Site characterization for CO<Subscript>2</Subscript> geologic storage and vice versa: the Frio brine pilot,Texas, USA as a case study

Careful site characterization is critical for successful geologic storage of carbon dioxide (CO₂) because of the many physical and chemical processes impacting CO₂ movement and containment under field conditions. Traditional site characterization techniques such as geological mapping, geophysical imaging, well logging, core analyses, and hydraulic well testing provide the basis for judging whether or not a site is suitable for CO₂ storage. However, only through the injection and monitoring of CO₂ itself can the coupling between buoyancy flow, geologic heterogeneity, and history-dependent multi-phase flow effects be observed and quantified. CO₂ injection and monitoring can therefore provide a valuable addition to the site-characterization process. Additionally, careful monitoring and verification of CO₂ plume development during the early stages of commercial operation should be performed to assess storage potential and demonstrate permanence. The Frio brine pilot, a research project located in Dayton, Texas (USA) is used as a case study to illustrate the concept of an iterative sequence in which traditional site characterization is used to prepare for CO₂ injection and then CO₂ injection itself is used to further site-characterization efforts, constrain geologic storage potential, and validate understanding of geochemical and hydrological processes. At the Frio brine pilot, in addition to traditional site-characterization techniques, CO₂ movement in the subsurface is monitored by sampling fluid at an observation well, running CO₂-saturation-sensitive well logs periodically in both injection and observation wells, imaging with crosswell seismic in the plane between the injection and observation wells, and obtaining vertical seismic profiles to monitor the CO₂ plume as it migrates beyond the immediate vicinity of the wells. Numerical modeling plays a central role in integrating geological, geophysical, and hydrological field observations.     

On CO<Subscript>2</Subscript> fluid flow and heat transfer behavior in the subsurface,following leakage from a geologic storage reservoir

Geologic storage of CO₂ is expected to produce plumes of large areal extent, and some leakage may occur along fractures, fault zones, or improperly plugged pre-existing wellbores. A review of physical and chemical processes accompanying leakage suggests a potential for self-enhancement. The numerical simulations presented here confirm this expectation, but reveal self-limiting features as well. It seems unlikely that CO₂ leakage could trigger a high-energy run-away discharge, a so-called “pneumatic eruption,” but present understanding is insufficient to rule out this possibility. The most promising avenue for increasing understanding of CO₂ leakage behavior is the study of natural analogues.     

Site characterisation of a basin-scale CO<Subscript>2</Subscript> geological storage system: Gippsland Basin,southeast Australia

Geological storage of CO₂ in the offshore Gippsland Basin, Australia, is being investigated by the Cooperative Research Centre for Greenhouse Gas Technologies (CO2CRC) as a possible method for storing the very large volumes of CO₂ emissions from the nearby Latrobe Valley area. A storage capacity of about 50 million tonnes of CO₂ per annum for a 40-year injection period is required, which will necessitate several individual storage sites to be used both sequentially and simultaneously, but timed such that existing hydrocarbon assets will not be compromised. Detailed characterisation focussed on the Kingfish Field area as the first site to be potentially used, in the anticipation that this oil field will be depleted within the period 2015–2025. The potential injection targets are the interbedded sandstones of the Paleocene-Eocene upper Latrobe Group, regionally sealed by the Lakes Entrance Formation. The research identified several features to the offshore Gippsland Basin that make it particularly favourable for CO₂ storage. These include: a complex stratigraphic architecture that provides baffles which slow vertical migration and increase residual gas trapping and dissolution; non-reactive reservoir units that have high injectivity; a thin, suitably reactive, lower permeability marginal reservoir just below the regional seal providing mineral trapping; several depleted oil fields that provide storage capacity coupled with a transient production-induced flow regime that enhances containment; and long migration pathways beneath a competent regional seal. This study has shown that the Gippsland Basin has sufficient capacity to store very large volumes of CO₂. It may provide a solution to the problem of substantially reducing greenhouse gas emissions from future coal developments in the Latrobe Valley.     

