# Patent

## Title
Process-based approach for the detection of deep gas invading the surface

## Abstract

The present invention includes a method for determining the level of deep gas in a near surface formation that includes: measuring CO2, O2, CH4, and N2 levels in percent by volume from one or more surface or near surface geological samples; adding the water vapor content to the measured CO2, O2, CH4, and N2 levels in percent by volume; normalizing the gas mixture to 100% by volume or 1 atmospheric total pressure; and determining the ratios of: O2 versus CO2 to distinguish in-situ vadose zone CO2 from exogenous deep leakage CO2; CO2 versus N2 to distinguish whether CO2 is being removed from the near surface formation or CO2 is added from an exogenous deep leakage input; or CO2 versus N2/O2 to determine the degree of oxygen influx, consumption, or both; wherein the ratios are indicative of natural in situ CO2 or CO2 from the exogenous deep leakage input.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application Ser. No. 61/840,224, filed Jun. 27, 2013, the entire contents of which are incorporated herein by reference.


STATEMENT OF FEDERALLY FUNDED RESEARCH
This invention was made with U.S. Government support by the U.S. Department of Energy through the Office of the Governor of Texas (contract DE-FG04-9OAL65847) and the National Energy Technology Laboratory (contract DE FG26-05NT42590) through the Southeast Regional Carbon Sequestration Partnership. The government has certain rights in this invention.


TECHNICAL FIELD OF THE INVENTION
The present invention relates in general to the field of gas detection, and more particularly, to a novel process-based approach for the detection of deep gas invading the surface.
BACKGROUND OF THE INVENTION
Without limiting the scope of the invention, its background is described in connection with detecting gas in the vadose zone.
Measurement, monitoring and verification (MMV) will be required at geologic carbon storage (GCS) sites to document that storage effectively retains CO2 in the subsurface [European Commission, 2009: US EPA, 2010a, b]. MMV can utilize many techniques deployed at a range of depths from the storage reservoir to the atmosphere, however techniques that monitor leakage through the near surface vadose zone are valuable because: (1) the vadose zone is the interface between subsurface storage and release to atmosphere, (2) gases moving through the shallow subsurface are easily and cheaply monitored, and (3) vadose zone monitoring can directly address concerns of landowners living above GCS sites [Shenk et al., 2011].
The most studied and currently widely accepted approach for vadose zone gas monitoring above GCS sites directly measures CO2 concentrations either by extracting vadose zone gas through hollow push probes or by measuring CO2 surface flux with accumulation chambers. Measurements are made in a grid pattern or in areas of concern, such as faults, fractures, or plugged and abandoned wells [Riding and Rochelle, 2009: Strazisar et al., 2009: Furche et al., 2010]. A minimum of 1 year of background concentration measurements is required prior to CO2 injection to document natural seasonal ranges in vadose zone CO2 apart from leakage. If CO2 concentrations statistically exceed the background range during the lifetime of a GCS project, a storage formation release may be indicated. This approach is herein referred to as a “CO2 concentration-based” approach.
A CO2 concentration-based approach has several drawbacks: (1) high variability of CO2 generated in situ could mask a moderate leakage signal; (2) 1 year of background characterization cannot account for CO2 variability from climatic, land use, and ecosystem variations over the lifetime (tens to hundreds of years) of a storage project; (3) background measurements require a long lead time potentially hindering a project's progress; and (4) background CO2 cannot be measured across all potential small diameter leak points within the area of review: therefore, if concerns arise in an area lacking local background measurements, no baseline data exist with which to compare monitored CO2 concentrations.
