CO2 emission from Dianshan Lake in summer, East China

Shallow fresh water bodies in peat areas could be an important contributor to greenhouse gases in the atmosphere.In this study,the partial pressure of CO2 in the surface water of the Dianshan Lake was investigated insitu in August 2011.The average pCO2 in the study area was 2300μatm and fluctuated within the range of 989–5000μatm.pCO2 showed a reverse trend to the variations of pH and DO in the surface water of the Dianshan Lake.The water to air diffusion flux of CO2 of the upstream,middle lake and downstream were respectively 63,33 and 14mmol/m2/d.On average,the diffusion flux of CO2 of the whole lake was 31 mmol/m2/d.Consequently,our results show that during the sampling season,the Dianshan Lake appears to be a great source of CO2.It is also demonstrated that respiration could be the dominant biochemical reaction in the Dianshan Lake in summer.     

Distribution,abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake,Nevada: An alkaline,meromictic lake

Distribution and isotopic composition (δ¹³C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20–35 m), reached uniform concentrations (55 μM/l) in the monimolimnion (35–64 m) and again increased with depth in monimolimnion bottom sediments (>400 μM/kg below 1 m sub-bottom depth). The μ¹³C[CH₄] values in bottom sediment below 1 m sub-bottom depth (<?70 per mil) increased with vertical distance up the core (δ¹³C[CH₄] = ?55 per mil at sediment surface). Monimolimnion δ¹³C[CH₄] values (?55 to ?61 per mil) were greater than most δ¹³C[CH₄] values found in the anoxic mixolimnion (92% of samples had δ¹³C[CH₄] values between ?20 and ?48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50–60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of $\text{CH}{}_4\text{[C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{]}$ were high (250–620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C₂-C₄ alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in δ¹³C[CH₄] and $\text{CH}{}_4\text{(C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{)}$ with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C₂ to C₄ alkane production by microorganisms.     

Methane production and consumption monitored by stable H and C isotope ratios at a crude oil spill site,Bemidji, Minnesota

Stable isotopic ratios of C and H in dissolved CH₄ and C in dissolved inorganic C in the ground water of a crude-oil spill near Bemidji, Minnesota, support the concept of CH₄ production by acetate fermentation with a contemporaneous increase in HCO₃⁻ concentration. Methane concentrations in the saturated zone decrease from 20.6 mg L⁻¹ to less than 0.001 mg L⁻¹ along the investigated flow path. Dissolved N₂ and Ar concentrations in the ground water below the oil plume are 25 times lower than background; this suggests that gas exsolution is removing dissolved CH₄ (along with other dissolved gases) from the ground water. Oxidation of dissolved CH₄ along the flow path seems to be minimal because no measurable change in isotopic composition of CH₄ occurs with distance from the oil body. However, CH₄ is partly oxidized to CO₂ as it diffuses upward from the ground water through a 5- to 7-m thick unsaturated zone; theδ¹³C of the remaining CH₄ increases, theδ¹³C of the CO₂ decreases, and the partial pressure of CO₂ increases.Calculations of C fluxes in the saturated and unsaturated zones originating from the degradation of the oil plume lead to a minimum estimated life expectancy of 110 years. This is a minimum estimate because the degradation of the oil body should slow down with time as its more volatile and reactive components are leached out and preferentially oxidized. The calculated life expectancy is an order of magnitude estimate because of the uncertainty in the average linear ground-water velocities and because of the factor of 2 uncertainty in the calculation of the effective CO₂ diffusion coefficient.     