Seal integrity and feasibility of CO<Subscript>2</Subscript> sequestration in the Teapot Dome EOR pilot: geomechanical site characterization

This paper reports a preliminary investigation of CO₂ sequestration and seal integrity at Teapot Dome oil field, Wyoming, USA, with the objective of predicting the potential risk of CO₂ leakage along reservoir-bounding faults. CO₂ injection into reservoirs creates anomalously high pore pressure at the top of the reservoir that could potentially hydraulically fracture the caprock or trigger slip on reservoir-bounding faults. The Tensleep Formation, a Pennsylvanian age eolian sandstone is evaluated as the target horizon for a pilot CO₂ EOR-carbon storage experiment, in a three-way closure trap against a bounding fault, termed the S1 fault. A preliminary geomechanical model of the Tensleep Formation has been developed to evaluate the potential for CO₂ injection inducing slip on the S1 fault and thus threatening seal integrity. Uncertainties in the stress tensor and fault geometry have been incorporated into the analysis using Monte Carlo simulation. The authors find that even the most pessimistic risk scenario would require ∼10 MPa of excess pressure to cause the S1 fault to reactivate and provide a potential leakage pathway. This would correspond to a CO₂ column height of ∼1,500 m, whereas the structural closure of the Tensleep Formation in the pilot injection area does not exceed 100 m. It is therefore apparent that CO₂ injection is not likely to compromise the S1 fault stability. Better constraint of the least principal stress is needed to establish a more reliable estimate of the maximum reservoir pressure required to hydrofracture the caprock.     

Time-lapse crosswell seismic and VSP monitoring of injected CO<Subscript>2</Subscript> in a brine aquifer

Seismic surveys successfully imaged a small scale CO₂ injection (1,600 ton) conducted in a brine aquifer of the Frio Formation near Houston, Texas. These time-lapse borehole seismic surveys, crosswell and vertical seismic profile (VSP), were acquired to monitor the CO₂ distribution using two boreholes (the new injection well and a pre-existing well used for monitoring) which are 30 m apart at a depth of 1,500 m. The crosswell survey provided a high-resolution image of the CO₂ distribution between the wells via tomographic imaging of the P-wave velocity decrease (up to 500 m/s). The simultaneously acquired S-wave tomography showed little change in S-wave velocity, as expected for fluid substitution. A rock physics model was used to estimate CO₂ saturations of 10–20% from the P-wave velocity change. The VSP survey resolved a large (∼70%) change in reflection amplitude for the Frio horizon. This CO₂ induced reflection amplitude change allowed estimation of the CO₂ extent beyond the monitor well and on three azimuths. The VSP result is compared with numerical modeling of CO₂ saturations and is seismically modeled using the velocity change estimated in the crosswell survey.     

CO<Subscript>2</Subscript> leakage through an abandoned well: problem-oriented benchmarks

The efficiency and sustainability of carbon dioxide (CO₂) storage in deep geological formations crucially depends on the integrity of the overlying cap-rocks. Existing oil and gas wells, which penetrate the formations, are potential leakage pathways. This problem has been discussed in the literature, and a number of investigations using semi-analytical mathematical approaches have been carried out by other authors to quantify leakage rates. The semi-analytical results are based on a number of simplifying assumptions. Thus, it is of great interest to assess the influence of these assumptions. We use a numerical model to compare the results with those of the semi-analytical model. Then we ease the simplifying restrictions and include more complex thermodynamic processes including sub- and supercritical fluid properties of CO₂ and non-isothermal as well as compositional effects. The aim is to set up problem-oriented benchmark examples that allow a comparison of different modeling approaches to the problem of CO₂ leakage.     

Low-temperature heat capacities of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and spinels of the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution

We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl₂O₄ and MgCr₂O₄. The data also include new low-temperature heat capacity measurements for MgAl₂O₄ spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl₂O₄ spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)₂O₄ spinels. We suggest a standard entropy for MgAl₂O₄ of 80.9 ± 0.6 J mol⁻¹ K⁻¹. For the solid solution between MgAl₂O₄ and MgCr₂O₄, we observe a linear increase of the standard entropies from 80.9 J mol⁻¹ K⁻¹ for MgAl₂O₄ to 118.3 J mol⁻¹ K⁻¹ for MgCr₂O₄.     