SUMMARY OF THE INVENTION
In one embodiment, the present invention includes a method of determining the level of deep gas in a near surface formation without the need for background monitoring comprising: measuring CO2, O2, CH4, and N2 levels in percent by volume (or mole fraction) from one or more surface or near surface geological samples; adding the water vapor content to the measured CO2, O2, CH4, and N2 levels in percent by volume (or mole fraction); normalizing the gas mixture to 100% by volume or 1 atmospheric total pressure; and determining the ratios of: O2 versus CO2 to distinguish the general CO2 production and consumption processes whether in-situ or from exogenous deep leakage CO2; CO2 versus N2 to further distinguish whether CO2 is being removed from the near surface formation or CO2 is added from an exogenous deep leakage input; or CO2 versus N2/O2 to determine the degree of oxygen influx, consumption, or both; wherein the ratios are indicative of natural in situ processes or from the exogenous deep leakage input. In one aspect, an in-situ vadose zone background level of carbon comprises at least one of biologic respiration, methane oxidation, or CO2 dissolution. In another aspect, the presence of a deep gas source of carbon is indicated if the of N2 is less than 76.4% in a water vapor saturated vadose zone environment. In another aspect if the vadose zone environment is dry, the presence of deep gas may be indicated if N2 above 78%. In another aspect, if the level of O2 is determined by gas chromatography without separation of O2 and Argon peaks, the method further comprises subtracting the level of Argon from the level of O2 to determine the actual level of O2. In another aspect, the amount of Argon is calculated equal to 1/63×N2 concentration. In another aspect, the water vapor is saturated. In another aspect, the amount of water vapor is 2.1 to 2.4%, 2.2 to 2.35%, or 2.3%. In another aspect, the deep CO2 gas versus CO2 from biological respiration is in the near surface formation if the level of N2 is below 76.4%. In another aspect, wherein an N2/O2 ratio greater than air indicates influx of air and/or O2 consumption. In another aspect, the water vapor content is measured or estimated. In another aspect, the samples are collected in a sealed container and later analyzed in a laboratory.
In one embodiment, the present invention includes a method of determining the level of deep gas in a near surface formation without the need for background monitoring comprising: measuring CO2, O2, CH4, and N2 levels in percent by volume from one or more surface or near surface geological samples; adding the water vapor content to the measured CO2, O2, CH4, and N2 levels in percent by volume and normalizing the gas mixture to 100% by volume or 1 atmospheric total pressure; and determining the ratios of: O2 versus CO2 to distinguish in-situ vadose zone CO2 from exogenous deep leakage CO2; CO2 versus N2 to distinguish whether CO2 is being removed from the near surface formation or CO2 is added from an exogenous deep leakage input; and CO2 versus N2/O2 to determine the degree of oxygen influx, consumption, or both; wherein the ratios are indicative of natural in situ CO2 or CO2 from the exogenous deep leakage input. In another aspect, an in-situ vadose zone background level of carbon comprises at least one of biologic respiration, methane oxidation, or CO2 dissolution. In another aspect, the presence of a deep gas source of carbon is indicated if the water saturated atmospheric value of N2 is less than 76.4%. In another if the level of O2 is determined by gas chromatography without separation of O2 and Argon peaks, the method further comprises subtracting the level of Argon from the level of O2 to determine the actual level of O2. In another aspect, the amount of Argon is calculated equal to 1/63×N2 concentration. In another aspect, the water vapor is saturated. In another aspect, the amount of water vapor is 2.1 to 2.4%, 2.2 to 2.35%, or 2.3%. In another aspect, the deep CO2 gas versus CO2 from biological respiration is in the near surface formation if the level of N2 is below 76.4%. In another aspect, wherein an N2/O2 ratio greater than air indicates influx of air and/or O2 consumption. In another aspect, the water vapor content is measured or estimated. In another aspect, the samples are collected in a sealed container and later analyzed in a laboratory.



BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which:
FIG. 1 is a graph that shows soil gas data from a natural CO2-rich playa site shown with general soil gas trends for common background processes of biologic respiration and methane oxidation (lines inside graph). Possible deviations are shown (inset). Gas compositions that plot below both the biological respiration and CH4 oxidation lines indicate CO2 dissolution and reaction with soil carbonate. Data representing a CO2 leak from depth into the vadose zone would plot above these trend lines in the exogenous gas input field.
FIG. 2 shows three graphs that show a comparison of trends in CO2 versus N2 for various natural playa zones (slope, annulus, floor). Dashed line indicates atmospheric N2 concentration in water vapor saturated soils (76.4%). Enrichment of N2 concentrations above atmospheric values (samples to the right of the dashed line) indicates that the background process of CO2 dissolution into recharging groundwater has occurred. If samples lie significantly to the left of the dashed line, exogenous gas input from deep reservoir leakage may be indicated.
