Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

汶川M_s 8.0地震破裂带CO_2、CH_4、Rn和Hg脱气强度

地震活动断裂带能够向大气释放大量的温室气体、放射性气体和有毒气体(CO_2、CH_4、Rn和Hg),并对大气环境的影响产生复杂的影响。利用静态暗箱法,对汶川M_s8.0地震破裂带CO_2、Rn和Hg脱气强度进行实地测量,并计算了CO_2和Hg脱气对大气的年贡献量。结果表明:(1)破裂带土壤气中CO_2、CH_4、Rn和Hg异常浓度最大值分别可以达到7.98%、2.38%、524.30k Bq/m~3和161.00ng/m~3;破裂带CO_2、Rn和Hg脱气平均通量是34.95g·m~(-2)d~(-1)、36.11m Bq·m~(-2)s~(-1)和26.56ng·m~(-2)h~(-1),最大值分别达到259.23g·m~(-2)d~(-1)、580.35m Bq·m~(-2)s~(-1)和387.67ng·m~(-2)h~(-1);(2)汶川Ms8.0地震破裂带向大气脱气的CO_2年贡献量是0.95Mt,Hg的年贡献量是15.94kg。汶川Ms8.0地震破裂带破裂CO_2、CH_4、Rn和Hg等的脱气强度,不仅与破裂带渗透率有关,还与断裂带浅部存在的气藏、煤层以及磷矿层等气体源有重要的联系。     

松辽盆地含CO_2火山岩气藏的形成和分布

松辽盆地特有的深部构造背景和裂谷演化特征,造成盆地内含CO_2火山岩气藏的形成和富集。松辽裂谷盆地中新生代火山岩浆活动发育,总体上具有多期喷发、分布广泛和储集条件良好的特点。火山活动以中心式喷发为主,主要发育中基性-酸性火山岩,发育流纹岩、凝灰岩等多种岩石类型,爆发相和溢流相2种火山岩相。中生代火山岩在盆地内分布广泛,营域组构成深层有利储层,新生代火山岩在盆地外围出露较多,而在盆内出露较少。盆地高含量的二氧化碳为无机幔源成因,由青山口期和新生代幔源岩浆脱气形成。含CO_2火山岩气藏的形成主要受深部构造背景、深大断裂和中新生代火山岩控制。已发现含CO_2火山岩气藏主要分布于古中央隆起带及其两侧断陷的营城组火山岩中,具有点状、带状分布,局部富集的特点。根据主控因素分析,预测了5个CO_2富集区带。     

Gas geochemistry of natural analogues for the studies of geological CO2 sequestration

Geological sequestration of anthropogenic CO₂ appears to be a promising method for reducing the amount of greenhouse gases released to the atmosphere. Geochemical modelling of the storage capacity for CO₂ in saline aquifers, sandstones and/or carbonates should be based on natural analogues both in situ and in the laboratory. The main focus of this paper has been to study natural gas emissions representing extremely attractive surrogates for the study and prediction of the possible consequences of leakage from geological sequestration sites of anthropogenic CO₂ (i.e., the return to surface, potentially causing localised environmental problems). These include a comparison among three different Italian case histories: (i) the Solfatara crater (Phlegraean Fields caldera, southern Italy) is an ancient Roman spa. The area is characterised by intense and diffuse hydrothermal activity, testified by hot acidic mud pools, thermal springs and a large fumarolic field. Soil gas flux measurements show that the entire area discharges between 1200 and 1500 tons of CO₂ per day; (ii) the Panarea Island (Aeolian Islands, southern Italy) where a huge submarine volcanic-hydrothermal gas burst occurred in November, 2002. The submarine gas emissions chemically modified seawater causing a strong modification of the marine ecosystem. All of the collected gases are CO₂-dominant (maximum value: 98.43 vol.%); (iii) the Tor Caldara area (Central Italy), located in a peripheral sector of the quiescent Alban Hills volcano, along the faults of the Ardea Basin transfer structure. The area is characterised by huge CO₂ degassing both from water and soil. Although the above mentioned areas do not represent a storage scenario, these sites do provide many opportunities to study near-surface processes and to test monitoring methodologies.     

