Atmospheric14C changes resulting from fossil fuel CO2 release and cosmic ray flux variability

A high-precision tree-ring record of the atmospheric¹⁴C levels between 1820 and 1954 is presented. Good agreement is obtained between measured and model calculated 19th and 20th century atmospheric Δ¹⁴C levels when both fossil fuel CO₂ release and predicted natural variations in¹⁴C production are taken into account. The best fit is obtained by using a ?-diffusion model with an oceanic eddy diffusion coefficient of 3 cm²/s, a CO₂ atmosphere-ocean gas exchange rate of 21 moles m^?2 yr^?1 and biospheric residence time of 60 years.For trees in the state of Washington the measured 1949–1951 atmospheric Δ¹⁴C level was20.0±1.2%. below the 1855–1864 level. Model calculations indicate that in 1950 industrial CO₂ emissions are responsible for at least 85% of the Δ¹⁴C decline, whereas natural variability accounts for the remaining 15%.     

Reduction of thermohaline circulation during deglaciation: the effect on atmospheric radiocarbon and CO2

A two-? ocean reservoir model is employed to examine the combined effects of vertical ocean circulation, organic matter extraction and cosmic ray production on the¹⁴C/¹²C in the atmosphere, ocean and sediment. In this model, dissolution of deep-sea calcium carbonate sediment is assumed to respond to the supply of particulate carbonate from the surface ocean and to the dissolved carbonate-ion concentration of the deep-sea.If the vertical ocean circulation decreased by 50% during the maximum rate of deglaciation, the atmospheric¹⁴C/¹²C would have increased concurrently by 10% relative to the pre-bomb present. Further, if cosmic ray production of¹⁴C was 50% greater than present at about 7800 years B.P. as suggested by archeomagnetic measurements, a double maximum of 10% occurs. The first is at about 10.5 ka and the second at 6.5 ka. This result is similar to the variation of¹⁴C/¹²C over the last 10,000 years calculated from the¹⁴C dates measured by Stuiver on the varved Lake of the Clouds. The result is not sensibly altered if 10¹⁷ moles of organic carbon is extracted from the ocean during sea-level rise.Reduction of the thermohaline ocean circulation by 50% over a one- to two-thousand-year interval would not be sensibly detected in the dating of deep-sea sediment. If Broecker's organic nutrient extraction occurs in conjunction with reduction of vertical circulation, a decrease in the atmospheric P_CO2 will precede the eventual rise.     

MEIC-global-CO2: A new global CO2 emission inventory with highly-resolved source category and sub-country information

CO₂ emission inventory provides fundamental data for climate research and emission mitigation. Currently, most global CO₂ emission inventories were developed with energy statistics from International Energy Agency(IEA) and were available at country level with limited source categories. Here, as the first step toward a high-resolution and dynamic updated global CO₂ emission database, we developed a data-driven approach to construct seamless and highly-resolved ene...     

Modeling vertical stratification of CO2 injected into a deep layered aquifer

The vertical stratification of carbon dioxide (CO₂) injected into a deep layered aquifer made up of high-permeability and low-permeability layers, such as Utsira aquifer at Sleipner site in Norway, is investigated with a Buckley–Leverett equation including gravity effects. In a first step, we study both by theory and simulation the application of this equation to the vertical migration of a light phase (CO₂), in a denser phase (water), in 1D vertical columns filled with different types of porous media: homogeneous, piecewise homogeneous, layered periodic and finally heterogeneous. For each case, we solve the associated Riemann problems and propose semi-analytical solutions describing the spatial and temporal evolution of the light phase saturation. These solutions agree well with simulation results. We show that the flux continuity condition at interfaces between high-permeability and low-permeability layers leads to CO₂ saturation discontinuities at these interfaces and, in particular, to a saturation increase beneath low-permeability layers. In a second step, we analyze the vertical migration of a CO₂ plume injected into a 2D layered aquifer. We show that the CO₂ vertical stratification under each low-permeability layer is induced, as in 1D columns, by the flux continuity condition at interfaces. As the injection takes place at the bottom of the aquifer the velocity and the flux function decrease with elevation and this phenomenon is proposed to explain the stratification under each mudstone layer as observed at Sleipner site.     