FIG. 3 is a graph that shows the gas composition relationships of CO2 versus N2/O2 for the playa study site. Trends for O2 consumption during biologic respiration and CH4 oxidation are shown. These relationships distinguish the amount of oxygen input and utilization. In a natural system with no exogenous input from depth, gases that undergo CO2 dissolution and mixing with air will migrate to lower CO2 concentrations and higher N2/O2 ratios.
FIG. 4 shows twelve graphs that summarize the vadose zone gas data from selected wells along a gas sampling transect extending from a background location to a vadose zone gas anomaly at the P-site at the Cranfield oil field. Systematic trends (previously discussed and identified in FIGS. 1-3, at sites 100, 101 and 103 of FIG. 5) indicate that gas concentration relationships can distinguish natural background processes from exogenous gas input.
FIG. 5 is a map showing gas sampling locations at the p-site, Cranfield oilfield. Data are reported for stations BG, 100, 101, 103. Additional drilling sites are labeled 102, 104, 105, 201, 202, 301, 302, 401 and 402. The main transect is indicated by the hashed line.
FIG. 6 is a graph of δ15N versus N2 concentrations for the study playa and for two other nearby playas in west Texas. Location information on additional playas as well as a discussion about nitrogen in playas can be found in Fryar et al. (2000). The data indicate little co-variation between the two parameters suggesting that although denitrification does occur, it is not significantly affecting nitrogen concentrations beneath playas.
FIG. 7 shows a cross section of CO2 (≦21.4%), CH4 (≦33.3%), and O2 (0-21%) gas concentrations along the main gas sampling transect at the Cranfield oil field near the soil gas anomaly (centered at 103, see FIG. 5 for numbered locations). Light colors indicate high concentrations; dark colors indicate low concentrations (scale at left). The cross section is presented to show the general distribution of gases in the subsurface. High concentrations of CO2 and CH4 correspond with low O2. Gas diffusion gradients favor lateral migration near the anomaly and vertical migration away from the anomaly. O2 appears to invade the subsurface at some distance from the anomaly epicenter migrating laterally at depth.
FIG. 8 shows an assessment of isotopic data from the Cranfield oil field using the system of Whiticar (1999). Blue triangle=station 101; red circles=anomaly well 103. The data indicate that CH4 from well 103 originates from a deep exogenous source (i.e. the oil and gas reservoir) and CO2 originates from methane oxidation. As expected, these relationships are less apparent at station 101, farther from the anomaly. The exogenous source of gas and the process of methane oxidation are successfully identified using the process-based method of analysis.



DETAILED DESCRIPTION OF THE INVENTION
While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.
To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims.
A critical issue for geologic carbon sequestration is the ability to detect CO2 leakage in the vadose zone. The present invention includes a new process-based approach to identify CO2 that has leaked from deep geologic storage reservoirs into the shallow subsurface. Whereas current CO2 concentration-based methods require years of background measurements to quantify variability of natural vadose zone CO2, this new approach examines chemical relationships between vadose zone N2, O2, CO2, and CH4 to promptly distinguish a leakage signal from background CO2. The method uses sequential inspection (1) O2 versus CO2 to distinguish in-situ vadose zone background processes (biologic respiration, methane oxidation, and CO2 dissolution) from exogenous deep leakage input, (2) CO2 versus N2 to further distinguish dissolution of CO2 from exogenous deep leakage input, and (3) CO2 versus N2/O2 to assess the degree of atmospheric mixing/dilution occurring in the system. The approach was developed at a natural CO2-rich analog site and successfully applied at a CO2-enhanced oil recovery operation where deep gases migrated into the vadose zone. The ability to identify CO2 leakage into the vadose zone without the need for background measurements could decrease uncertainty in leakage detection and expedite implementation of future geologic CO2 storage projects.
To address the problem of separating signal (leaked) from background (in situ generated) CO2 in the vadose zone, the present invention includes, for the first time, a powerful, yet simple geochemical approach to GCS leakage monitoring that does not require background monitoring. Instead, relationships among major fixed gases (CO2, N2, O2, CH4) are used to identify processes that produce and consume vadose zone CO2. It was found herein that the major in situ vadose zone processes in this analysis can distinguish: biologic respiration, CH4 oxidation, dissolution of CO2 and reaction with soil carbonate, and atmospheric mixing.