Soil temperature and moisture controls on surface fluxes and profile concentrations of greenhouse gases in karst area in central part of Guizhou Province, southwest China

In order to better understand the spatiotemporal variations and interrelationships of greenhouse gases (GHG), monthly surface fluxes and profile concentrations of GHG (CO₂, N₂O and CH₄) in karst areas in the Guizhou Province, southwest China, were measured from June 2006 to May 2007. GHG fluxes showed high variability, with a range of 460.9?C1,281.2?mg?m^?2?h^?1 for CO₂, ?25.4 to 81.5???g?m^?2?h^?1 for N₂O and ?28.7 to ?274.9???g?m^?2?h^?1 for CH₄, but no obvious seasonal change trends of the fluxes existed. Profile concentrations of CO₂, N₂O and CH₄ varied between 0.5 and 31.5?mL?L^?1, 0.273 and 0.734, and 0.1 and 3.5???L?L^?1, respectively. In general, concentrations of CO₂ and N₂O increased with depth, while CH₄ had an inverse trend. However, in October, November and January, the reversal of depth patterns of GHG concentrations took place below 15?cm, close to the soil?Crock interface. The spatiotemporal distribution of CO₂ in soil profile was significantly positively correlated with that of N₂O (p?<?0.05?C0.01) and negatively correlated with that of CH₄ (p?<?0.01). The correlation analysis showed that soil temperature and moisture may be responsible for GHG dynamics in the soils, rather than the exchange of GHG between land and atmosphere.     

Detailed compositional analysis of gas seepage at the National Carbon Storage Test Site,Teapot Dome,Wyoming, USA

A baseline determination of CO₂ and CH₄ fluxes and soil gas concentrations of CO₂ and CH₄ was made over the Teapot Dome oil field in the Naval Petroleum Reserve No. 3 (NPR-3) in Wyoming, USA. This was done in anticipation of experimentation with CO₂ sequestration in the Pennsylvanian Tensleep Sandstone underlying the field at a depth of 1680 m.The baseline data were collected during the winter, 2004 in order to minimize near-surface biological activity in the soil profile. The baseline data were used to select anomalous locations that may be the result of seeping thermogenic gas, along with background locations. Five 10-m holes were drilled, 3 of which had anomalous gas microseepage, and 2 were characterized as “background.” These were equipped for nested gas sampling at depths of 10-, 5-, 3-, 2-, and 1-m depths. Methane concentrations as high as 170,000 ppmv (17%) were found, along with high concentrations of C₂H₆, C₃H₈, n-C₄H₁₀, and i-C₄H₁₀. Much smaller concentrations of C₂H₄ and C₃H₆ were observed indicating the beginning of hydrocarbon oxidation in the anomalous holes. The anomalous 10-m holes also had high concentrations of isotopically enriched CO₂, indicating the oxidation of hydrocarbons. Concentrations of the gases decreased upward, as expected, indicating oxidation and transport into the atmosphere. The ancient source of the gases was confirmed by ¹⁴C determinations on CO₂, with radiocarbon ages approaching 38 ka within 5 m of the surface.Modeling was used to analyze the distribution of hydrocarbons in the anomalous and background 10-m holes. Diffusion alone was not sufficient to account for the hydrocarbon concentration distributions, however the data could be fit with the addition of a consumptive reaction. First-order rate constants for methanotrophic oxidation were obtained by inverse modeling. High rates of oxidation were found, particularly near the surface in the anomalous 10-m holes, demonstrating the effectiveness of the process in the attenuation of CH₄ microseepage. The results also demonstrate the importance of CH₄ measurements in the planning of a monitoring and verification program for geological CO₂ sequestration in sites with significant remaining hydrocarbons (i.e. spent oil reservoirs).     

Carbon Dioxide and Methane Dynamics in Three Coastal Systems of Cadiz Bay (SW Spain)

The partial pressure of CO₂ (pCO₂) and concentration of dissolved CH₄ in surface waters have been studied in three coastal systems connected to Cadiz Bay (southwestern coast of Spain) over different time scales. The concentration of CH₄ varied from 1 to 4200 nmol kg^?1 (192.1 ± 463.6 nmol kg^?1) and the saturation percent from 19 to 159,577% (6645 ± 16,921%), and pCO₂ from 315 to 3240 μatm (841.9 ± 466.3 μatm), with saturation percent values varying between 72 and 981% (220 ± 133%). The seasonal variation of pCO₂ mainly depends on the temperature. On the contrary, the annual distribution of dissolved CH₄ is associated with the precipitation regime. In addition, pCO₂ and dissolved CH₄ showed spatial variation. pCO₂ increased toward the inner part of the systems, with the proximity to the discharge points from human activities. Dissolved CH₄ is influenced by both anthropogenic inputs and natural processes such as benthic supply and exchange with the adjacent salt marshes. pCO₂ and dissolved CH₄ also varied with the tides: The highest concentrations were measured during the ebb, which suggests that the systems export CO₂ and CH₄ to the Bay and adjacent Atlantic Ocean.     