CO<Subscript>2</Subscript> absorption by alkaline soils and its implication to the global carbon cycle

Motivated by the rapid increase in atmospheric CO₂ due to human activities since the Industrial Revolution, and the climate changes it produced, the world’s concerned scientific community has made a huge effort to investigate the global carbon cycle. However, the results reveal that the global CO₂ budget cannot be balanced, unless a “missing sink” is invoked. Although numerous studies claimed to find the “missing sink”, none of those claims has been widely accepted. This current study showed that alkaline soil on land are absorbing CO₂ at a rate of 0.3–3.0 μmol m⁻² s⁻¹ with an inorganic, non-biological process. The intensity of this CO₂ absorption is determined by the salinity, alkalinity, temperature and water content of the saline/alkaline soils, which are widely distributed on land. Further studies revealed that high salinity or alkalinity positively affected the CO₂ absorbing intensity, while high temperature and water content had a negative effect on the CO₂ absorbing intensity of these soils. This inorganic, non-biological process of CO₂ absorption by alkaline soils might have significant implications to the global carbon budget accounting.     

Invasion of anthropogenic CO<Subscript>2</Subscript> recorded in planktonic foraminifera from the northern Gulf of Aqaba

The stable carbon isotopic composition of the planktonic foraminifera Globigerinoides sacculifer and G. ruber (white) and sedimentary organic matter from the northern Gulf of Aqaba have been investigated to estimate changes in ¹³C_DIC in surface waters during the last 1,000 years. The high sedimentation rates at the core sites (about 54 cm/Kyear) provide high temporal resolution (~10 years). Recent sediments at the top of the cores reflect conditions younger than 1950. The ¹³C records of the planktonic foraminifera from three multicores display similar trends, showing a uniform and consistent pattern before the 1750s, and a gradual decrease of approximately 0.63 over the last two centuries. This decrease seems to track the decrease of ¹³C_DIC in surface waters, which is mainly caused by the increase of anthropogenic input of ¹³C-depleted CO₂ into the atmosphere. Similarly, a trend towards lighter values of the carbon isotopic composition of sedimentary organic matter (¹³C_org) during the last 200 years supports the interpretation obtained from the planktonic foraminiferal ¹³C. Furthermore, direct measurements of seawater show that ¹³C of the dissolved inorganic carbon (DIC) in the northern Gulf of Aqaba has decreased by about 0.44 during the period 1979–2000. The average annual decrease is 0.021, which is similar to that observed globally. The ¹³C values of planktonic foraminifera combined with organic matter ¹³C from marine sediments are good indicators for reconstructing past changes in atmospheric CO₂ concentrations from the northern Gulf of Aqaba.     

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

Geochemical Eccentricity of Ground Water Allied to Weathering of Basalts from the Deccan Volcanic Province,India: Insinuation on CO<Subscript>2</Subscript> Consumption

Analyses of 72 samples from Upper Panjhara basin in the northern part of Deccan Plateau, India, indicate that geochemical incongruity of groundwater is largely a function of mineral composition of the basaltic lithology. Higher proportion of alkaline earth elements to total cations and HCO₃>Cl + SO₄ reflect weathering of primary silicates as chief source of ions. Inputs of Cl, SO₄, and NO₃ are related to rainfall and localized anthropogenic factors. Groundwater from recharge area representing Ca + Mg–HCO₃ type progressively evolves to Ca + Na–HCO₃ and Na–Ca–HCO₃ class along flow direction replicates the role of cation exchange and precipitation processes. While the post-monsoon chemistry is controlled by silicate mineral dissolution + cation exchange reactions, pre-monsoon variability is attributable chiefly to precipitation reactions + anthropogenic factors. Positive correlations between Mg vs HCO₃ and Ca + Mg vs HCO₃ supports selective dissolution of olivine and pyroxene as dominant process in post-monsoon followed by dissolution of plagioclase feldspar and secondary carbonates. The pre-monsoon data however, points toward the dissolution of plagioclase and precipitation of CaCO₃ supported by improved correlation coefficients between Na + Ca vs HCO₃ and negative correlation of Ca vs HCO₃, respectively. It is proposed that the eccentricity in the composition of groundwater from the Panjhara basin is a function of selective dissolution of olivine > pyroxene followed by plagioclase feldspar. The data suggest siallitization (L < R and R _k) as dominant mechanism of chemical weathering of basalts, stimulating monosiallitic (kaolinite) and bisiallitic (montmorillonite) products. The chemical denudation rates for Panjhara basin worked out separately for the ground and surface water component range from 6.98 to 36.65 tons/km²/yr, respectively. The values of the CO₂ consumption rates range between 0.18 × 10⁶ mol//km²/yr (groundwater) and 0.9 × 10⁶ mol/km²/yr (surface water), which indicates that the groundwater forms a considerable fraction of CO₂ consumption, an inference, that is, not taken into contemplation in most of the studies.     