Vadose zone processes. In the absence of carbon cycling processes, vadose zone gases are dominated by the atmosphere (in dry air, 78% N2, 21% O2, 0.039% CO2, 1.8 ppm CH4), which invades the subsurface via barometric pumping and diffusion. Root and microbial respiration in the vadose zone increases CO2 and decreases O2 relative to the atmosphere [Hanson et al., 2000] and is affected by temperature, soil moisture content, nutrient availability and oxygen supply which vary on diurnal, seasonal, and longer-term climatic timescales [e.g. Luo and Zhou, 2006]. Microbial respiration commonly produces CO2 wherever organic matter, O2, and soil moisture coexist, but when O2 and other electron acceptors such as nitrate and sulfate are depleted, CH4 is eventually produced [Konhauser, 2006]. If CH4 migrates into oxic zones or if environmental change allows O2 influx, CH4 is oxidized to CO2 [Whalen et al., 1990], potentially mimicking a storage formation leak signal. CH4 oxidation is therefore important to identify wherever in situ CH4 is produced or above oil and gas fields where CH4 may seep from deep reservoirs into the vadose zone over geologic time. Soil gas CO2 may be consumed by dissolution into infiltrating water and reaction with carbonate mineral phases [Striegl and Armstrong, 1990], forming a significant CO2 sink. Vadose zone gas concentrations are also affected by invasion of atmosphere into the subsurface [Osterkamp and Wood, 1987], which can be induced by barometric pressure changes but may also result from pressure gradients caused by dissolution of gas into recharging water [Smith and Arah, 1991: Romanak, 1997: Nicot and Bennett, 1998].
Beginning with atmospheric gas concentrations, vadose zone processes alter soil gas geochemistry in predictable ways on the basis of either reaction stoichiometry or decoupling of gas components. Gas concentrations are measured in percent (volume or molar); therefore, any non-reactive addition or subtraction of a gas component will, by definition, dilute or concentrate, respectively, all other gases in similar proportions. The fixed composition of atmosphere, which dominates the vadose zone in the absence of background or leakage processes, provides the starting point from which to assess reactions. N2 is a good measure of dilution and/or enrichment of a gas mixture owing to its abundance in air and non-reactivity which is compromised only in extreme cases of denitrification [Fryar et al., 2000]. Denitrification can be identified by N2 that is depleted in 15N relative to atmosphere (δ15N=0‰) [Mariotti et al., 1981], or by Ar/N2 that is significantly less than 0.0119 [Martin et al, 1995].
The process in soils posing the greatest challenge to CO2 concentration based monitoring is CO2 production by oxidation of organic matter during aerobic microbial respiration. This process is represented as:

CH2O+O2→CO2+H2O  (1)

where O2 consumption and CO2 production result in a predictable trend (slope of −1) originating from atmospheric concentrations) on a graph of CO2 versus O2 (FIG. 1). During methane oxidation,

CH4+2O2→CO2+2H2O  (2)

O2 consumption and CO2 production produce a trend with a slope of −2 on the same graph. CO2 values higher than expected from corresponding O2 values signal an exogenous CO2 source, indicating a potential leak, and CO2 values lower than expected from corresponding O2 values signal a CO2 sink.

Study sites. The process-based leakage detection approach was developed at a natural CO2-rich ephemeral playa lake in west Texas, USA. Here, known vadose zone processes were coupled with their corresponding soil gas signatures. This information was then successfully applied at an oil field in Mississippi at the site of a plugged and abandoned well to identify anomalous near-surface CO2 and CH4 soil gas signals.