Extension of the specific interaction model to include gas solubilities in high temperature brines

A semi-empirical model for gas solubilities in high temperature brines was developed by modification of the Pitzer interaction model (Pitzer, 1973) and evaluated by least-squares fitting to available P-T-X data for carbon dioxide, hydrogen sulfide, and methane in pure water and in aqueous sodium chloride solutions. Over the range of experimental data used (25°–350°C, NaCl concentration 0–6 m, P_CO2 1–150 atm. P_CH4 1–30 atm, P_CH4 1–1700 atm), standard deviations of fit in the natural logarithm of the Henry's law ratio were 0.096 for CO₂, 0.093 for H₂S and 0.116 for CH₄.The model has several advantages. First, it has a theoretical basis which can easily be extended for the inclusion of more than one salt or gas. Second, the equations simplify to the empirically derived equation of Setschenow, in the limit of infinite dilution. Finally, the model is easily integrated into a framework of equations which can yield all of the thermodynamic properties of the system.An example in which values of the model parameters for interaction of gas with salt may be used to estimate the effect of dissolved gas or salt solubility is given.     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

Carbon dioxide concentration and atmospheric flux in the Hudson River

We made direct measurements of the partial pressure of CO₂ (P_{CO 2}) in the tidal-freshwater portion of the Hudson River Estuary over a 3.5-yr period. At all times the Hudson was supersaturated in CO₂ with respect to the atmosphere. P_{CO 2} in surface water averaged 1125±403 (SD) μatm while the atmosphere averaged 416±68 μatm. Weekly samples at a single, mid-river station showed a pronounced and reproducible seasonal cycle with highest values (～2000 μatm) in mid-to-late summer, and lowest values (～500 μatm) generally in late winter. Samples taken along the length of the 190-km section of river showed a general decline in CO₂ from north to south. This decline was most pronounced in summer and very slight in spring. Diel and vertical variation were small relative to the standing stock of CO₂. Over six diel cycles, all taken during the algal growing season, the mean range was 300±114 μatm. CO₂ tended to increase slightly with depth, but the gradient was small, about 0.5 μmol m^?1, or an increase of 190 μatm from top to within 1 m of the bottom. For a large subset of the samples (n=452) we also calculated CO₂ from measurements of pH and total DIC. Calculated and measured values of CO₂ were in reasonably good agreement and a regression of calculated versus measured values had a slope of 0.85±0.04 and an r₂ of 0.60. Combining our measurements with recent experimental studies of gas exchange in the Hudson, we estimate that the Hudson releases CO₂ at a rate of 70–162 g C m^?2 yr^?1 from the river to the atmosphere.     

Stable carbon isotope composition and concentrations of CO2 and CH4 in the deep catotelm of a peat bog