The oxygen minimum zone (OMZ) off Chile as intense source of CO2 and N2O

The oxygen minimum zones (OMZs) are recognized as intense sources of N₂O greenhouse gas (GHG) and could also be potential sources of CO₂, the most important GHG for the present climate change. This study evaluates, for one of the most intense and shallow OMZ, the Chilean East South Pacific OMZ, the simultaneous N₂O and CO₂ fluxes at the air–sea interface. Four cruises (2000–2002) and 1 year of monitoring (21°–30°–36°S) off Chile allowed the determination of the CO₂ and N₂O concentrations at the sea surface and the analysis of fluxes variations associated with different OMZ configurations. The Chilean OMZ area can be an intense GHG oceanic local source of both N₂O and CO₂. The mean N₂O fluxes are 5–10 times higher than the maximal previous historical source in an OMZ open area as in the Pacific and Indian Oceans. For CO₂, the mean fluxes are also positive and correspond to very high oceanic sources. Even if different coupling and decoupling between N₂O and CO₂ are observed along the Chilean OMZ, 65% of the situations represent high CO₂ and/or N₂O sources. The high GHG sources are associated with coastal upwelling transport of OMZ waters rich in N₂O and probably also in CO₂, located at a shallow depth. The integrated OMZ role on GHG should be better considered to improve our understanding of the past and future atmospheric CO₂ and N₂O evolutions.     

Stability of forsterite + CO2 and its bearing on the role of CO2 in the mantle

An experimental determination of the reaction MgCO₃ + MgSiO₃ = Mg₂SiO₄ + CO₂ between 20 and 40 kbars and in the range 1000–1500°C yields an average pressure effect on the equilibrium of 44 bars/°C. This result shows that the assemblage forsterite and carbon dioxide is not stable under most pressure and temperature conditions expected in the upper mantle. Hypotheses requiring the presence of free CO₂ in the low-velocity zone, CO₂ as a drive mechanism for kimberlite emplacement, or action of a free CO₂ phase in ultramafic rocks may need considerable revision.     

Quantifying the impact of mineralogical heterogeneity on reactive transport modeling of CO2+O2 in-situ leaching of uranium

CO₂+ O₂ in-situ leaching(ISL) of sandstonetype uranium ore represents the third generation of solution mining in China.In this study,reactive transport modeling of the interaction between hydrodynamic and geochemical reactions is performed to enable better prediction and regulation of the CO₂+ O₂ in-situ leaching process of uranium.Geochemical reactions between mining solutions and rock,and the kinetic uranium dissolution controlled by O₂(aq...     

CO2/CaCl2 solution interfacial tensions under CO2 geological storage conditions: Influence of cation valence on interfacial tension

The effectiveness of CO₂ storage in deep saline aquifers and hydrocarbon reservoirs is governed, among other factors, by the interfacial tension between the injected CO₂ and formation water (brine). Experimental data on CO₂/water and CO₂/NaCl solution have revealed that the interfacial tension depends on the pressure, temperature and water salinity. However, there is still a lack of data for other salts (such as MgCl₂ and CaCl₂) which are also present in aquifers and carbonate reservoirs.     

Origin and source of CO2 in natural gas from the eastern Sichuan Basin

The CO2 contents of natural gas from the eastern Sichuan Basin were mainly less than 2%,and they were generally large when the H2S contents were over 5%.The natural gas in the eastern Sichuan Basin showed high δ13C1 values uncorrelated with H2S contents,and the oil-associated gas generally displayed carbon isotopic reversal between methane and ethane,whereas the coal-derived gas samples displayed positive series.The δ13C values of CO2 in the natural gas could be divided into two types,one with low values(-24‰--12‰)and the other with high values(-8‰-4‰).The natural gas had low R/Ra values and broad CO2/3He values distinct from the mantle-derived gas,and the CO2 was typical of crustal origin.Natural gas with high δ13CCO2 values is distributed in the north region of the eastern Sichuan Basin,and CO2 in H2S-poor and H2S-free reservoirs was mainly derived from the thermal decomposition of carbonate rocks under Permian magmatism and high heat flow,whereas CO2 in the gas reservoirs with high TSR extent was derived mainly from the dedolomitization of carbonate reservoirs under acidic formation water,and the CO2 of TSR origin generally entered into the secondary calcite.The CO2 in natural gas in the south-central region of the eastern Sichuan Basin,which had been rarely affected by the Emeishan mantle plume,displayed low δ13C values and was of organic origin.Though the natural gas in Wolonghe gas field had experienced TSR,the low reaction extent and weak acidity of formation water could hardly have resulted in the dedolomitization,and therefore CO2 in the natural gas was mainly of TSR origin with low δ13C values.     

Capillary pressure for the sand–CO2–water system under various pressure conditions. Application to CO2 sequestration

Accurate modeling of storage of carbon dioxide (CO₂) in heterogeneous aquifers requires experiments of the capillary pressure as function of temperature and pressure. We present a method with which static drainage and imbibition capillary pressures can be measured continuously as a function of saturation at various temperature (T) and pressure (P) conditions. The measurements are carried out at (T, P) conditions of practical interest. Static conditions can be assumed as small injection rates are applied. The capillary pressure curves are obtained for the unconsolidated sand–distilled water–CO₂ system. The experimental results show a decrease of drainage and imbibition capillary pressure for increasing CO₂ pressures and pronounced dissolution rate effects for gaseous CO₂. Significant capillary pressure fluctuations and negative values during imbibition are observed at near critical conditions. The measurement procedure is validated by a numerical model that simulates the experiments.     