Playa Natural Analog: The playa lakes of west Texas are broad, gently sloping circular basins ( ̃1 to 2 km in diameter) that accumulate and transmit surface runoff through a thick ( ̃60 m) vadose zone. Geomorphic areas associated with playas, which include: slope, annulus, and floor, systematically differ in water flux, organic carbon content, and inorganic soil carbonate, creating spatial variability in the main factors that affect natural vadose zone CO2 production and consumption [Osterkamp and Wood, 1987; Romanak, 1997]. These systematic differences provide an opportunity to link various natural CO2 cycling processes to their vadose zone soil gas signatures. The low-angle playa slope defines the outer edge of the playa basin and transmits storm runoff onto playa floors [Gustayson and Winkler, 1988]. The annulus, a sort of “bathtub ring” defined by a break in slope around the lake's shoreline, transmits water through silty sediments only during high water levels [Hovorka, 1996; Scanlon et al., 1997]. Organic-rich clays and silty clay loams of the flat playa floor pond water before transmitting it along shrink-swell fractures and root tubules through clay deposits [Hovorka, 1996: Scanlon et al., 1997]. Beneath playa floors, dissolved organic carbon is microbially oxidized to produce CO2 which dissolves soil carbonate to create piping and secondary pores as large as 7 mm in diameter (Osterkamp and Wood, 1987).
The specific playa studied herein is located at 35° 25′ 2.2′′ N, 101° 30′ 8.4′′ W, with a diameter of 0.8 km. Soil gas collected during 10 sampling trips between August 1992 and May 1995 was analyzed for CO2, O2, N2, CH4, δ13C of CO2, and 15N of N2 from 23 stations containing 54 semi-permanent soil gas wells at depths ranging from 0.6 to 13.7 m. Stations were installed along radial transects extending through slope, annulus and floor areas to identify variations in soil gas concentrations under varying environmental conditions.
Industrial Oil Field Site. Methods applied at the playa study were applied at an area named the P-site at the Cranfield oil field 18 km east of Natchez Miss., USA (31° 34′ 11.8′′ N, 91° 9′ 27.4′′ W) where oil production from the Tuscaloosa Formation (3050 m began in 1944 [Hines, 1950]. Depletion of the field by 1966 was followed by plugging and abandonment of approximately 100 wells in the 31 km2 oil field. CO2-enhanced oil recovery (EOR) began in 2008 by Denbury Resources Inc.
Vadose zone monitoring at the P-site began before local CO2 injection. At the site, 13 multi-depth gas sampling stations with a total of 39 gas wells as deep as 3 m were installed in various locations around an 1124 m2 gravel pad. One transect extends from an open pit used during 1950s oil production, across the gravel pad near a plugged and abandoned well, and out onto a grassy clearing defined as a background location. Data from portions of this major transect collected over a one-year period.
At both study sites, semi-permanent gas wells were used to sample gas from different depths within the vadose zone (see Well Station Construction, below). This installation type provides: (1) depth profiles of subsurface gas distribution, (2) potential for repeat sampling with exact spatial matching, and (3) sediment samples for assessment of parameters important to reactive transport modeling, soil contamination, or soil/water interactions. Boreholes were as deep as 14 m and well placement was targeted to areas of concern identified through reconnaissance sampling using a standard push probe.
Well Station Construction. Semi-permanent soil gas sampling stations were comprised of multiple sampling tubes (0.64-cm copper tubing at the playa and 0.32-cm stainless steel tubing at Cranfield) installed at depths of interest within each 5-cm diameter borehole. [Note: Wells can generally be installed in any size borehole that will accommodate the number of wells desired however larger diameter holes require more material for back-filling. Generally 5 cm diameter boreholes are desirable and will accommodate up to four wells]. Before drilling, all underground infrastructures were identified to avoid hitting gas or electrical lines. At the down-hole end of the Cranfield gas sampling wells, 152 mm stainless steel mesh screens (Geoprobe 15-cm vapor implants) were connected with Swagelok gas-tight fittings. Screens were set in 20-30 cm of quartz sand. The borehole was then backfilled with wetted bentonite clay chips to isolate the sampling interval until the next sampling level was reached. The process was repeated until all gas sampling wells were set in sand pack and their sampling intervals isolated with bentonite. Each gas sampling well was carefully labeled with its depth and topped with either a rubber tip (playa) or a noflow Swagelok quick connect stem (SS-QM2-D-200) that stops air from entering the tube until it is joined to the sampling hose with a quick connect body (SS-QM2-B-200) (Cranfield). All gas well tubing was cut at similar heights above ground surface ( ̃0.3 to 0.5 meters). When the borehole was filled to within 0.5 m of ground surface, a PVC protector pipe was installed over the sampling tubes, inserted into the remaining space within the borehole and secured by adding wetted bentonite around the annulus to hold it in place. The pipe was capped and labeled and protected the gas sampling wells from environmental damage.
