The evolution of the atmosphere of the earth

Computer simulations of the evolution of the Earth's atmospheric composition and surface temperature have been carried out. The program took into account changes in the solar luminosity, variations in the Earth's albedo, the greenhouse effect, variation in the biomass, and a variety of geochemical processes. Results indicate that prior to two billion years ago the Earth had a partially reduced atmosphere, which included N₂, CO₂, reduced carbon compounds, some NH₃, but no free H₂. Surface temperatures were higher than now, due to a large greenhouse effect. When free O₂ appeared the temperature fell sharply. Had Earth been only slightly further from the Sun, runaway glaciation would have occured at that time. Simulations also indicate that a runaway greenhouse would have occured early in Earth's history had Earth been only a few percent closer to the Sun. It therefore appears that, taking into account the possibilities of either runaway glaciation or a runaway greenhouse effect, the continously habitable zone about a solar-type star is rather narrow, extending only from roughly 0.95 to 1.01 AU.     

New atmospheric pCO2 estimates from palesols during the late Paleocene/early Eocene global warming interval

The late Paleocene to early Eocene was one of the warmest intervals in Earth's history. Superimposed on this long-term warming was an abrupt short-term extreme warm event at or near the Paleocene/Eocene boundary and centered in the higher latitudes. This short-term climate warming was associated with a major benthic foraminiferal extinction and a dramatic 3–4% drop in the ocean's carbon isotopic composition. It has been suggested that the late paleocene/early Eocene global warming was caused by an enhanced greenhouse effect associated with higher levels of atmospheric CO₂ relative to present levels. We present carbon isotopic data from the co-existing paleosols organic matter and carbonates from a terrestrial sequence in the Paris Basin, France that contradict the notion that an increase in atmospheric CO₂ level was the cause of extreme warming for this time interval. Atmospheric pCO₂ estimates for the Late Paleocene/early Eocene estimated from the terrestrial carbon isotopic record spanning the Paleocene/Eocene transition, are indistinguishable from each other and were generally between 300 and 700 ppm.     

CO2 Snow on Mars and Early Earth: Experimental Constraints

Greenhouse warming due to carbon dioxide atmospheres may be responsible for maintaining the early Earth's surface temperature above freezing and may even have allowed for liquid water on early Mars. However, the high levels of CO₂ required for such warming should have also resulted in the formation of CO₂ clouds. These clouds, depending on their particle size, could lead to either warming or cooling. The particle size in turn is determined by the nucleation and growth conditions. Here we present laboratory studies of the nucleation and growth of carbon dioxide on water ice under martian atmospheric conditions. We find that a critical saturation, S=1.34, is required for nucleation, corresponding to a contact parameter between solid water and solid carbon dioxide of m=0.95. We also find that after nucleation occurs, growth of CO₂ is very rapid, and we report the growth rates at a number of supersaturations. Because growth would be expected to continue until the CO₂ pressure is lowered to its vapor pressure, we expect particles larger than those being currently suggested for the present and past martian atmospheres. Using this information in a microphysical model described in a companion paper, we find that CO₂ clouds are best described as “snow,” having a relatively small number of large particles.     

Stabilization and global climate policy

Academic and political debates over long-run climate policy often invoke “stabilization” of atmospheric concentrations of greenhouse gases (GHGs), but only rarely are non-CO₂ greenhouse gases addressed explicitly. Even though the majority of short-term climate policies propose trading between gases on a global warming potential (GWP) basis, discussions of whether CO₂ concentrations should be 450, 550, 650 or perhaps as much as 750 ppm leave unstated whether there should be no additional forcing from other GHGs beyond current levels or whether separate concentration targets should be established for each GHG. Here, we use an integrated modeling framework to examine multi-gas stabilization in terms of temperature, economic costs, carbon uptake and other important consequences. We show that there are significant differences in both costs and climate impacts between different “GWP equivalent” policies and demonstrate the importance of non-CO₂ GHG reduction on timescales of up to several centuries.     