Experimental identification of CO2–water–rock interactions caused by sequestration of CO2 in Westphalian and Buntsandstein sandstones of the Campine Basin (NE-Belgium)

Geological sequestration of CO₂ is one of the options studied to reduce greenhouse gas emissions. Although the feasibility of this concept is proven, apart from literature data on modelling still little is known about the CO₂–water–rock interactions induced by CO₂-injection.To evaluate the effect of CO₂–water–rock interactions on three sandstone aquifers in NE-Belgium an experimental setup was built. Eighteen experiments were performed in which sandstones were exposed to supercritical CO₂. CO₂–water–rock interactions were deduced from the evolution of aqueous concentrations of 25 species and a thorough characterisation of the sandstones before and after treatment. The results show that dissolution of ankerite/dolomite and Al-silicates could enhance porosity/permeability. The observed precipitation of end-member carbonates could increase storage capacity if it exceeds carbonate dissolution. Precipitation of the latter and of K-rich clays as observed, however, can hamper the injection.     

Flue gas and pure CO2 sorption properties of coal: A comparative study

Presently many research projects focus on the reduction of anthropogenic CO₂ emissions. It is intended to apply underground storage techniques such as flue gas injection in unminable coal seams. In this context, an experimental study has been performed on the adsorption of pure CO₂ and preferential sorption behavior of flue gas. A coal sample from the Silesian Basin in Poland (0.68% V Rr), measured in the dry and wet state at 353 K has been chosen for this approach. The flue gas used was a custom class industrial flue gas with 10.9% of CO₂, 0.01% of CO, 9% of H₂, 3.01% of CH₄, 3.0% of O₂, 0.106% of SO₂ and nitrogen as balance.Adsorption isotherms of CO₂ and flue gas were measured upto a maximum of 11 MPa using a volumetric method. Total excess sorption capacities for CO₂ on dry and wet Silesia coal ranged between 1.9 and 1.3 mmol/g, respectively. Flue gas sorption capacities on dry and wet Silesia coal were much lower and ranged between 0.45 and 0.2 mmol/g, respectively, at pressures of 8 MPa. The low sorption capacity of wet coal has resulted from water occupying some of the more active adsorption sites and hence reducing the heterogeneity of adsorption sites relative to that of dry coal. Desorption tests with flue gas were conducted to study the degree of preferential sorption of the individual components. These experiments indicate that CO₂ is by far the prefered sorbing component under both wet and dry conditions. This is followed by CH₄. N₂ adsorbs very little on the coal in the presence of CO₂ and CH₄. It is also observed that the adsorption of CO₂ onto coal is not significantly hindered by the addition of other gases, other than dilution effect of the pressure.In addition to the sorption experiments, the density of the flue gas mixture has been determined up to 18 MPa at 318 K. A very good precision of these measurements were documented by volumetric methods.     

The use of tracers to assess leakage from the sequestration of CO2 in a depleted oil reservoir,New Mexico,USA

Geological sequestration of CO₂ in depleted oil reservoirs is a potentially useful strategy for greenhouse gas management and can be combined with enhanced oil recovery. Development of methods to estimate CO₂ leakage rates is essential to assure that storage objectives are being met at sequestration facilities. Perfluorocarbon tracers (PFTs) were added as three 12 h slugs at about one week intervals during the injection of 2090 tons of CO₂ into the West Pearl Queen (WPQ) depleted oil formation, sequestration pilot study site located in SE New Mexico. The CO₂ was injected into the Permian Queen Formation. Leakage was monitored in soil–gas using a matrix of 40 capillary adsorbent tubes (CATs) left in the soil for periods ranging from days to months. The tracers, perfluoro-1,2-dimethylcyclohexane (PDCH), perfluorotrimethylcyclohexane (PTCH) and perfluorodimethylcyclobutane (PDCB), were analyzed using thermal desorption, and gas chromatography with electron capture detection. Monitoring was designed to look for immediate leakage, such as at the injection well bore and at nearby wells, and to develop the technology to estimate overall CO₂ leak rates based on the use of PFTs. Tracers were detected in soil–gas at the monitoring sites 50 m from the injection well within days of injection. Tracers continued to escape over the following years. Leakage appears to have emanated from the vicinity of the injection well in a radial pattern to about 100 m and in directional patterns to 300 m. Leakage rates were estimated for the 3 tracers from each of the 4 sets of CATs in place following the start of CO₂ injection. Leakage was fairly uniform during this period. As a first approximation, the CO₂ leak rate was estimated at about 0.0085% of the total CO₂ sequestered per annum.     