Field GC Analysis. A Masterflex E/S portable peristaltic pump was used to draw soil-gas from wells at a flow rate of approximately 50 to 100 cc/min and deliver the sample to the gas chromatograph (GC) through tygon tubing directly plumbed to the inlet of the GC sample loop. During sampling, either an in-line pressure gauge for monitoring well pressure or a flow meter for monitoring flow rate were used to verify that no vacuum pressure developed risking dilution with ambient air or cross contamination from other sampling depths. Prior to GC analysis, the sample line to the well was purged for a sufficient time to void 2-3 well/sample line volumes. Sampling at each well continued until three runs with stable concentrations within ±10% relative difference) for each analyte were obtained. The GC was calibrated using air and certified low and high standard gas mixtures (Scot brand) spanning expected nominal concentration ranges before, during, and after each day's sampling. The precision for both detectors is ±2%.
On-site analysis of major gas compounds (CO2, O2, N2, and CH4) was accomplished at both sites using a portable gas chromatograph (SRI 8610) fixed with a CTR2 binary column (Porapak Q and molecular sieve), thermal conductivity (TCD) and flame ionization (FID) detectors, hydrogen carrier gas at various flow rates (35-46 mls/min), and isothermal temperatures of 30-45° C. A methanizer on the FID brought detection limits for CO2 down to atmospheric concentrations. This chromatographic method does not separate argon (Ar) from O2, therefore, Ar was estimated at 1/83 of N2 and subtracted from the O2 measurement which is acceptable when denitrification is insignificant N2 [Smith and Arah, 1991]. 2.2% water vapor representing saturated water vapor pressure was added to all measurements. All sample measurements were normalized to 100% for comparison purposes due to slight differences in the inlet pressures at the GC sample loop from variations in pumping rates.
Laboratory Analysis. Gas samples for δ13C and δ15N were collected in stainless steel gas cylinders with Swagelok fittings at the playa site and in pre-evacuated Cali 5-bond gas bags at Cranfield. Carbon isotopes for the playa study were analyzed by mass spectrometer at Coastal Isotope Laboratories in Austin Tex. (δ13C relative to PDB standard with a precision of ±0.2%). δ15N was measured by mass spectrometer at the Department of Environmental Sciences at the University of Virginia with atmospheric nitrogen as the standard and precision±0.15%). δ13C of CO2 and CH4 and δD of CH4 at Cranfield were collected in preevacuated Cali 5-bond gas bags and analyzed at Isotech Laboratories (Champaign, Ill.) using a GC-CIRMS system. This method employs a GC combustion unit interfaced with a mass spectrometer (Delta V Plus or Delta Plus Advantage). Samples are injected into the GC split/splitless injector and are separated by the GC column. Each individual hydrocarbon (CH4) component is combusted and the resultant CO2 is introduced directly into the mass spectrometer. Hydrogen isotopic values for methane are completed using the same system, but the gas is channeled through a high-temperature pyrolysis furnace instead of through the combustion furnace. The pyrolysis furnace converts methane into H2 and carbon, and the H2 gas is introduced directly into the mass spectrometer. Nitrogen isotopic data for elemental nitrogen (N2) is generated using the same system. For measurement of isotopes of CO2, the gas does not pass through a combustion furnace but is channeled directly from the GC outlet to the collection trap. Stated precision for δ13C is ±0.3% and for δD±2.0%.
Major gas compounds (CO2, O2, N2, and CH4) were analyzed on-site at both study areas using a portable gas chromatograph. Samples were also collected for laboratory isotope analyses including δ13C of CO2 and CH4, δD of CH4, and 15N of N2. Playa samples were collected in stainless steel gas cylinders with Swagelok fittings and analyzed either by mass spectrometer at Coastal Laboratories, Austin, Tex. (δ13C of CO2) or at the University of Virginia (δ15N of N2). Isotopes of Cranfield gases (δ13C of CO2 and CH4, and δD of CH4) were collected in Cali-5-bond bags and analyzed at Isotech Laboratories, Champaign, Ill. by mass spectrometer.
