Common freshwater cyanobacteria grow in 100% CO2

Cyanobacteria and similar organisms produced most of the oxygen found in Earth's atmosphere, which implies that early photosynthetic organisms would have lived in an atmosphere that was rich in CO2 and poor in O2. We investigated the tolerance of several cyanobacteria to very high (>20 kPa) concentrations of atmospheric CO2. Cultures of Synechococcus PCC7942, Synechocystis PCC7942, Plectonema boryanum, and Anabaena sp. were grown in liquid culture sparged with CO2-enriched air. All four strains grew when transferred from ambient CO2 to 20 kPa partial pressure of CO2 (pCO2), but none of them tolerated direct transfer to 40 kPa pCO2. Synechococcus and Anabaena survived 101 kPa (100%) pCO2 when pressure was gradually increased by 15 kPa per day, and Plectonema actively grew under these conditions. All four strains grew in an anoxic atmosphere of 5 kPa pCO2 in N2. Strains that were sensitive to high CO2 were also sensitive to low initial pH (pH 5-6). However, low pH in itself was not sufficient to prevent growth. Although mechanisms of damage and survival are still under investigation, we have shown that modern cyanobacteria can survive under Earth's primordial conditions and that cyanobacteria-like organisms could have flourished under conditions on early Mars, which probably had an atmosphere similar to early Earth's.     

The carbonate-silicate cycle and CO2/climate feedbacks on tidally locked terrestrial planets

Atmospheric gaseous constituents play an important role in determining the surface temperatures and habitability of a planet. Using a global climate model and a parameterization of the carbonate-silicate cycle, we explored the effect of the location of the substellar point on the atmospheric CO(2) concentration and temperatures of a tidally locked terrestrial planet, using the present Earth continental distribution as an example. We found that the substellar point's location relative to the continents is an important factor in determining weathering and the equilibrium atmospheric CO(2) level. Placing the substellar point over the Atlantic Ocean results in an atmospheric CO(2) concentration of 7 ppmv and a global mean surface air temperature of 247 K, making ～30% of the planet's surface habitable, whereas placing it over the Pacific Ocean results in a CO(2) concentration of 60,311 ppmv and a global temperature of 282 K, making ～55% of the surface habitable.     

Mass-independent fractionation of sulfur isotopes in Archean sediments: strong evidence for an anoxic Archean atmosphere

Mass-independent fractionation (MIF) of sulfur isotopes has been reported in sediments of Archean and Early Proterozoic Age (> 2.3 Ga) but not in younger rocks. The only fractionation mechanism that is consistent with the data on all four sulfur isotopes involves atmospheric photochemical reactions such as SO2 photolysis. We have used a one-dimensional photochemical model to investigate how the isotopic fractionation produced during SO2 photolysis would have been transferred to other gaseous and particulate sulfur-bearing species in both low-O2 and high-O2 atmospheres. We show that in atmospheres with O2 concentrations < 10(-5) times the present atmospheric level (PAL), sulfur would have been removed from the atmosphere in a variety of different oxidation states, each of which would have had its own distinct isotopic signature. By contrast, in atmospheres with O2 concentrations > or = 10(-5) PAL, all sulfur-bearing species would have passed through the oceanic sulfate reservoir before being incorporated into sediments, so any signature of MIF would have been lost. We conclude that the atmospheric O2 concentration must have been < 10(-5) PAL prior to 2.3 Ga.     

Spectral signatures of photosynthesis. II. Coevolution with other stars and the atmosphere on extrasolar worlds