Experimental and numerical study on the fracture of rocks during injection of CO<Subscript>2</Subscript>-saturated water

Geological sequestration of CO₂ into depleted hydrocarbon reserviors or saline aquifers presents the enormous potential to reduce greenhouse gas emission from fossil fuels. However, it may give rise to a complicated coupling physical and chemical process. One of the processes is the hydro-mechanical impact of CO₂ injection. During the injection project, the increase of pore pressures of storing formations can induce the instability, which finally results in a catastrophic failure of disposal sites. This paper focuses mainly on the role of CO₂-saturated water in the fracturing behavior of rocks. To investigate how much the dissolved CO₂ can influence the pore pressure change of rocks, acoustic emission (AE) experiments were performed on sandstone and granite samples under triaxial conditions. The main innovation of this paper is to propose a time dependent porosity method to simulate the abrupt failure process, which is observed in the laboratory and induced by the pore pressure change due to the volume dilatancy of rocks, using a finite element scheme associated with two-phase characteristics. The results successfully explained the phenomena obtained in the physical experiments.     

CO<Subscript>2</Subscript>-rich fluid inclusions with chalcopyrite daughter mineral from the Fenghuangshan Cu–Fe–Au deposit,China: implications for metal transport in vapor

CO₂-rich fluid inclusions containing opaque mineral crystals were found in the Fenghuangshan skarn-porphyry Cu–Fe–Au deposit in Tongling, Anhui, China. These inclusions show variable CO₂ contents and are accompanied by aqueous inclusions, both occurring as secondary inclusions in quartz and being locally associated with chalcopyrite mineralization. Laser Raman microspectroscopic analyses confirm the predominance of CO₂ in the vapor and the presence of H₂S as high as 8 mol%, and identify the opaque mineral with yellow reflectance color in the inclusions as chalcopyrite. More than half of the CO₂-bearing inclusions contains chalcopyrite, whereas few of the associated aqueous inclusions do so. The chalcopyrite, occupying less than 1% (volume) of the inclusions, is interpreted to be a daughter mineral, and calculated Cu concentrations in the inclusions range from 0.1 to 3.4 wt%. Copper is inferred to have been transported in CO₂-dominated fluids as HS⁻ complexes. The occurrence of chalcopyrite daughter crystals in CO₂-rich fluid inclusions indicates that CO₂-rich vapor has the capacity of transporting large amounts of Cu, and possibly Au. This finding has significant implications for metal transport and mineralization in hydrothermal systems enriched in CO₂, such as orogenic-type and granitic intrusion-related gold deposits.     

Dissolution of Carbonate Sediments Under Rising <Emphasis Type="Italic">p</Emphasis>CO<Subscript>2</Subscript> and Ocean Acidification: Observations from Devil’s Hole,Bermuda

Rising atmospheric pCO₂ and ocean acidification originating from human activities could result in increased dissolution of metastable carbonate minerals in shallow-water marine sediments. In the present study, in situ dissolution of carbonate sedimentary particles in Devil’s Hole, Bermuda, was observed during summer when thermally driven density stratification restricted mixing between the bottom water and the surface mixed layer and microbial decomposition of organic matter in the subthermocline layer produced pCO₂ levels similar to or higher than those levels anticipated by the end of the 21st century. Trends in both seawater chemistry and the composition of sediments in Devil’s Hole indicate that Mg-calcite minerals are subject to selective dissolution under conditions of elevated pCO₂. The derived rates of dissolution based on observed changes in excess alkalinity and estimates of vertical eddy diffusion ranged from 0.2 mmol to 0.8 mmol CaCO₃ m⁻² h⁻¹. On a yearly basis, this range corresponds to 175–701 g CaCO₃ m⁻² year⁻¹; the latter rate is close to 50% of the estimate of the current average global coral reef calcification rate of about 1,500 g CaCO₃ m⁻² year⁻¹. Considering a reduction in marine calcification of 40% by the year 2100, or 90% by 2300, as a result of surface ocean acidification, the combination of high rates of carbonate dissolution and reduced rates of calcification implies that coral reefs and other carbonate sediment environments within the 21st and following centuries could be subject to a net loss in carbonate material as a result of increasing pCO₂ arising from burning of fossil fuels.     