A review of the carbon dioxide greenhouse problem

An enhanced “greenhouse effect” due to an increase in atmospheric CO₂ is expected to produce significant climatic changes. If the combustion of fossil fuels is the only anthropogenic source of atmospheric CO₂, measurements show that 54% resides in the atmosphere. The largest reservoir for the remaining 46% is the oceans. Known oceanic processes can account for 35% and the major uncertainty appears to be the role played by the intermediate waters. If, however, deforestation is as large a source of additional atmospheric CO₂ as some have suggested, carbon balance cannot be obtained with presently identified removal processes. Various computer models have been used to calculate the effects of increasing atmospheric CO₂. These include energy balance, radiative-convective and general circulation models (GCM's). Many feedback mechanisms must be considered including water vapour, clouds, oceans and the cryosphere. Although representing a considerable advance over other models, GCM's still require many approximations, of which the treatment of oceans and clouds are the most questionable. These models predict, for the scenario of the doubling of atmospheric CO₂, an increase in global surface temperature of about 3°C with larger increases, up to 10° at higher latitudes. Significant changes in evaporation and precipitation patterns are also indicated.     

Thick and thin models of the evolution of carbon dioxide on Mars

We present results from a new simulation code that accounts for the evolution of the reservoirs of carbon dioxide on Mars, from its early years to the present. We establish a baseline model parameter set that produces results compatible with the present (i.e., Patm?6.5 mbar with permanent CO₂ ice cap) for a wide range of initial inventories. We find that the initial inventory of CO₂ broadly determines the evolutionary course of the reservoirs of CO₂. The reservoirs include the atmosphere, ice cap, adsorbed CO₂ in the regolith, and carbonate rocks. We track the evolution of the free inventory: the atmosphere, ice cap and regolith. Simulations begin at 4.53 Gyr before present with a rapid loss of free inventory to space in the early Noachian. Models that assume a relatively small initial inventory (?5 bar) have pronounced minima in the free inventory of CO₂ toward the end of the Noachian. Under baseline parameters, initial inventories below ∼4.5 bar result in a catastrophic loss of the free inventory to space. The current free inventory would be then determined by the balance between outgassing, sputtering losses and chemical weathering following the end of the late bombardment. We call these “thin” models. They generically predict small current free inventories in line with expectations of a small present CO₂ ice cap. For “thick” models, with initial inventories ?5 bar, a surplus of 300-700 mbar of free CO₂ remains during the late-Noachian. The histories of free inventory in time for thick models tend to converge within the last 3.5 Gyr toward a present with an ice cap plus atmospheric inventory of about 100 mbar. For thick models, the convergence is largely due to the effects of chemical weathering, which draws down higher free inventories more rapidly than the low. Thus, thick models have ?450 mbar carbonate reservoirs, while thin models have ?200 mbar. Though both thick and thin scenarios can reproduce the current atmospheric pressure, the thick models imply a relatively large current CO₂ ice cap and thin models, little or none. While the sublimation of a massive cap at a high obliquity would create a climate swing of greenhouse warming for thick models, under the thin model, mean temperatures and pressures would be essentially unaffected by increases in obliquity.     

The natural latitudinal distribution of atmospheric CO2

Although poorly understood, the north–south distribution of the natural component of atmospheric CO₂ offers information essential to improving our understanding of the exchange of CO₂ between the atmosphere, oceans, and biosphere. The natural or unperturbed component is equivalent to that part of the atmospheric CO₂ distribution which is controlled by non-anthropogenic CO₂ fluxes from the ocean and terrestrial biosphere. Models should be able to reproduce the true north–south gradient in CO₂ due to the natural component before they can reliably estimate present-day CO₂ sources and sinks and predict future atmospheric CO₂. We have estimated the natural latitudinal distribution of atmospheric CO₂, relative to the South Pole, using measurements of atmospheric CO₂ during 1959–1991 and corresponding estimates of anthropogenic CO₂ emissions to the atmosphere. Key features of the natural latitudinal distribution include: (1) CO₂ concentrations in the northern hemisphere that are lower than those in the southern hemisphere; (2) CO₂ concentration differences that are higher in the tropics (associated with outgassing of the oceans) than those currently measured; and (3) CO₂ concentrations over the southern ocean that are relatively uniform. This natural latitudinal distribution and its sensitivity to increasing fossil fuel emissions both indicate that near-surface concentrations of atmospheric CO₂ in the northern hemisphere are naturally lower than those in the southern hemisphere. Models that find the contrary will also mismatch present-day CO₂ in the northern hemisphere and incorrectly ascribe that region as a large sink of anthropogenic CO₂.     