As photosynthesis on Earth produces the primary signatures of life that can be detected astronomically at the global scale, a strong focus of the search for extrasolar life will be photosynthesis, particularly photosynthesis that has evolved with a different parent star. We take previously simulated planetary atmospheric compositions for Earth-like planets around observed F2V and K2V, modeled M1V and M5V stars, and around the active M4.5V star AD Leo; our scenarios use Earth's atmospheric composition as well as very low O2 content in case anoxygenic photosynthesis dominates. With a line-by-line radiative transfer model, we calculate the incident spectral photon flux densities at the surface of the planet and under water. We identify bands of available photosynthetically relevant radiation and find that photosynthetic pigments on planets around F2V stars may peak in absorbance in the blue, K2V in the red-orange, and M stars in the near-infrared, in bands at 0.93-1.1 microm, 1.1-1.4 microm, 1.5-1.8 microm, and 1.8-2.5 microm. However, underwater organisms will be restricted to wavelengths shorter than 1.4 microm and more likely below 1.1 microm. M star planets without oxygenic photosynthesis will have photon fluxes above 1.6 microm curtailed by methane. Longer-wavelength, multi-photo-system series would reduce the quantum yield but could allow for oxygenic photosystems at longer wavelengths. A wavelength of 1.1 microm is a possible upper cutoff for electronic transitions versus only vibrational energy; however, this cutoff is not strict, since such energetics depend on molecular configuration. M star planets could be a half to a tenth as productive as Earth in the visible, but exceed Earth if useful photons extend to 1.1 microm for anoxygenic photosynthesis. Under water, organisms would still be able to survive ultraviolet flares from young M stars and acquire adequate light for growth.     

Substrate limitation for methanogenesis in hypersaline environments

Motivated by the increasingly abundant evidence for hypersaline environments on Mars and reports of methane in its atmosphere, we examined methanogenesis in hypersaline ponds in Baja California Sur, Mexico, and in northern California, USA. Methane-rich bubbles trapped within or below gypsum/halite crusts have δ13C values near -40‰. Methane with these relatively high isotopic values would typically be considered thermogenic; however, incubations of crust samples resulted in the biological production of methane with similar isotopic composition. A series of measurements aimed at understanding the isotopic composition of methane in hypersaline systems was therefore undertaken. Methane production rates, as well as the concentrations and isotopic composition of the particulate organic carbon (POC), were measured. Methane production was highest from microbial communities living within gypsum crusts, whereas POC content at gypsum/halite sites was low, generally less than 1% of the total mass. The isotopic composition of the POC ranged from -26‰ to -10‰. To determine the substrates used by the methanogens, 13C-labeled methylamines, methanol, acetate, and bicarbonate were added to individual incubation vials, and the methane produced was monitored for 13C content. The main substrates used by the methanogens were the noncompetitive substrates, the methylamines, and methanol. When unlabeled trimethylamine (TMA) was added to incubating gypsum/halite crusts in increasing concentrations, the isotopic composition of the methane produced became progressively lower; the lowest methane δ13C values occurred when the most TMA was added (1000 μM final concentration). This decrease in the isotopic composition of the methane produced with increasing TMA concentrations, along with the high in situ methane δ13C values, suggests that the methanogens within the crusts are operating at low substrate concentrations. It appears that substrate limitation is decreasing isotopic fractionation during methanogenesis, which results in these abnormally high biogenic methane δ13C values.     

Production of oxidants by ion irradiation of water/carbon dioxide frozen mixtures

We present new experimental results on the formation of oxidants, such as hydrogen peroxide, ozone, and carbonic acid, under ion irradiation of icy mixtures of water/carbon dioxide at different ratios and temperatures (16 and 80 K). Pure water ice layers and mixtures with carbon dioxide were irradiated by 200 keV He+ ions. We found that the CO(2)/H(2)O ratio progressively decreased to a value of about 0.1, the H(2)O(2) production increased with increasing CO(2) abundance at both 16 and 80 K, and the CO and H(2)CO(3) production increased with increasing CO(2) abundance at 16 K. At 80 K, the synthesis of CO was less efficient because of the high volatility of the molecule that partially sublimed from the target. The production of carbonic acid was connected with the production of CO(3). O(3) was detected only after ion irradiation of CO(2)-rich mixtures. The experimental results are discussed with regard to the relevance they may have in the production of an energy source for a europan or a martian biosphere.     