CO2气综合识别技术及应用

CO₂气藏由于其物理、化学性质的特殊性,CO₂气勘探与烃类气既有相同又有区别,综合应用多种资料和多种技术方法是识别CO₂气(层)藏的有效手段。利用区域地质分析、地球物理和地球化学勘探方法综合评价非烃气的分布,提出钻探目标,通过非烃色谱测量法和红外线CO₂气体浓度测量法实现CO₂气层钻井现场动态检测,利用气体色谱检测相关录井参数资料、核测井密度中子孔隙度差值综合解释CO₂气层,有效地识别CO₂气。主要介绍CO₂气藏综合勘探技术的关键的新技术方法,如地球化学方法、录井和测井综合识别的关键技术方法等。     

四川盆地理论CO_2地质利用与封存潜力评估

结合CO_2地质利用与封存技术机理,在国际权威潜力评估公式的基础上,系统地提出了适合中国地质背景的次盆地尺度CO_2封存潜力评估方法及关键参数取值。同时,以四川盆地为例,依次开展了枯竭油田地质封存与CO_2强化石油开采、枯竭气田与CO_2强化采气、不可采煤层地质封存与CO_2驱替煤层气,以及咸水层地质封存技术的CO_2地质封存潜力。结果表明,四川盆地利用深部咸水层与枯竭天然气田CO_2地质封存潜力最大,期望值分别达154.20×10~8t和53.73×10~8t。其中,枯竭天然气田因成藏条件好、勘探程度高、基础建设完善,为四川盆地及其周边利用枯竭气田CO_2地质封存技术实现低碳减排提供了早期示范机会。CO_2地质利用与封存潜力评估方法,对进一步开展全国次盆地尺度理论封存潜力评估与工程规划具有重要意义。     

The CO2-He-Ar-H2O systematics of the manus back-arc basin: resolving source composition from degassing and contamination effects

We report new stepped heating He, Ar, CO₂ and water data on a petrogenetically diverse suite of lavas from the Manus back-arc basin, where a plume component has previously been identified. The aim of this study is to evaluate the superimposed effects of degassing and contamination in order to identify mantle source characteristics. CO₂ abundances and carbon isotopes in both the vesicle ([CO₂] up to 180ppm; δ¹³C as low as -33.6 ‰) and glass ([CO₂] up to 270ppm; δ¹³C as low as -34.3 ‰) phases reveal that samples have been modified by varying degrees of degassing. High water concentration samples (back-arc basin basalts (BABB) and arc type samples) show the highest degrees of degassing (i.e. lower δ¹³C values and lower CO₂ contents). The results are modelled for both the glass and vesicle phases using batch and fractional degassing models. Parental melt compositions can be constrained to show the following CO₂ concentration trend: arc-type > BABB s.r. (southern rift) > MORB-2, E-MORB, X-BABB (extreme BABB), BABB > MORB-1 and MORB-smt. ⁴He/⁴⁰Ar∗ ratios of samples (14.6-1100) are consistent with residual volatiles from a degassed source. Variations in CO₂/³He values are likely due to degassing, followed by contamination from a crustal source (either the subducting Solomon Sea Plate or the pre-existing crust through which the lavas erupt), as evidenced by high K₂O/TiO₂ ratios and low δ¹³C. The CO₂/³He of the Manus plume is best estimated by the MORB-smt and MORB-1 samples at 3.1 ± 0.6 x 10⁹. This value is similar to previous estimates of plume CO₂/³He values, which are either equal to or slightly greater than the upper mantle average of 2 x 10⁹.     

The Starzach site in Southern Germany: a site with naturally occurring CO<Subscript>2</Subscript> emissions recovering from century-long gas mining as a natural analog for a leaking CCS reservoir

In this paper, we present the Starzach site, a region featuring numerous natural CO₂ emission spots, such as mofettes, that reappeared after a longer period of extensive industrial CO₂ mining. We discuss the results of a detailed literature study on the geological setting and the activities related to the gas mining in combination with own measurements to introduce the site as an example on how gas leakage from an insecure CCS reservoir could manifest at the surface. The site is in particular interesting for such investigations as the CO₂ emissions started to replenish after the end of the CO₂ mining and offers the unique possibility to investigate an increase in degassing activity as it might be expected for an active CCS site where leakage is suspected. Based on the geological setting and soil, gas emission, and isotope investigations, we further discuss the source of the CO₂ emission and the gas ascent to the ground surface via deep-reaching faults, latter being so far excluded by previous work. The combination of our extensive literature review and recent field investigations allowed us to draw new geological conclusions for the site that were under discussion for a long time and to give insight into the site’s potential for CCS-related analog studies in the future.     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。     