Continental-scale comparisons of terrestrial carbon sinks estimated from satellite data and ecosystem modeling 1982–1998

A simulation model based on satellite observations of monthly vegetation cover was used to estimate monthly carbon fluxes in terrestrial ecosystems from 1982 to 1998. The NASA–CASA model was driven by vegetation properties derived from the Advanced Very High Resolution Radiometer (AVHRR) and radiative transfer algorithms that were developed for Moderate Resolution Imaging Spectroradiometer (MODIS). For the terrestrial biosphere, predicted net ecosystem production (NEP) flux for atmospheric CO₂ has varied widely between an annual source of −0.9 Pg C per year and a sink of +2.1 Pg C per year. The southern hemisphere tropical zones (SHT, between 0° and 30°S) have a major influence over the predicted global trends in interannual variability of NEP. In contrast, the terrestrial NEP sink for atmospheric CO₂ on the North American (NA) continent has been fairly consistent between +0.2 and +0.3 Pg C per year, except during relatively cool annual periods when continental NEP fluxes are predicted to total to nearly zero. The predicted NEP sink for atmospheric CO₂ over Eurasia (EA) increased notably in the late 1980s and has been fairly consistent between +0.3 and +0.55 Pg C per year since 1988. High correlations can be detected between the El Niño Southern Oscillation (ENSO) and predicted NEP fluxes on the EA continent and for the SHT latitude zones, whereas NEP fluxes for the North American continent as a whole do not correlate strongly with ENSO events over the same time series since 1982. These observations support the hypothesis that regional climate warming has had notable but relatively small-scale impacts on high latitude ecosystem (tundra and boreal) sinks for atmospheric CO₂.     

Carbon dioxide: Adsorption on palagonite and partitioning in the Martian regolith

We report new CO₂ adsorption measurements on palagonites. These results are used together with earlier results on basalt and nontronite adsorption to derive a “generic” relationship which is valid to within a factor of 3 for likely mixtures of basalt and weathering products of basalt. The relationship involves only t, P_CO2, and the specific surface area, and is relatively insensitive to mineralogy. It is used to predict the distribution and exchange of CO₂ on Mars. We conclude: (1) One to two orders of magnitude more CO₂ is adsorbed on the regolith than is present in the atmosphere and cap. (2) Nonetheless, most of the initially degassed CO₂ must have been lost to space or must be present as carbonates, especially if there was enough degassed CO₂ to provide a significant early greenhouse effect. (3) Given the derived relationship, the CO₂ vapor pressure curve, and the constraint that the system exhibits the current P_CO2 at the current obliquity, it is possible to predict approximately the atmospheric pressure at any obliquity (with or without a cap) without knowing the total available CO₂ inventory, the regolith mass, the regolith distribution, or its mineralogy, any better than those parameters are currently known.     

Role of H2O and CO2 Ices in Martian Climate Changes

In order to study the stability of martian climate, we constructed a two-dimensional (horizontal-vertical) energy balance model. The long-term CO₂ mass exchange process between the atmosphere and CO₂ ice caps is investigated with particular attention to the effect of planetary ice distribution on the climate stability. Our model calculation suggests that high atmospheric pressure presumed for past Mars would be unstabilized if H₂O ice widely prevailed. As a result, a cold climate state might have been achieved by the condensation of atmospheric CO₂ onto ice caps. On the other hand, the low atmospheric pressure, which is buffered by the CO₂ ice cap and likely close to the present pressure, would be unstabilized if the CO₂ ice albedo decreased. This may have led the climate into a warm state with high atmospheric pressure owing to complete evaporation of CO₂ ice cap. Through the albedo feedback mechanisms of H₂O and CO₂ ices in the atmosphere-ice cap system, Mars may have experienced warm and cold climates episodically in its history.     

The Martian paleoclimate and enhanced atmospheric carbon dioxide

Current evidence indicates that the Martian surface is abundant with water presently in the form of ice, while the atmosphere was at one time more massive with a past surface pressure of as much as 1 atm of CO₂. In an attempt to understand the Martian paleoclimate, we have modeled a past CO₂H₂O greenhouse and find global temperatures which are consistent with an earlier presence of liquid surface water, a finding which agrees with the extensive evidence for past fluvial erosion. An important aspect of the CO₂H₂O greenhouse model is the detailed inclusion of CO₂ hot bands. For a surface pressure of 1 atm of CO₂, the present greenhouse model predicts a global mean surface temperature of 294°K, but if the hot bands are excluded, a surface temperature of only 250°K is achieved.     