甲烷-乙烷混合推进剂深度过冷技术的实验研究

针对甲烷采用液氮过冷可能发生甲烷冰堵风险,提出了在甲烷中添加乙烷,制备凝固温度更低的甲烷-乙烷混合推进剂的新方案,搭建实验系统测试了甲烷-乙烷凝固温度变化规律。研究发现,随着甲烷含量提高,混合推进剂凝固温度先降低后升高。当甲烷、乙烷比例为0.71∶0.29时,混合推进剂达到最低凝固温度,约73.0 K。当采用常压饱和液氮对混合推进剂过冷时,控制甲烷含量在0.52~0.81间可避免推进剂冻结。相较于常压饱和甲烷,防冻结区的混合推进剂密度提高了24.0%~38.4%,液相存在温区增大至35.7 K~40.5 K。此外,甲烷-乙烷混合推进剂具有理论比冲高、再生冷却性能佳、结焦与积碳小等优势。所提出的甲烷-乙烷混合推进剂在火星探测等任务中具有可观的应用前景。     

The physics,biology, and environmental ethics of making mars habitable

The considerable evidence that Mars once had a wetter, more clement, environment motivates the search for past or present life on that planet. This evidence also suggests the possibility of restoring habitable conditions on Mars. While the total amounts of the key molecules--carbon dioxide, water, and nitrogen--needed for creating a biosphere on Mars are unknown, estimates suggest that there may be enough in the subsurface. Super greenhouse gases, in particular, perfluorocarbons, are currently the most effective and practical way to warm Mars and thicken its atmosphere so that liquid water is stable on the surface. This process could take approximately 100 years. If enough carbon dioxide is frozen in the South Polar Cap and absorbed in the regolith, the resulting thick and warm carbon dioxide atmosphere could support many types of microorganisms, plants, and invertebrates. If a planet-wide martian biosphere converted carbon dioxide into oxygen with an average efficiency equal to that for Earth's biosphere, it would take > 100,000 years to create Earth-like oxygen levels. Ethical issues associated with bringing life to Mars center on the possibility of indigenous martian life and the relative value of a planet with or without a global biosphere.     

Survival of methanogens during desiccation: implications for life on Mars

The relatively recent discoveries that liquid water likely existed on the surface of past Mars and that methane currently exists in the martian atmosphere have fueled the possibility of extant or extinct life on Mars. One possible explanation for the existence of the methane would be the presence of methanogens in the subsurface. Methanogens are microorganisms in the domain Archaea that can metabolize molecular hydrogen as an energy source and carbon dioxide as a carbon source and produce methane. One factor of importance is the arid nature of Mars, at least at the surface. If one is to assume that life exists below the surface, then based on the only example of life that we know, liquid water must be present. Realistically, however, that liquid water may be seasonal just as it is at some locations on our home planet. Here we report on research designed to determine how long certain species of methanogens can survive desiccation on a Mars soil simulant, JSC Mars-1. Methanogenic cells were grown on JSC Mars-1, transferred to a desiccator within a Coy anaerobic environmental chamber, and maintained there for varying time periods. Following removal from the desiccator and rehydration, gas chromatographic measurements of methane indicated survival for varying time periods. Methanosarcina barkeri survived desiccation for 10 days, while Methanobacterium formicicum and Methanothermobacter wolfeii were able to survive for 25 days.     

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.).     

Haze aerosols in the atmosphere of early Earth: manna from heaven

An organic haze layer in the upper atmosphere of Titan plays a crucial role in the atmospheric composition and climate of that moon. Such a haze layer may also have existed on the early Earth, providing an ultraviolet shield for greenhouse gases needed to warm the planet enough for life to arise and evolve. Despite the implications of such a haze layer, little is known about the organic material produced under early Earth conditions when both CO(2) and CH(4) may have been abundant in the atmosphere. For the first time, we experimentally demonstrate that organic haze can be generated in different CH(4)/CO(2) ratios. Here, we show that haze aerosols are able to form at CH(4) mixing ratios of 1,000 ppmv, a level likely to be present on early Earth. In addition, we find that organic hazes will form at C/O ratios as low as 0.6, which is lower than the predicted value of unity. We also show that as the C/O ratio decreases, the organic particles produced are more oxidized and contain biologically labile compounds. After life arose, the haze may thus have provided food for biota.     

