodies, in-situ resource utilization (ISRU) methods are critical for the success and feasibility of these habitation missions. Ionic liquids (ILs) are currently being studied at NASA’s Marshall Space Flight Center (MSFC) to harvest elemental metals from meteorites and regolith minerals. Additionally, the Bosch process is being explored as a life support system at MSFC for oxygen (O₂) regeneration, rendering a byproduct of elemental carbon (C). In this investigation, the viability of casting ductile iron (DI) using IL-sourced iron (IL-Fe) and Bosch C was studied given the range of applications and performance of DI as an as-cast alloy. Ingots were produced using commercial elements to simulate the use of IL-Fe with C sourced from the byproduct C of the Bosch process. Samples were cast and compared to commercially available 65–45-12 DI with phase transformation diagrams, microstructures, and hardness. Results showed that IL-sourced elements are a viable source of elemental alloying materials for a range of DI alloys, with some limitations.     

Soil carbon distribution and site characteristics in hyper-arid soils of the Atacama Desert: A site with Mars-like soils

The soil carbon content and its relation to site characteristics are important in evaluating current local, regional, and global soil C storage and projecting future variations in response to climate change. In this study we analyzed the concentration of organic and inorganic carbon and their relationship with in situ climatic and geological characteristics in 485 samples of surface soil and 17 pits from the hyper-arid area and 51 samples with 2 pits from the arid–semiarid region from the Atacama Desert located in Peru and Chile. The soil organic carbon (SOC) in hyperarid soils ranged from 1.8 to 50.9 μg C per g of soil for the 0–0.1 m profile and from 1.8 to 125.2 μg C per g of soil for the 0–1 m profile. The analysis of climatic (temperature and precipitation), elevation, and some geologic characteristics (landforms) associated with hyper-arid soils explained partially the SOC variability. On the other hand, soil inorganic carbon (SIC) contents, in the form of carbonates, ranged from 200 to 1500 μg C per g of soil for the 0–0.1 m profile and from 200 to 3000 μg C per g of soil for the 0–1.0 m profile in the driest area. The largest accumulations of organic and inorganic carbon were found near to arid–semiarid areas. In addition, the elemental carbon concentrations show that the presence of other forms of inorganic carbon (e.g. graphite, etc.) was negligible in these hyperarid soils. Overall, the top 1 m soil layer of hyperarid lands contains ∼11.6 Tg of organic carbon and 344.6 Tg of carbonate carbon. The total stored carbon was 30.8-fold the organic carbon alone. To our knowledge, this is the first study evaluating the total budget carbon on the surface and shallow subsurface on ∼160,000 km² of hyperarid soils.     

Biomass recycle as a means to improve the energy efficiency of CELSS algal culture systems.

Algal cultures can be very rapid and efficient means to generate biomass and regenerate the atmosphere for closed environmental life support systems. However, as in the case of most higher plants, a significant fraction of the biomass produced by most algae cannot be directly converted to a useful food product by standard food technology procedures. This waste biomass will serve as an energy drain on the overall system unless it can be efficiently recycled without a significant loss of its energy content. We report experiments in which cultures of the algae Scenedesmus obliquus were grown in the light and at the expense of an added carbon source, which either replaced or supplemented the actinic light. As part of these experiments we tested hydrolyzed waste biomass from these same algae to determine whether the algae themselves could be made part of the biological recycling process. Results indicate that hydrolyzed algal (and plant) biomass can serve as carbon and energy sources for the growth of these algae, suggesting that the efficiency of the closed system could be significantly improved using this recycling process.     

基于MIV的碳钢大气腐蚀速率影响因子权重分析

通过平均影响值（MIV）影响因子权重分析算法,以碳钢Q235、Ste355、St12和Q450腐蚀速率的暴露时间、气候因素和环境因素数据为依据,以|MIV|值为评价依据,定量分析15种影响因子（暴露时间、平均温度、平均相对湿度、日照时数、降水量、平均风速、海盐粒子浓度、SO₂、HCl、NO₂、H₂S、硫酸盐化速率、NH₃、降尘量-非水溶性、降尘量-水溶性）对碳钢腐蚀速率影响的权重大小。结果表明: 当MIV调节率从5%逐步递增至25%时,同种影响因子对腐蚀速率的影响权重变化不大,但4种碳钢对各影响因子的敏感度略有不同;气候因素对腐蚀速率影响最大,其次为暴露时间,环境因素中SO₂和降尘量对腐蚀速率影响较大;平均相对湿度、日照时数、平均温度是影响腐蚀速率最主要的3个因子。      

Direct radiative forcing from black carbon aerosols over urban environment

There is growing evidence that the earth’s climate is changing and will likely continue to change in the future. It is still debated whether these changes are due to natural variability of the climate system or a result of increases in the concentration of greenhouse gases in the atmosphere. Black carbon (BC) has become the subject of interest for a variety of reasons. BC aerosol may cause environmental as well as harmful health effects in densely inhabited regions. BC is a strong absorber of radiation in the visible and near-infrared part of the spectrum, where most of the solar energy is distributed. Black carbon is emitted into the atmosphere as a byproduct of all combustion processes, viz., vegetation burning, industrial effluents and motor vehicle exhausts, etc. In this paper, we present results from our measurements on black carbon aerosols, total aerosol mass concentration and aerosol optical depth over an urban environment namely Hyderabad during January to May, 2003. Diurnal variations of BC indicate high BC concentrations during 6:00–9:00 and 19:00–23:00 h. Weekday variations of BC concentrations increase gradually from Monday to Wednesday and gradually decrease from Thursday to Sunday. Analysis of traffic density along with meteorological parameters suggests that the primary determinant for BC concentration levels and patterns is traffic density. Seasonal variations of BC suggest that the BC concentrations are high during dry season compared to rainy season due to the scavenging by air. The fraction of BC to total mass concentration has been observed to be 7% during January to May. BC showed positive correlation with total mass concentration and aerosol optical depth at 500 nm. Radiative transfer calculations suggests that during January to May, diurnal averaged aerosol forcing at the surface is −33 Wm² and at the top of the atmosphere (TOA) above 100 km it is observed to be +9 Wm⁻². The results have been discussed in detail in the paper.