N2-CH4（CO2）混合气体在线标样制备及其拉曼定量因子测定

利用混合气体的标准样品对激光拉曼探针进行标定,可以快速准确地对包裹体中的无机及有机气相组分进行定量分析。而常用的商用钢瓶装混合气体标样,存在费用高、气体组成单一固定等缺点。本文设计了一套在线标样制备装置,提出一种在线配置不同浓度和压力条件下混合气体标样的方法。利用高纯度(纯度99.999%)的N2、CH4以及CO2钢瓶气,经过在线混合增压,在5 MPa和10 MPa条件下制备了N2摩尔分数为30%、50%和70%的N2-CH4以及N2-CO2混合气体在线标样。该方法制备的标样与70%N2+30%CO2的商用钢瓶气标样对比表明,CO2与N2的拉曼相对峰高以及相对峰面积值的误差在4%以内,具有较高的准确度和重现性。通过不同压力和浓度条件下CH4以及CO2的拉曼相对定量因子测定表明,气体的相对定量因子在5~10 MPa压力条件下与压力及组成无关。地质样品应用结果表明,本方法可以方便、灵活、准确地按任意比例将两瓶及两瓶以上纯气体钢瓶样品进行混合及增压,为激光拉曼标定、气体组成原位测量等提供了一种新的技术思路。     

Geologic factors controlling CO2 storage capacity and permanence: case studies based on experience with heterogeneity in oil and gas reservoirs applied to CO2 storage

A variety of structural and stratigraphic factors control geological heterogeneity, inferred to influence both sequestration capacity and effectiveness, as well as seal capacity. Structural heterogeneity factors include faults, folds, and fracture intensity. Stratigraphic heterogeneity is primarily controlled by the geometry of depositional facies and sandbody continuity, which controls permeability structure. The permeability structure, in turn, has implications for CO₂ injectivity and near-term migration pathways, whereas the long-term sequestration capacity can be inferred from the production history. Examples of Gulf Coast oil and gas reservoirs with differing styles of stratigraphic heterogeneity demonstrate the impact of facies variability on fluid flow and CO₂ sequestration potential. Beach and barrier-island deposits in West Ranch field in southeast Texas are homogeneous and continuous. In contrast, Seeligson and Stratton fields in south Texas, examples of major heterogeneity in fluvial systems, are composed of discontinuous, channel-fill sandstones confined to narrow, sinuous belts. These heterogeneous deposits contain limited compartments for potential CO₂ storage, although CO₂ sequestration effectiveness may be enhanced by the high number of intraformational shale beds. These field examples demonstrate that areas for CO₂ storage can be optimized by assessing sites for enhanced oil and gas recovery in mature hydrocarbon provinces.     

The rise of trees and their effects on Paleozoic atmospheric CO2 and O2

The rise of large vascular plants during the mid-Paleozoic brought about a major increase in the rates of weathering of silicate minerals that induced a drop in the level of atmospheric CO₂ and contributed, via the atmospheric greenhouse effect, to global cooling and the initiation of the most long lived and a really extensive glaciation of the past 550 million years. Sedimentary burial of the microbiologically resistant remains of the plants resulted during the Permo-Carboniferous in both further lowering of CO₂ and in elevation of atmospheric O₂. Evidence of changes in CO₂ and O₂ are provided by mathematical models, studies of paleosols, fossil plants, fossil insects, and the effects of modern plants on silicate weathering, and by laboratory studies of the effects of changes in O₂ on plants and insects. To cite this article: R.A. Berner, C. R. Geoscience 335 (2003).     

二氧化碳羽流地热系统的碳封存经济分析

【研究目的】 二氧化碳羽流地热系统（CPGS）在取热的同时可实现CO₂地质封存，在碳达峰与碳中和背景下，CPGS碳封存的经济性是众多学者关注的要点。【研究方法】 以松辽盆地泉头组为例，采用数值模拟方法对比分析了注入压力、井间距与回注温度对热提取率的影响，在供暖情景下，计算了CPGS供暖效益与碳封存成本，并与常规水热型地热系统供暖效益进行了对比。【研究结果】 受携热介质转变与热突破影响，CPGS开采井温度呈现“降低-稳定-降低”的趋势，其中井间距对开采井温降影响显著，井间距越小开采井温降越明显；热提取率与回注压力呈现正相关性，与回注温度呈现负相关性，井间距对热提取率影响不显著；CPGS与常规水热型地热系统相比，采热量呈现“高-低-高”三个阶段，其中回注压力越小、回注温度与储层温度越接近，实现CPGS较水介质多采热能所需的时间越短。【结论】 仅考虑CO₂价格与取热效益，供暖收益抵消部分碳封存成本后，井间距对CO₂封存单位成本影响最为显著，井间距越小，CO₂封存单位成本降低越迅速，在注采井间距300 m条件下，持续开采30 a后CO₂封存单位成本可降至160元/t。     