Long-term manipulations of intact microbial mat communities in a greenhouse collaboratory: simulating earth's present and past field environments

Photosynthetic microbial mat communities were obtained from marine hypersaline saltern ponds, maintained in a greenhouse facility, and examined for the effects of salinity variations. Because these microbial mats are considered to be useful analogs of ancient marine communities, they offer insights about evolutionary events during the >3 billion year time interval wherein mats co-evolved with Earth's lithosphere and atmosphere. Although photosynthetic mats can be highly dynamic and exhibit extremely high activity, the mats in the present study have been maintained for >1 year with relatively minor changes. The major groups of microorganisms, as assayed using microscopic, genetic, and biomarker methodologies, are essentially the same as those in the original field samples. Field and greenhouse mats were similar with respect to rates of exchange of oxygen and dissolved inorganic carbon across the mat-water interface, both during the day and at night. Field and greenhouse mats exhibited similar rates of efflux of methane and hydrogen. Manipulations of salinity in the water overlying the mats produced changes in the community that strongly resemble those observed in the field. A collaboratory testbed and an array of automated features are being developed to support remote scientific experimentation with the assistance of intelligent software agents. This facility will permit teams of investigators the opportunity to explore ancient environmental conditions that are rare or absent today but that might have influenced the early evolution of these photosynthetic ecosystems.     

A regenerable carbon dioxide removal and oxygen recovery system for the Japanese Experiment Module

The Japanese Space Station Program is now under Phase B study by the National Space Development Agency of Japan in participation with the U.S. Space Station Program. A Japanese Space Station participation will be a dedicated pressurized module to be attached to the U.S. Space Station, and is called Japanese Experiment Module (JEM). Astronaut scientists will conduct various experimental operations there. Thus an environment control and life support system is required. Regenerable carbon dioxide removal and collection technique as well as oxygen recovery technique has been studied and investigated for several years. A regenerable carbon dioxide removal subsystem using steam desorbed solid amine and an oxygen recovery subsystem using Sabatier methane cracking have a good possibility for the application to the Japanese Experiment Module. Basic performance characteristics of the carbon dioxide removal and oxygen recovery subsystem are presented according to the results of a fundamental performance test program. The trace contaminant removal process is also investigated and discussed. The solvent recovery plant for the regeneration of various industrial solvents, such as hydrocarbons, alcohols and so on, utilizes the multi-bed solvent adsorption and steam desorption process, which is very similar to the carbon dioxide removal subsystem. Therefore, to develop essential components including adsorption tank (bed), condenser. process controller and energy saving system, the technology obtained from the experience to construct solvent recovery plant can be easily and effectively applicable to the carbon dioxide removal subsystem. The energy saving efficiency is evaluated for blower power reduction, steam reduction and waste heat utilization technique. According to the above background, the entire environment control and life support system for the Japanese Experiment Module including the carbon dioxide removal and oxygen recovery subsystem is evaluated and proposed.     

Biomarker response to galactic cosmic ray-induced NOx and the methane greenhouse effect in the atmosphere of an Earth-like planet orbiting an M dwarf star

Planets orbiting in the habitable zone of M dwarf stars are subject to high levels of galactic cosmic rays (GCRs), which produce nitrogen oxides (NOx) in Earth-like atmospheres. We investigate to what extent these NO(Mx) species may modify biomarker compounds such as ozone (O3) and nitrous oxide (N2O), as well as related compounds such as water (H2O) (essential for life) and methane (CH4) (which has both abiotic and biotic sources). Our model results suggest that such signals are robust, changing in the M star world atmospheric column due to GCR NOx effects by up to 20% compared to an M star run without GCR effects, and can therefore survive at least the effects of GCRs. We have not, however, investigated stellar cosmic rays here. CH4 levels are about 10 times higher on M star worlds than on Earth because of a lowering in hydroxyl (OH) in response to changes in the ultraviolet. The higher levels of CH4 are less than reported in previous studies. This difference arose partly because we used different biogenic input. For example, we employed 23% lower CH4 fluxes compared to those studies. Unlike on Earth, relatively modest changes in these fluxes can lead to larger changes in the concentrations of biomarker and related species on the M star world. We calculate a CH4 greenhouse heating effect of up to 4K. O3 photochemistry in terms of the smog mechanism and the catalytic loss cycles on the M star world differs considerably compared with that of Earth.     