A method for shipboard measurement of CO2 partial pressure in seawater

A dynamic method suitable for shipboard measurement of the partial pressure of CO₂ exerted by a seawater sample has been developed. The system consists of a paddle-wheel-type gas-water equilibrator and an infrared gas analyzer. Since the system is open to the atmosphere at the in-take and the exhaust ends, it can be operated stably on shipboard conditions. A precision of ±2% has been obtained for shipboard measurement of pCO₂.     

Geochemical features of the geothermal CO2-watercarbonate rock system and analysis on its CO2 sources

Taking Huanglong Ravine and Kangding, Sichuan, and Xiage, Zhongdian, Yunnan, as examples, the authors summarize the hydrogeochemical and carbon stable isotopic features of the geothermal CO₂-water-carbonate rock system and analyze the CO₂ sources of the system. It was found that the hydrogeochemical and carbon stable isotopic features of such a system are different from those of shallow CO₂-water-carbonate rock system, which is strongly influenced by biosphere. The former has higher CO₂ partial pressure, and is rich in heavy carbon stable isotope. In addition, such a geothermal system is also different from that developed in igneous rock. The water in the latter system lacks Ca²⁺, and thus, there are few tufa deposits on ground surface, but it is rich in light carbon stable isotope. Further analysis shows that CO₂ of the geothermal CO₂-water-carbonate rock system is a mixture of metamorphic CO₂ and magmatic CO₂.     

Shock-induced CO2 loss from CaCO3; implications for early planetary atmospheres

We report new results of shock recovery experiments on single crystal calcite. Recovered samples are subjected to thermogravimetric analysis. This yields the maximum amount of post-shock CO₂, the decarbonization interval, ΔT, and the energy of association (or vaporization), ΔEV, for the removal of remaining CO₂ in shock-loaded calcite. Comparison of post-shock CO₂ with that initially present determines shock-induced CO₂ loss as a function of shock pressure. Incipient to complete CO₂ loss occurs over a pressure range of 10to 70GPa. The latter pressure should be considered a lower bound. Comparable to results on hydrous minerals, ΔT and ΔEV decrease systematically with increasing shock pressure. This indicates that shock loading leads to both the removal of structural volatiles and weakening of bonds between the volatile species and remainder of the crystal lattice.Optical and scanning electron microscopy (SEM) reveal structural changes, which are related to the shock-loading. Comparable to previous findings on shocked antigorite is the occurrence of dark, diffuse areas, which can be resolved as highly vesicular areas as observed with a scanning electron microscope. These areas are interpreted as representing quenched partial melts, into which shock-released CO₂ has been injected.The experimental results are used to place bonds on models of impact production of CO₂ during accretion of the terrestrial planets.     

Melting relationships in CaO-CO2 and MgO-CO2 to 36 kilobars with comments on CO2 in the mantle

The melting curves of CaCO₃ and MgCO₃ have been extended to pressures of 36 kb by experiments in piston-cylinder apparatus. At 30 kb, the melting temperatures of calcite and magnesite are 1610°C and 1585°C, respectively. New data for the magnesite dissociation reaction permit the location of an invariant point for the assemblage magnesite + periclase + liquid + vapor near 26 kb-1550°C. New data are also presented for the calcite-aragonite transition at 800°C, 950°C and 1100°C. At pressures above 36–50 kb, calcite and magnesite melt at temperatures lower than the solidus of dry mantle peridotite. Natural and experimental evidence suggests that carbon dioxide in the Earth's mantle could be present in a variety of forms: (a) a free vapor phase, (b) vapor dissolved in silicate magma, (c) crystalline carbonate, (d) carbonatite liquid, (e) carbon-bearing silicate analogs, or (f) carbonato-silicates (such as scapolite, spurrite, tilleyite, and related compounds).     

微囊藻CO2-浓缩机制基因型的动态变化及其对CO2的竞争效应

由于具有高效的CO₂-浓缩机制,蓝藻在低CO₂浓度条件下具有竞争优势。然而,随着大气中CO₂浓度急剧增加,蓝藻CO₂-浓缩机制如何响应的研究较少。因此,本文以常见水华蓝藻——微囊藻为研究对象,通过对滇池微囊藻水华动态及不同CO₂-浓缩机制基因型进行监测,探讨蓝藻CO₂-浓缩机制基因的微进化特征及其动态变化。同时,设置高(0.08%)、中(0.04%)、低(0.02%)CO₂浓度(V/V)进一步揭示微囊藻不同CO₂-浓缩机制基因微进化对CO₂的竞争效应。结果表明:滇池无机碳浓度在4个采样点存在空间差异性,均呈现先降低后升高的趋势,并以HCO₃^-为主要无机碳存在形式。调查期间,东大河、观音山、洛龙河和生态所4个采样点的微囊藻均以sbtA基因型占绝对优势,相对丰度远高于bicA基因型。在不同水华时期,bicA基因型和sbtA基因型呈现相反的变化趋势,即从...     