Capturing and storage of CO<Subscript>2</Subscript> by micron-nano minerals: Evidence from the nature

The increase of CO2 in atmosphere is a main factor leading to "greenhouse effect", which causes more and more serious global environmental problems. The reduction of CO2 is a challenge for the survival of human beings, and it is also a big technical problem. CO2 fluid-rock interaction is a key scientific problem involved in geo-logical storage. The CO2 fluid-rock interaction has a variety of multi-scale changes. Due to great differences in the quantity of surface atoms and surface energy between micron-nano-sized minerals, and ions and crystals, the speed and efficiency of CO2 fluid-rock interaction on a micron-nano scale are much higher than those on other scales. As is known from the natural world, the micron-nano structures of pores and the surface chemical modification of natural porous minerals (zeolite, diatomite, sepiolite, palygorskite, halloysite, etc.) should be further investigated, which can be used as the micron-nano -mineral porous materials with high capacity and high efficiency for capturing CO2. Through simulating the adsorption capacity and process of CO2 by minerals in the natural world, the micron-nano technology is applied to calcium- and magnesium-based minerals (olivine, pyroxene, feldspar, clay, etc.) so as to improve the activity of calcium and magnesium and enlarge the reaction contact area. In this way, the efficiency of capturing and storage of CO2 by calcium- and magnesium-based minerals can be greatly improved. These minerals can also be used as the micron-nano-mineral materials with large capacity and high efficiency for capturing and storing CO2.     

First-principles simulation of high-pressure polymorphs in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>

We have used density functional theory to investigate the stability of MgAl₂O₄ polymorphs under pressure. Our results can reasonably explain the transition sequence of MgAl₂O₄ polymorphs observed in previous experiments. The spinel phase (stable at ambient conditions) dissociates into periclase and corundum at 14 GPa. With increasing pressure, a phase change from the two oxides to a calcium-ferrite phase occurs, and finally transforms to a calcium-titanate phase at 68 GPa. The calcium-titanate phase is stable up to at least 150 GPa, and we did not observe a stability field for a hexagonal phase or periclase + Rh₂O₃(II)-type Al₂O₃. The bulk moduli of the phases calculated in this study are in good agreement with those measured in high-pressure experiments. Our results differ from those of a previous study using similar methods. We attribute this inconsistency to an incomplete optimization of a cell shape and ionic positions at high pressures in the previous calculations.     

Equation of state,structural behaviour and phase diagram of synthetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as a function of pressure and temperature

The behaviour of synthetic Mg-ferrite (MgFe₂O₄) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K₀=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa^–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by _a0+_a1*(T–298)+_a2/(T–298)², where _a0=9.1(1) 10^–6 K^–1, _a1=4.9(2) 10^–9 K^–2 and _a2= 5.1(5) 10^–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol^–1 and =–17.6(± 1.2) kJ mol^–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe₂O₄, which shows that the high-pressure transition from spinel to orthorombic CaMn₂O₄-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe₂O₃.     

On leakage and seepage of CO2 from geologic storage sites into surface water

Geologic carbon sequestration is the capture of anthropogenic carbon dioxide (CO₂) and its storage in deep geologic formations. The processes of CO₂ seepage into surface water after migration through water-saturated sediments are reviewed. Natural CO₂ and CH₄ fluxes are pervasive in surface-water environments and are good analogues to potential leakage and seepage of CO₂. Buoyancy-driven bubble rise in surface water reaches a maximum velocity of approximately 30 cm s⁻¹. CO₂ rise in saturated porous media tends to occur as channel flow rather than bubble flow. A comparison of ebullition versus dispersive gas transport for CO₂ and CH₄ shows that bubble flow will dominate over dispersion in surface water. Gaseous CO₂ solubility in variable-salinity waters decreases as pressure decreases leading to greater likelihood of ebullition and bubble flow in surface water as CO₂ migrates upward.     