Aqueous corrosion of phosphide minerals from iron meteorites: a highly reactive source of prebiotic phosphorus on the surface of the early Earth

We present the results of an experimental study of aqueous corrosion of Fe-phosphide under conditions relevant to the early Earth. The results strongly suggest that iron meteorites were an important source of reactive phosphorus (P), a requirement for the formation of P-based life. We further demonstrate that iron meteorites were an abundant source of phosphide minerals early in Earth history. Phosphide corrosion was studied in five different solutions: deionized water, deionized water buffered with sodium bicarbonate, deionized water with dissolved magnesium and calcium chlorides, deionized water containing ethanol and acetic acid, and deionized water containing the chlorides, ethanol, and acetic acid. Experiments were performed in the presence of both air and pure Ar gas to evaluate the effect of atmospheric chemistry. Phosphide corrosion in deionized water results in a metastable mixture of mixed-valence, P-bearing ions including pyrophosphate and triphosphate, key components for metabolism in modern life. In a pH-buffered solution of NaHCO(3), the condensed and reduced species diphosphonate is an abundant corrosion product. Corrosion in ethanol- and acetic acid-containing solutions yields additional P-bearing organic molecules, including acetyl phosphonate and a cyclic triphosphorus molecule. Phosphonate is a major corrosion product of all experiments and is the only P-bearing molecule that persists in solutions with high concentrations of magnesium and calcium chlorides, which suggests that phosphonate may have been a primitive oceanic source of P. The stability and reactivity of phosphonate and hypophosphite in solution were investigated to elucidate reaction mechanisms and the role of mineral catalysts on P-solution chemistry. Phosphonate oxidation is rapid in the presence of Fe metal but negligible in the presence of magnetite and in the control sample. The rate of hypophosphite oxidation is independent of reaction substrate.     

Coronal mass ejection (CME) activity of low mass M stars as an important factor for the habitability of terrestrial exoplanets. II. CME-induced ion pick up of Earth-like exoplanets in close-in habitable zones

Atmospheric erosion of CO2-rich Earth-size exoplanets due to coronal mass ejection (CME)-induced ion pick up within close-in habitable zones of active M-type dwarf stars is investigated. Since M stars are active at the X-ray and extreme ultraviolet radiation (XUV) wave-lengths over long periods of time, we have applied a thermal balance model at various XUV flux input values for simulating the thermospheric heating by photodissociation and ionization processes due to exothermic chemical reactions and cooling by the CO2 infrared radiation in the 15 microm band. Our study shows that intense XUV radiation of active M stars results in atmospheric expansion and extended exospheres. Using thermospheric neutral and ion densities calculated for various XUV fluxes, we applied a numerical test particle model for simulation of atmospheric ion pick up loss from an extended exosphere arising from its interaction with expected minimum and maximum CME plasma flows. Our results indicate that the Earth-like exoplanets that have no, or weak, magnetic moments may lose tens to hundreds of bars of atmospheric pressure, or even their whole atmospheres due to the CME-induced O ion pick up at orbital distances 相似文献   

Clathrate hydrates of oxidants in the ice shell of Europa

Europa's icy surface is radiolytically modified by high-energy electrons and ions, and photolytically modified by solar ultraviolet photons. Observations from the Galileo Near Infrared Mapping Spectrometer, ground-based telescopes, the International Ultraviolet Explorer, and the Hubble Space Telescope, along with laboratory experiment results, indicate that the production of oxidants, such as H2O2, O2, CO2, and SO2, is a consequence of the surface radiolytic chemistry. Once created, some of the products may be entrained deeper into the ice shell through impact gardening or other resurfacing processes. The temperature and pressure environments of regions within the europan hydrosphere are expected to permit the formation of mixed clathrate compounds. The formation of carbon dioxide and sulfur dioxide clathrates has been examined in some detail. Here we add to this analysis by considering oxidants produced radiolytically on the surface of Europa. Our results indicate that the bulk ice shell could have a approximately 1.7-7.6% by number contamination of oxidants resulting from radiolysis at the surface. Oxidant-hosting clathrates would consequently make up approximately 12-53% of the ice shell by number relative to ice, if oxidants were entrained throughout. We examine, in brief, the consequences of such contamination on bulk ice shell thickness and find that clathrate formation could lead to substantially thinner ice shells on Europa than otherwise expected. Finally, we propose that double occupancy of clathrate cages by O2 molecules could serve as an explanation for the observation of condensed-phase O2 on Europa. Clathrate-sealed, gas-filled bubbles in the near surface ice could also provide an effective trapping mechanism, though they cannot explain the 5771 A (O2)2 absorption.     