Investigation of CO2 behavior and study on design of optimal injection into Gorae-V aquifer

This study presents the Bottom-hole pressure (BHP) behavior with different wettabilities and the optimal design scheme to effectively inject CO₂ into the Gorae-V aquifer. As a result, the injection rate and injectivity were increased as the wettability condition became more water-wet. However, the more wettability condition becomes water-wet, the more the ultimate CO₂ injection volume decreases. When the injectivity was 346 ton/day/Mpa at the Gorae-V aquifer, the aquifer can sustain CO₂ injection at a rate of 2,425 tons per day over this time period. A design for a complete CCS system was developed based on the existing off-shore pipeline in combination with new on-shore CO₂ transport infrastructure, and a pressure of 12.8 MPa is required at the CO₂ source to maintain this injection rate.     

Sources, degassing, and contamination of CO2, H2O, He, Ne, and Ar in basaltic glasses from Kolbeinsey Ridge, North Atlantic

New volatile data (CO₂, H₂O, He, Ne, and Ar) are presented for 24 submarine basaltic glasses from the Kolbeinsey Ridge, Tjörnes Fracture Zone and Mohns Ridge, North Atlantic. Low CO₂ and He contents indicate that magmas were strongly outgassed with the extent of degassing increasing toward the south, as expected from shallower ridge depths. Ne and Ar are significantly more abundant in the southernmost glasses than predicted for degassed melt. The strong atmospheric isotopic signal associated with this excess Ne and Ar suggests syn- or posteruptive contamination by air. Degassing, by itself, cannot generate the large variations in δ¹³C values of dissolved CO₂ or coupled CO₂-Ar variations. This suggests that δ¹³C values were also affected by some other processes, most probably melt-crust interaction. Modelling indicates that degassing had a negligible influence on water owing to its higher solubility in basaltic melt than the other volatiles. Low H₂O contents in the glasses reflect melting of a mantle source that is not water-rich relative to the source of N-MORB.Before eruption, Kolbeinsey Ridge melts contained ∼400 ppm CO₂ with δ¹³C of −6‰, 0.1 to 0.35 wt.% H₂O, ³He/⁴He ∼11 R_A, and CO₂/³He of ∼2 × 10⁹. We model restored volatile characteristics and find homogeneous compositions in the source of Kolbeinsey Ridge magmas. Relative to the MORB-source, He and Ne are mildly fractionated while the ⁴⁰Ar/³⁶Ar may be low. The ³He/⁴He ratios in Tjörnes Fracture Zone glasses are slightly higher (13.6 R_A) than on Kolbeinsey Ridge, suggesting a greater contribution of Icelandic mantle from the south, but the lack of ³He/⁴He variation along the Kolbeinsey Ridge is inconsistent with active dispersal of Icelandic mantle beyond the Tjörnes Fracture Zone.     

CO2 solubility in Martian basalts and Martian atmospheric evolution

To understand possible volcanogenic fluxes of CO₂ to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO₂ solubility. CO₂ contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe³⁺/Fe^T was measured by Mössbauer spectroscopy. The CO₂ contents of glasses show no dependence on Fe³⁺/Fe^T and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO₂ contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol⁻¹ cm⁻² for the integrated area under the carbonate doublet at 1430 and 1520 cm⁻¹. The experimentally determined CO₂ solubilities allow calibration of the thermodynamic parameters governing dissolution of CO₂ vapor as carbonate in silicate melt, K_II, (Stolper and Holloway, 1988) as follows: , ΔV⁰ = 20.85 ± 0.91 cm³ mol⁻¹, and ΔH⁰ = −17.96 ± 10.2 kJ mol⁻¹. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO₂ dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and f_O2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO₂ contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO₂ at IW and 0.24 wt.% of CO₂ at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO₂ to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO₂ to an early Martian greenhouse is plausible.