Vertical profiles of concentration and C-isotopic composition of dissolved methane and carbon dioxide were observed over 26 months in the catotelm of a deep (6.5 m) peat bog in Switzerland. The dissolved concentrations of these gases increase with depth while CO₂ predominates over CH₄ (CO₂ ca. 5 times CH₄). This pattern can be reproduced by a reaction-advection-ebullition model, where CO₂ and CH₄ are formed in a ratio of 1:1. The less soluble methane is preferentially lost via outgassing (bubbles). The isotopic fractionation between CO₂ and CH₄ also increases with depth, with α_C values ranging from 1.045 to 1.075. The isotopic composition of the gases traces the passage of respiration-derived CO₂ (from the near surface) through a shallow zone with methanogenesis of low isotopic fractionation (splitting of fermentation-derived acetate). This solution then moves through the catotelm, where methanogenesis occurs by CO₂ reduction (large isotopic fractionation). In the upper part of the catotelm the C-13-depleted respiration-derived CO₂ pool buffers the isotopic composition of CO₂; the δ¹³C of CO₂ increases only slowly. At the same time strongly depleted CH₄ is formed as CO₂ reduction consumes the depleted CO₂. In the lower part of the catotelm, the respiration-derived CO₂ and shallow CH₄ become less important and CO₂ reduction is the dominant source of CO₂ and CH₄. Now, the δ¹³C values of both gases increase until equilibrium is reached with respect to the isotopic composition of the substrate. Thus, the δ¹³C values of methane reach a minimum at intermediate depth, and the deep methane has δ¹³C values comparable to shallow methane. A simple mixing model for the isotopic evolution is suggested. Only minor changes of the observed patterns of methanogenesis (in terms of concentration and isotopic composition) occur over the seasons. The most pronounced of these is a slightly higher rate of acetate splitting in spring.     

Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

The major source of methane (CH₄) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH₄ and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH₄ up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH₄ included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments.Isotopic analyses included δ¹³C, δD, ¹⁴C, and ³H on select CH₄ samples and δD and δ¹⁸O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had δ¹³C values from −79 to −82‰, typical of natural “drift gas” generated by microbial CO₂-reduction. The CH₄ from the shallow lacustrine deposits had δ¹³C values from −63 to −76‰, interpreted as a mixture between CH₄ generated by microbial fermentation and the CO₂-reduction processes within the subsurface sediments. The δD values of all the CH₄ samples were quite negative ranging from −272 to −299‰. Groundwater sampled from the deeper zones also showed quite negative δD values that explained the light δD observed for the CH₄. Radiocarbon analyses of the CH₄ showed decreasing ¹⁴C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH₄ detected in the till deposits of this site was microbial CH₄ generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH₄ from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH₄ could not be completely ruled out.     

Effect of elevated CO2 on carbon pools and fluxes in a brackish marsh

The effects of long-term exposure to elevated atmospheric CO₂ (ambient + 340 ppmv) on carbon cycling were investigated for two plant communities in a Chesapeake Bay brackish marsh, one dominated by the C₃ sedgeSchoenplectus americanus and the other by the C₄ grassSpartina patens. Elevated CO₂ resulted in a significant increase in porewater concentrations of DIC at 30 cm depth (p < 0.1). The CO₂ treatment also yielded increases in DOC (15 to 27%) and dissolved CH₄ (12–18%) in the C₃ marsh (means for several depths over the period of June 1998 and June 1999), but not at a significant level. Elevated CO₂ increased mean ecosystem emissions of CO₂ (34–393 g C m⁻² yr⁻¹) and CH₄ (0.21–0.40 g C m⁻² yr⁻¹) in the C₃ community, but the effects were only significant on certain dates. For example, CO₂ enrichment increased C export to the atmosphere in the C₃ community during one of two winter seasons measured (p = 0.09). In the C₄ community, gross photosynthesis responded relatively weakly to elevated CO₂ (18% increase, p > 0.1), and the concomitant effects on dissolved carbon concentrations, respiration, and CH₄ emissions were small or absent. We concluded that elevated CO₂ has the potential to increase dissolved inorganic carbon export to estuaries.     