The case for a wet,warm climate on early Mars

Theoretical arguments are presented in support of the idea that Mars possessed a dense CO₂ atmosphere and a wet, warm climate early in its history. Calculations with a one-dimensional radiative-convective climate model indicate that CO₂ pressures between 1 and 5 bars would have been required to keep the surface temperature above the freezing point of water early in the planet's history. The higher value corresponds to globally and orbitally averaged conditions and a 30% reduction in solar luminosity; the lower value corresponds to conditions at the equator during perihelion at times of high orbital eccentricity and the same reduced solar luminosity.The plausibility of such a CO₂ greenhouse is tested by formulating a simple model of the CO₂ geochemical cycle on early Mars. By appropriately scaling the rate of silicate weathering on present Earth, we estimate a weathering time constant of the order of several times 10⁷ years for early Mars. Thus, a dense atmosphere could have persisted for a geologically significant time period (∼10⁹years) only if atmospheric CO₂ was being continuously resupplied. The most likely mechanism by which this might have been accomplished is the thermal decomposition of carbonate rocks induced directly and indirectly (through burial) by intense, global-scale volcanism. For plausible values of the early heat flux, the recycling time constant is also of the order of several times 10⁷ years. The amount of CO₂ dissolved in standing bodies of water was probably small; thus, the total surficial CO₂ inventory required to maintain these conditions was approximately 2 to 10 bars. The amount of CO₂ in Mars' atmosphere would eventually have dwindled, and the climate cooled, as the planet's internal heat engine ran down. A test for this theory will be provided by spectroscopic searches for carbonates in Mars' crust.     

Liquid water on Mars: An energy balance climate model for CO2/H2O atmospheres

Geologic evidence of the prior existence of liquid water on Mars suggests surface temperatures T_s were once considerably warmer than at present; and that such a condition may have arisen from a larger atmospheric greenhouse. Here we develop a simple climate model for a CO₂/H₂O Mars atmosphere including water vapor-longwave opacity feedback in the atmosphere and temperature-albedo feedback at surface icecaps, under the assumption that once the Martian surface pressure was p_s ≥ 1 atm CO₂. Longwave flux to space is computed as a function of T_s and p_s using band-absorption models for the effect of the 15-μm fundamental, and the 10- and 15-μm hot bands, of the CO₂ molecule; as well as the pure rotation bands and e continuum of H₂O. The derived global radiative balance predicts a global mean surface temperature of 283°K at 1 atm CO₂. When the emission model is coupled to a latitudinally resolved energy balance climate model, including the effect of poleward heat transfer by atmospheric baroclinic eddies, the solutions vary, depending on p_s. We considered two cases: (1) the present Mars (p_s ? 0.007 atm) with pressure-buffering by solid CO₂ icecaps, and limited poleward heat flux by the atmosphere; and (2) a hypothetical “hot Mars” (p_s ? 1.0 atm), whose much higher CO₂ amount augmented by H₂O evaporative feedback yields a theoretical T_s distribution with latitude admitting liquid water over 95% of the surface, water icecaps at the poles, and a diminished equator-to-pole temperature gradient relative to the present.     

The maximal runaway temperature of Earth-like planets

In Simpson’s (Simpson, G.C. [1927]. Mem. R. Meteorol. Soc. II (16), 69–95) classical derivation of the temperature of the Earth in the semi-gray model, the surface temperature diverges as the fourth root of the thermal radiation’s optical depth. No resolution to this apparent paradox was yet obtained under the strict semi-gray approximation. Using this approximation and a simplified approach, we study the saturation of the runaway greenhouse effect.First we generalize the problem of the semi-gray model to cases in which a non-negligible fraction of the stellar radiation falls on the long-wavelength range, and/or that the planetary long-wavelength emission penetrates into the transparent short wavelength domain of the absorption.Second, applying the most general assumptions and independently of any particular properties of an absorber, we show that the greenhouse effect saturates and that any Earth-like planet has a maximal temperature which depends on the type of and distance to its main-sequence star, its albedo and the primary atmospheric components which determine the cutoff frequency below which the atmosphere is optically thick. For example, a hypothetical convection-less planet similar to Venus, that is optically thin in the visible, could have at most a surface temperature of 1200–1300 K irrespective of the nature of the greenhouse gas.We show that two primary mechanisms are responsible for the saturation of the runaway greenhouse effect, depending on the value of λ_cut, the wavelength above which the atmosphere becomes optically thick. Unless λ_cut is small and resides in the optical region, saturation is achieved by radiating the thermal flux of the planet through the short wavelength tail of the thermal distribution. This has an interesting observational implication, the radiation from such a planet should be skewed towards the NIR. Otherwise, saturation takes place by radiating through windows in the FIR.     