The use of sulfur hexafluoride (SF6) as a tracer of septic tank effluent in the Florida Keys

To determine the fate and movement of sewage derived contaminants and their possible interaction with surface waters in the Florida (USA) Keys, two types of experiments were conducted using SF₆ as an artificial tracer. The first type of experiment examined fluid flow from septic tanks placed in Miami Oolite on Big Pine Key, where there is a shallow freshwater lens overlying saline groundwaters. Here groundwater transport rates were constrained to be between 0.11 and 1.87 m/h, travelling in an easterly direction. The second type of experiment took place on Key Largo where there is no freshwater aquifer and the matrix of the aquifer is solely the more porous Key Largo limestone. Here we injected the tracer into a shallow well which was screened from 0.6 to 10 m. This allowed us to evaluate groundwater movement in the shallow upper portion of the aquifer, the area to which inputs by septic tanks occur. Groundwater transport rates in the Upper Keys were as great as 3.7 m/h and were controlled by the Atlantic tide. SF₆ laden groundwater plumes moved back and forth due to tidal pumping and reached nearby surface waters within 8 h.     

A stochastic model for daily subsurface CO2 concentration and related soil respiration

Near-surface soil CO₂ gas-phase concentration (C) and concomitant incident rainfall (P_i) and through-fall (P_t) depths were collected at different locations in a temperate pine forest every 30 min during the 2005 and 2006 growing seasons (and then averaged to the daily timescale). At the daily scale, C temporal variations were well described by a sequence of monotonically decreasing functions interrupted by large positive jumps induced by rainfall events. A stochastic model was developed to link rainfall statistics responsible for these jumps to near-surface C dynamics. The model accounted for the effect of daily rainfall variability, both in terms of timing and amount of water, and permitted an analytical derivation of the C probability density function (pdf) using the parameters of the rainfall pdf. Given the observed positive correlation between daily C and soil CO₂ fluxes to the atmosphere (F_s), the effects of various rainfall regimes on the statistics of F_s can be deduced from the behavior of C under different climatic conditions. The predictions from this analytical model are consistent with flux measurements reported in manipulative experiments that varied rainfall amount and frequency.     

三峡水库CO2、CH4通量监测分析研究

自成库以来,三峡水库CO₂、CH₄等温室气体通量较蓄水前发生明显改变。如何科学认识和客观评估三峡水库修建及运行对其CO₂、CH₄等温室气体通量的影响备受关注。本文简要回顾了自2009年以来在三峡水库开展CO₂、CH₄等温室气体通量监测与分析工作,综述认为,现阶段三峡水库温室气体排放以水-气界面扩散释放为主要途径。陆源输入的有机碳是主导三峡水库CO₂、CH₄产生的主要碳源,但在局部区段或时段自源性有机碳的贡献亦十分显著。同蓄水前相比,三峡水库碳排放量呈现为净增加,淹没效应约占水库C净增量的20%,库区内点面源污染负荷并未对CO₂排放的净增量产生显著贡献,阻隔效应和生态系统重建效应对三峡水库碳排放的净增量产生显著贡献。近10年来,监测方法比对、监测点位优化等工作在一定程度上完善了三峡水库温室气体通量监测体系。新方法、新技术的引入也为三峡水库温室气体通量监测分析提供了有利支撑和保障,但复杂水文环境...     

Quantifying CO2 fluxes from soil surfaces to the atmosphere

Measurements of CO₂ fluxes from ground surface of the atmosphere (soil respiration) are needed to quantify biotic and abiotic reaction rates in unsaturated zones and to gain insight into the importance of these processes on global warming. The use of three techniques (dynamic closed chambers, static chambers, and gradient calculations) to determine soil respiration was assessed by measuring fluxes of microbially produced CO₂ from an unsaturated mesocosm (2.4 m dia.×3.2 m thick) and two unsaturated minicosms (0.58 m dia.×1.2 m thick), one maintained at 18–23 °C (HT) and the other at 5 °C (LT). By injecting known and constant CO₂ fluxes into the bottom of the HT minicosm and measuring the resulting fluxes, it was shown that the dynamic closed chamber (DCCS) technique yielded accurate measurements of fluxes over the range observed from natural unsaturated media. Over this same range, results showed that the concentration gradient method yielded reasonable estimates of fluxes but its accuracy was limited by uncertainties in both the concentration gradient and the gaseous diffusion coefficient in the soil atmosphere. The static chamber method underestimated the actual flux at higher CO₂ fluxes and when adsorption times of >24 h were used.