Hydrocarbon gases associated with permafrost in the Mackenzie Delta,Northwest Territories,Canada

Molecular and isotopic analyses of core gas samples from 3 permafrost research core holes (92GSCTAGLU, 92GSCKUMAK, 92GSCUNIPKAT; sample core depths ranging from 0.36 to 413.82 m) in the Mackenzie Delta of the Northwest Territories of Canada reveal the presence of hydrocarbon gases from both microbial and thermogenic sources. Analyses of most headspace and blended gas samples from the ice-bonded permafrost portion of the core holes yielded C₁/(C₂+C₃) hydrocarbon gas ratios and CH₄–C isotopic compositions (δ¹³C CH₄) indicative of microbially sourced CH₄ gas. However, near the base of ice-bonded permafrost and into the underlying non-frozen stratigraphic section, an increase in ethane (C₂) concentrations, decreases in C₁/(C₂+C₃) hydrocarbon gas ratios, and CH₄–C isotopic (δ¹³C CH₄) data indicate the presence of hydrocarbon gases derived from a thermogenic source. The thermogenic gas below permafrost in the Mackenzie Delta likely migrated from deeper hydrocarbon accumulations and/or directly from thermally mature hydrocarbon source rocks.     

Sources and flux of natural gases from Mono Lake,California

The ability to identify a formation mechanism for natural gas in a particular environment requires consideration of several geochemical factors when there are multiple sources present. Four primary sources of methane have been identified in Mono Lake. Two of these sources were associated with numerous natural gas seeps which occur at various locations in the lake and extend beyond its present boundary; the two other gas sources result from current microbiological processes. In the natural gas seeps, we observed flow rates as high as 160 moles CH₄ day⁻¹, and estimate total lakewide annual seep flux to be 2.1 × 10⁶ moles CH₄. Geochemical parameters (δ¹³CH₄,δDCH₄,CH₄/[C₂H₆+ C₃H₈]) andδ¹⁴CH₄measurements revealed that most of the seeps originate from a paleo-biogenic (δ¹³CH₄ = about −70%.). natural gas deposit of Pleistocene age which underlies the current and former lakebed. Gas seeps in the vicinity of hot springs had, in combination with the biogenic gas, a prominent thermogenic gas component resulting from hydrothermal alteration of buried organic matter.Current microbiological processes responsible for sources of natural gas in the lake included pelagic meth- anogenesis and decomposition of terrestrial grasses in the littoral zone. Methanogenesis in the pelagic sediments resulted in methane saturation (2–3 mM at 50 cm; δ₁₃CH₄ = about −85%.). Interstitial sulfate decreased from 133 mM at the surface to 35 mM by 110 cm depth, indicating that sulfate-reduction and methanogenesis operated concurrently. Methane diffused out of the sediments resulting in concentrations of about 50 μM in the anoxic bottom waters. Methane oxidation in the oxic/anoxic boundry lowered the concentration by >98%, but values in surface waters (0.1–1.3μM) were supersaturated with respect to the atmosphere. The δ¹³CH₄ (range = −21.8 to −71.8%.) of this unoxidized residual methane was enriched in ¹³C relative to methane in the bottom water and sediments. Average outward flux of this methane was 2.77 × 10⁷ moles yr⁻¹. A fourth, but minor source of methane (δ¹³CH₄ = −55.2%.) was associated with the decomposition of terrestrial grasses taking place in the lake's recently expanded littoral zone.     

Thermal decarboxylation of acetic acid: Implications for origin of natural gas

Laboratory experiments on the thermal decarboxylation of solutions of acetic acid at 200°C and 300°C were carried out in hydrothermal equipment allowing for on-line sampling of both the gas and liquid phases for chemical and stable-carbon-isotope analyses. The solutions had ambient pH values between 2.5 and 7.1; pH values and the concentrations of the various acetate species at the conditions of the experiments were computed using a chemical model.Results show that the concentrations of acetic acid, and not total acetate in solution, control the reaction rates which follow a first order equation based on decreasing concentrations of acetic acid with time. The decarboxylation rates at 200°C (1.81 × 10^?8 per second) and 300°C (8.17 × 10^?8 per second) and the extrapolated rates at lower temperatures are relatively high. The activation energy of decarboxylation is only 8.1 kcal/mole. These high decarboxylation rates, together with the distribution of short-chained aliphatic acid anions in formation waters, support the hypothesis that acid anions are precursors for an important portion of natural gas.Results of the δ¹³C values of CO₂, CH₄, and total acetate show a reasonably constant fractionation factor of about 20 permil between CO₂ and CH₄ at 300°C. The δ¹³C values of CO₂ and CH₄ are initially low and become higher as decarboxylation increases.     