Mars CO2 cycle: Effects of airborne dust and polar cap ice emissivity

Mars General Circulation Model (GCM) simulations are presented to illustrate the importance of the ice emissivity of the seasonal CO₂ polar caps in regulating the effects of airborne dust on the martian CO₂ cycle. Simulated results show that atmospheric dust suppresses CO₂ condensation when the CO₂ ice emissivity is high but enhances it when the CO₂ ice emissivity is low. This raises the possibility that the reason for the repeatable nature of the CO₂ cycle in the presence of a highly variable dust cycle is that the CO₂ ice emissivity is “neutral” - the value that leads to no change in CO₂ condensation with changing atmospheric dust. For this GCM, the “neutral” emissivity is approximately 0.55, which is low compared to observed cap emissivities. This inconsistency poses a problem for this hypothesis. However, it is clear that the CO₂ ice emissivity is a critical physical parameter in determining how atmospheric dust affects the CO₂ cycle on Mars.     

Warming the early earth—CO2 reconsidered

Despite a fainter Sun, the surface of the early Earth was mostly ice-free. Proposed solutions to this so-called “faint young Sun problem” have usually involved higher amounts of greenhouse gases than present in the modern-day atmosphere. However, geological evidence seemed to indicate that the atmospheric CO₂ concentrations during the Archaean and Proterozoic were far too low to keep the surface from freezing. With a radiative-convective model including new, updated thermal absorption coefficients, we found that the amount of CO₂ necessary to obtain 273 K at the surface is reduced up to an order of magnitude compared to previous studies. For the late Archaean and early Proterozoic period of the Earth, we calculate that CO₂ partial pressures of only about 2.9 mb are required to keep its surface from freezing which is compatible with the amount inferred from sediment studies. This conclusion was not significantly changed when we varied model parameters such as relative humidity or surface albedo, obtaining CO₂ partial pressures for the late Archaean between 1.5 and 5.5 mb. Thus, the contradiction between sediment data and model results disappears for the late Archaean and early proterozoic.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

Tolerance of allogromiid Foraminifera to severely elevated carbon dioxide concentrations: Implications to future ecosystem functioning and paleoceanographic interpretations

Increases in the partial pressure of carbon dioxide (pCO₂) in the atmosphere will significantly affect a wide variety of terrestrial fauna and flora. Because of tight atmospheric–oceanic coupling, shallow-water marine species are also expected to be affected by increases in atmospheric carbon dioxide concentrations. One proposed way to slow increases in atmospheric pCO₂ is to sequester CO₂ in the deep sea. Thus, over the next few centuries marine species will be exposed to changing seawater chemistry caused by ocean–atmospheric exchange and/or deep-ocean sequestration. This initial case study on one allogromiid foraminiferal species (Allogromia laticollaris) was conducted to begin to ascertain the effect of elevated pCO₂ on benthic Foraminifera, which are a major meiofaunal constituent of shallow- and deep-water marine communities. Cultures of this thecate foraminiferan protist were used for 10–14-day experiments. Experimental treatments were executed in an incubator that controlled CO₂ (15 000; 30 000; 60 000; 90 000; 200 000 ppm), temperature and humidity; atmospheric controls (i.e., ~ 375 ppm CO₂) were executed simultaneously. Although the experimental elevated pCO₂ values are far above foreseeable surface water pCO₂, they were selected to represent the spectrum of conditions expected for the benthos if deep-sea CO₂ sequestration becomes a reality. Survival was assessed in two independent ways: pseudopodial presence/absence and measurement of adenosine triphosphate (ATP), which is an indicator of cellular energy. Substantial proportions of A. laticollaris populations survived 200 000 ppm CO₂ although the mean of the median [ATP] of survivors was statistically lower for this treatment than for that of atmospheric control specimens. After individuals that had been incubated in 200 000 ppm CO₂ for 12 days were transferred to atmospheric conditions for ~ 24 h, the [ATP] of live specimens (survivors) approximated those of the comparable atmospheric control treatment. Incubation in 200 000 ppm CO₂ also resulted in reproduction by some individuals. Results suggest that certain Foraminifera are able to tolerate deep-sea CO₂ sequestration and perhaps thrive as a result of elevated pCO₂ that is predicted for the next few centuries, in a high-pCO₂ world. Thus, allogromiid foraminiferal “blooms” may result from climate change. Furthermore, because allogromiids consume a variety of prey, it is likely that they will be major players in ecosystem dynamics of future coastal sedimentary environments.     