Biosignatures of early earths

A major goal of NASA's Origins Program is to find habitable planets around other stars and determine which might harbor life. Determining whether or not an extrasolar planet harbors life requires an understanding of what spectral features (i.e., biosignatures) might result from life's presence. Consideration of potential biosignatures has tended to focus on spectral features of gases in Earth's modern atmosphere, particularly ozone, the photolytic product of biogenically produced molecular oxygen. But life existed on Earth for about 1(1/2) billion years before the buildup of atmospheric oxygen. Inferred characteristics of Earth's earliest biosphere and studies of modern microbial ecosystems that share some of those characteristics suggest that organosulfur compounds, particularly methanethiol (CH(3)SH, the sulfur analog of methanol), may have been biogenic products on early Earth. Similar production could take place on extrasolar Earth-like planets whose biota share functional chemical characteristics with Earth life. Since methanethiol and related organosulfur compounds (as well as carbon dioxide) absorb at wavelengths near or overlapping the 9.6-microm band of ozone, there is potential ambiguity in interpreting a feature around this wavelength in an extrasolar planet spectrum.     

The potential feasibility of chlorinic photosynthesis on exoplanets

The modern search for life-bearing exoplanets emphasizes the potential detection of O(2) and O(3) absorption spectra in exoplanetary atmospheres as ideal signatures of biology. However, oxygenic photosynthesis may not arise ubiquitously in exoplanetary biospheres. Alternative evolutionary paths may yield planetary atmospheres tinted with the waste products of other dominant metabolisms, including potentially exotic biochemistries. This paper defines chlorinic photosynthesis (CPS) as biologically mediated photolytic oxidation of aqueous Cl(-) to form halocarbon or dihalogen products, coupled with CO(2) assimilation. This hypothetical metabolism appears to be feasible energetically, physically, and geochemically, and could potentially develop under conditions that approximate the terrestrial Archean. It is hypothesized that an exoplanetary biosphere in which chlorinic photosynthesis dominates primary production would tend to evolve a strongly oxidizing, halogen-enriched atmosphere over geologic time. It is recommended that astronomical observations of exoplanetary outgoing thermal emission spectra consider signs of halogenated chemical species as likely indicators of the presence of a chlorinic biosphere. Planets that favor the evolution of CPS would probably receive equivalent or greater surface UV flux than is produced by the Sun, which would promote stronger abiotic UV photolysis of aqueous halides than occurred during Earth's Archean era and impose stronger evolutionary selection pressures on endemic life to accommodate and utilize halogenated compounds. Ocean-bearing planets of stars with metallicities equivalent to, or greater than, the Sun should especially favor the evolution of chlorinic biospheres because of the higher relative seawater abundances of Cl, Br, and I such planets would tend to host. Directed searches for chlorinic biospheres should probably focus on G0-G2, F, and A spectral class stars that have bulk metallicities of +0.0 Dex or greater.     

Photochemical synthesis of citric acid cycle intermediates based on titanium dioxide

The emergence of the citric acid cycle is one of the most remarkable occurrences with regard to understanding the origin and evolution of metabolic pathways. Although the chemical steps of the cycle are preserved intact throughout nature, diverse organisms make wide use of its chemistry, and in some cases organisms use only a selected portion of the cycle. However, the origins of this cycle would have arisen in the more primitive anaerobic organism or even back in the proto-metabolism, which likely arose spontaneously under favorable prebiotic chemical conditions. In this context, we report that UV irradiation of formamide in the presence of titanium dioxide afforded 6 of the 11 carboxylic acid intermediates of the reductive version of the citric acid cycle. Since this cycle is the central metabolic pathway of contemporary biology, this report highlights the role of photochemical processes in the origin of the metabolic apparatus.