Salting-out of methane in single-salt solutions at 25°C and below 800 psia

Aqueous solubilities of methane at 25°C have been determined in single-salt solutions equilibrated with a CH₄ gas phase at 350, 550, and 750 psia. Measurements were made over a range of ionic strengths in NaCl, KCl, CaCl₂, MgCl₂, Na₂SO₄, K₂SO₄, MgSO₄, Na₂CO₃, K₂CO₃, NaHCO₃, and KHCO₃ aqueous solutions.At 25°C and constant pressure and methane fugacity, methane solubilities were largely controlled by the stoichiometric ionic strength, I, and the cation of the salt. Except for an increased salting-out due to HCO₃^?, the anion effect was relatively insignificant. Different but consistent solubility trends were followed in monovalent and divalent cation salt solutions as a function of I. Solubilities increased in salt solutions having a common anion in the following cation sequence: Na⁺ < K⁺ ? Ca²⁺ < Mg²⁺.The molal salting coefficient, k_m, for each salt was constant under the experimental conditions of the study, k_m is defined by $\text{log}\text{γ}\text{ch}{}_4\text{I}$ where $\text{γ}\text{ch}{}_4$, the molal activity coefficient, is the methane solubility ratio () measured at constant temperature, pressure, and CH₄ fugacity. Single-salt k_m values are as follows: 0.121, NaCl (4m); 0.121, Na₂SO₄ (1m); 0.118, Na₂CO₃ (1.5m); 0.146, NaHCO₃ (0.5m); 0.101, KCl (4m); 0.108, K₂SO₄ (0.5m); 0.111, K₂CO₃ (2m); 0.145, KHCO₃ (0.5m); 0.071, CaCl₂ (2m); 0.063, MgCl₂ (2m); and 0.066, MgSO₄ (1.5m) where the molalities in parentheses refer to the maximum salt concentrations used in this study.     

Stable carbon isotope behaviour of natural seepage of deep underground C-rich methane detected along a fault zone and adsorbed in mudstone: Tokyo Bay area,Japan

Gas was sampled regionally, including by drilling into faults, in the South Kanto gas-field around Tokyo Bay, Japan. Gas samples were collected from cores in a gas sampling container immediately after drilling. A value of δ¹³C₁ = −44.3‰ was obtained for gas in the container and δ¹³C₁ = −36.3‰ for seeping gas in a fault zone. However, typical CH₄ in this dissolved-in-water gas-field is mainly depleted in ¹³C, and δ¹³C₁ values range from −66‰ to −68‰ owing to microbial degradation of organic material. ¹³C-rich CH₄ is so far uncommon in the South Kanto gas-field. Seepages were observed from the surface along the north–south fault zone. The natural gas is stored below the sandstone layer by impermeable mudstone underlying the boundary at a depth of 30 m. Gas seepages were not observed below a depth of 40 m. Gas rises along the fault zone dissolved-in-groundwater up to the shallow region and then separates from the groundwater. ¹³C-rich CH₄ (adsorbed CH₄) was found to have desorbed from drilled mudstone core samples taken at depths of 1400–1900 m in the main gas-production strata. Similarly, ¹³C-rich CH₄ was found in black shale overlying the oceanic crust forming part of a sedimentary accretionary prism underling the Tokyo region. It also appears in the spring-water of spa wells, originating at a depth of 1200–1500 m along a tectonic line. Methane generated by microbial degradation of organic material through CO₂ reduction in the South Kanto gas-field mainly originates as biogenic gas mixed with a small amount of ¹³C-rich CH₄, derived from thermogenic gas without oil components in strata. It is assumed that ¹²C-rich CH₄ is easily detached from core or pore water through gas production, whereas ¹³C-rich CH₄ is strongly adsorbed on the surfaces of particles. The ¹³C-rich CH₄ rises along the major tectonic line or up the 50 m wide normal fault zone from relatively deep sources in the Kanto region.     