Climate and carbon cycle changes under the overshoot scenario

The “overshoot scenario” is an emissions scenario in which CO₂ concentration in the atmosphere temporarily exceeds some pre-defined, “dangerous” threshold (before being reduced to non-dangerous levels). Support for this idea comes from its potential to achieve a balance between the burdens of current and future generations in dealing with global warming. Before it can be considered a viable policy, the overshoot scenario needs to be examined in terms of its impacts on the global climate and the environment. In, particular, it must be determined if climate change cause by the overshoot scenario is reversible or not, since crossing that “dangerous” CO₂ threshold could result in climate change from which we might not be able to recover. In this study, we quantify the change in several climatic and environmental variables under the overshoot scenario using a global climate model of intermediate complexity. Compared to earlier studies on the overshoot scenario, we have an explicit carbon cycle model that allows us to represent carbon-climate feedbacks and force the climate model more realistically with CO₂ emissions rates rather than with prescribed atmospheric pCO₂. Our standard CO₂ emissions rate is calculated on the basis of historical atmospheric pCO₂ data and the WRE S650 non-overshoot stabilization profile. It starts from the preindustrial year 1760, peaks in the year 2056, and ends in the year 2300. A variety of overshoot scenarios were constructed by increasing the amplitude of the control emissions peak but decreasing the peak duration so that the cumulative emissions remain essentially constant. Sensitivity simulations of various overshoot scenarios in our model show that many aspects of the global climate are largely reversible by year 2300. The significance of the reversibility, which takes roughly 200 years in our experiments, depends on the time horizon with which it is viewed or the number of future generations for whom equity is sought. At times when the overshoot scenario has emissions rates higher then the control scenario, the transient changes in atmospheric and oceanic temperatures and surface ocean pH can be significant, even for moderate overshoot scenarios that remain within IPCC SRES emissions scenarios. The large transient changes and the centennial timescale of climate reversibility suggest that the overshoot might not be the best mitigation approach, even if it technically follows the optimal economic path.     

Chemical pathway analysis of the Martian atmosphere: CO2-formation pathways

The chemical composition of a planetary atmosphere plays an important role for atmospheric structure, stability, and evolution. Potentially complex interactions between chemical species do not often allow for an easy understanding of the underlying chemical mechanisms governing the atmospheric composition. In particular, trace species can affect the abundance of major species by acting in catalytic cycles. On Mars, such cycles even control the abundance of its main atmospheric constituent CO₂. The identification of catalytic cycles (or more generally chemical pathways) by hand is quite demanding. Hence, the application of computer algorithms is beneficial in order to analyze complex chemical reaction networks. Here, we have performed the first automated quantified chemical pathways analysis of the Martian atmosphere with respect to CO₂-production in a given reaction system. For this, we applied the Pathway Analysis Program (PAP) to output data from the Caltech/JPL photochemical Mars model. All dominant chemical pathways directly related to the global CO₂-production have been quantified as a function of height up to 86 km. We quantitatively show that CO₂-production is dominated by chemical pathways involving HO_x and O_x. In addition, we find that NO_x in combination with HO_x and O_x exhibits a non-negligible contribution to CO₂-production, especially in Mars’ lower atmosphere. This study reveals that only a small number of chemical pathways contribute significantly to the atmospheric abundance of CO₂ on Mars; their contributions to CO₂-production vary considerably with altitude. This analysis also endorses the importance of transport processes in governing CO₂-stability in the Martian atmosphere. Lastly, we identify a previously unknown chemical pathway involving HO_x, O_x, and HO₂-photodissociation, contributing 8% towards global CO₂-production by chemical pathways using recommended up-to-date values for reaction rate coefficients.