Low-temperature heat capacities,entropies and enthalpies of Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> polymorphs,and α−β−γ and post-spinel phase relations at high pressure

The low-temperature isobaric heat capacities (C _p) of β- and γ-Mg₂SiO₄ were measured at the range of 1.8–304.7 K with a thermal relaxation method using the Physical Property Measurement System. The obtained standard entropies (S°₂₉₈) of β- and γ-Mg₂SiO₄ are 86.4 ± 0.4 and 82.7 ± 0.5 J/mol K, respectively. Enthalpies of transitions among α-, β- and γ-Mg₂SiO₄ were measured by high-temperature drop-solution calorimetry with gas-bubbling technique. The enthalpies of the α−β and β−γ transitions at 298 K (ΔH°₂₉₈) in Mg₂SiO₄ are 27.2 ± 3.6 and 12.9 ± 3.3 kJ/mol, respectively. Calculated α−β and β−γ transition boundaries were generally consistent with those determined by high-pressure experiments within the errors. Combining the measured ΔH°₂₉₈ and ΔS°₂₉₈ with selected data of in situ X-ray diffraction experiments at high pressure, the ΔH°₂₉₈ and ΔS°₂₉₈ of the α−β and β−γ transitions were optimized. Calculation using the optimized data tightly constrained the α−β and β−γ transition boundaries in the P, T space. The slope of α−β transition boundary is 3.1 MPa/K at 13.4 GPa and 1,400 K, and that of β−γ boundary 5.2 MPa/K at 18.7 GPa and 1,600 K. The post-spinel transition boundary of γ-Mg₂SiO₄ to MgSiO₃ perovskite plus MgO was also calculated, using the optimized data on γ-Mg₂SiO₄ and available enthalpy and entropy data on MgSiO₃ perovskite and MgO. The calculated post-spinel boundary with a Clapeyron slope of −2.6 ± 0.2 MPa/K is located at pressure consistent with the 660 km discontinuity, considering the error of the thermodynamic data.     

Effects of nitrogen on the ecosystem respiration,CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O emissions to the atmosphere from the freshwater marshes in northeast China

Freshwater marshes could be a source of greenhouse gases emission because they contain large amounts of soil carbon and nitrogen. These emissions are strongly influenced by exogenous nitrogen. We investigate the effects of exogenous nitrogen on ecosystem respiration (CO₂), CH₄ and N₂O emissions from freshwater marshes in situ in the Sanjiang Plain Northeast of China during the growing seasons of 2004 and 2005, using a field fertilizer experiment and the static opaque chamber/GC techniques. The results show that there were no significant differences in patterns of seasonal variations of CO₂ and CH₄ among the fertilizer and non-fertilizer treatments, but the seasonal patterns of N₂O emission were significantly influenced by the exogenous nitrogen. Seasonal averages of the CO₂ flux from non-fertilizer and fertilizer were 987.74 and 1,344.35 mg m ⁻² h ⁻¹, respectively, in 2004, and 898.59 and 2,154.17 mg m ⁻² h ⁻¹, respectively, in 2005. And the CH₄ from the control and fertilizer treatments were 6.05 and 13.56 mg m ⁻² h ⁻¹ and 0.72 and 1.88 mg m ⁻² h ⁻¹, respectively, in 2004 and 2005. The difference of N₂O flux between the fertilizer and non-fertilizer treatments is also significant either in 2004 and 2005. On the time scale of 20-, 100-, and 500-year periods, the integrated global warming potential (GWP) of CO₂ + CH₄ + N₂O released during the two growing seasons for the treatment of fertilizer was 97, 94 and 89%, respectively, higher than that for the control, which suggested that the nitrogen fertilizer can enhance the GWP of the CH₄ and N₂O either in long time or short time scale.