CaCO3 solubility in marine sediments: Evidence for equilibrium and non-equilibrium behavior

Studies of the ion concentration product (ICP) [Ca²⁺] × [CO₃^2?]in the pore waters of marine sediments have been carried out using in situ sampling techniques. For sediments near the sedimentwater interface the ICP of the pore waters is indistinguishable from that predicted from laboratory studies of calcite solubility at 1 atm. The pressure dependence of calcite solubility is also consistent with laboratory studies.At depths greater than ten to fifteen cm enhanced solubility is almost always seen. In some instances ICP gradients occur in the upper 15 cm. The ICP increases indicate that calcite solubility cannot be adequately described by a single thermodynamic equilibrium constant.     

Coupled phase and aqueous species equilibrium of the H2O-CO2-NaCl-CaCO3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite

A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H₂O-CO₂-NaCl-CaCO₃ system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H⁺, Na⁺, Ca²⁺, , Ca(OH)⁺, OH⁻, Cl⁻, , , CO_2(aq) and CaCO_3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO_2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T-P-m range, hence calcite solubility, CO₂ gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data.One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO₂ can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility.The functionality of pH value, alkalinity, CO₂ gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl_(aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.     

The P-V̄-T-X-f O2 evolution of H2O-CO2-CH4-bearing fluid in a wolframite vein: Reconstruction from fluid inclusion studies

Aqueous-carbonaceous and later pure aqueous fluid inclusions in quartz from a ferberite (Fe_.95Mn_.05 WO₄) vein within the low-grade metamorphic aureole of the Borne granite (French Massif Central) have been studied by microthermometry and Raman spectrometry. The bulk V?-X properties of the aqueous-carbonaceous inclusions have been derived using the equation of state of Heyenet al. (1982) for the low-temperature CO₂-CH₄ system. A P-T path has been proposed for their trapping using the equations of state of Jacobs and Kerrick (1981a) for the H₂O-CO₂-CH₄ system. Two main episodes were reconstructed for the history of the aqueous-carbonaceous fluid. (1) Primary H₂O-CO₂-CH₄ vapourrich inclusions in quartz indicated the early circulation of a low-density fluid (65 mole% H₂O-34 mole% CO₂-1 mole% CH₄ and traces of N₂: d = 0.35 gcm^?3) at around 550° ± 50°C and 700 ± 100 bar. Fluid cooled approximately isobarically to 450°-400°C and was progressively diluted by H₂O with a concomitant increase in density. The fO₂ of the H₂OCO₂-CH₄ fluid, estimated from the equilibrium CO₂ + 2H₂O CH₄ + 2O₂, first ranged from 10^?22 to 10^?27 bar, close to the Q-F-M buffer. Within analytical errors, these values were consistent with the presence of graphite in equilibrium with the fluid. (2) A drop in PCO₂, and therefore a drop in fO₂, was recorded by the secondary liquid-rich inclusions in quartz. The inclusions, formed at and below 400°C, were composed of H₂O and CH₄ only, and fO₂ at that stage was below that fixed by the graphite-fluid equilibrium. This second episode in the fluid-rock system could be explained by the drop of temperature below the blocking temperature of the graphite-fluid equilibrium. According to this interpretation, the blocking of the graphite-fluid equilibrium occurred at T ≥ 370°C and probably at 400°C on account of the pressure correction. Mass spectrometric data show that ferberite contains H₂O, CO₂ and CH₄ in fluid inclusions, which lie in the gap of the V?-X properties of the aqueouscarbonaceous fluid in quartz. Deposition of ferberite probably occurred at around 400°C, the previously inferred blocking temperature, resulting from either the drop in PCO₂, the drop fO₂ and/or the related pH-increase.It is concluded that the existence of a blocking-temperature for the graphite-fluid chemical equilibrium may be a critical factor for maintaining a stable fluid pressure gradient in geothermal systems occurring under greenschist facies conditions in graphite-bearing rocks.