Natural Analog Playa Site. In the playa, maximum concentrations of CO2 (slope: 5.0%, annulus: 10.5%, floor: 17.2%) and CH4 (slope: 0%, annulus: 2.2%, floor: 0.9%), coupled with minimum O2 (slope: 15.6%, annulus: 0.1%, and floor 0.0%) indicate that microbial CO2 and CH4 production is relatively low in the slope, where organic carbon content and water flux is low, and high in the floor, where organic carbon content and water flux is high. The annulus is a transitional zone, behaving like the slope when dry and the floor when high water levels allow water infiltration through annulus sediments.
FIG. 5 is a map showing gas sampling locations at the p-site, Cranfield oilfield. Data are reported for stations BG, 100, 101, 103. Additional drilling sites are labeled 102, 104, 105, 201, 202, 301, 302, 401 and 402. The main transect is indicated by the hashed line.
Gas compositions from the slope and annulus, and a few from the floor, cluster between trends for microbial respiration and CH4 oxidation on a graph of CO2 versus O2 with some analytical scatter (FIG. 1). Many samples from the playa floor lie below both trend lines indicating a loss of CO2 from the gas phase. Samples that indicate this loss of CO2 (most gas compositions from the floor and some from the annulus) generally also exhibit N2 values enriched above atmospheric values (FIG. 2). Nitrogen isotope ratios of gas sampled from three area playas show insignificant denitrification, indicated by a lack of covariation between N2 and 15N(R2=0.0254) for 15 samples (FIG. 6). Comparison of N2 and CO2 concentrations from each playa zone (FIG. 2) shows the following relationships: (1) N2 values in the slope (74.0-79.0%) resemble those of the atmosphere, (2) N2 values in the floor (74.8-92.4%) are predominantly enriched relative to the atmosphere, and (3) N2 signatures in the annulus (74.3-98.1%) are mixed, depending on whether the annulus was wet and undergoing infiltration or dry.
N2 concentrations enriched relative to the atmosphere suggest the dissolution of CO2 into recharging groundwater enhanced by concurrent dissolution of soil carbonate. The loss of CO2 from the gas phase enriches the percent concentration of N2 above atmospheric values. N2 enrichment is augmented by advection of the atmosphere into soil pores driven by the pressure differential created from loss of CO2 gas [Smith and Arah, 1991: Nicot and Bennett, 1998].
Oxygen consumption during CH4 oxidation, and to a lesser degree from microbial respiration, is identified by N2/O2 above the atmospheric ratio of 3.8 (FIG. 3), in the absence of significant denitrification. Whereas both atmospheric mixing and CO2 dissolution retain a 3.8 ratio, O2 consumption increases this ratio. At the playa, O2 consumption from microbial respiration increases N2/O2 to as high as 10, whereas CH4 oxidation coupled with air influx increases this ratio to as high as 60 (FIG. 3). N2/O2 is therefore an indicator of the magnitude of oxygen influx and consumption, which can be an indicator of CH4 oxidation and discriminates microbial respiration and carbonate dissolution from CH4 oxidation which is an especially important distinction in hydrocarbon fields where oxidized CH4 seepage could be mistaken for a CO2 leak.
Industrial Site Cranfield Results. The base concept that background processes can be distinguished from a leakage signal using soil gas geochemical relationships was tested at the Cranfield oil field. Here, a persistent CO2 (44.7%) and CH4 (33.5%) anomaly is centered along a 55 m soil gas sampling transect near a plugged and abandoned well (FIGS. 5 and 7). CO2 and CH4 concentrations decrease and O2 generally increases away from the anomaly along the 43 m that separate the anomaly and background locations. Gas sampled from the anomaly shows isotopic relationships for CH4 (δ13C −36.7 to −42.4‰: δD −305.0 to −310.2‰) and CO2 (δ13C, −18.6 to −19.8‰) that are consistent with a deep thermogenic CH4 source and CO2 derived from CH4 oxidation (Whiticar, 1999: FIG. 8. These data confirm that the vadose-zone anomaly is exogenous gas originating from depth and provides an unambiguous setting in which to test the potential of the process-based method to perform in less obvious leakage detection scenarios.
To further confirm the methodology, key gas concentration relationships (CO2 vs. O2, CO2 vs. N2, and CO2 vs. N2/O2) developed at the playa site were systematically observed from the background well toward the anomaly (FIG. 4). In the background well, gas compositions fall well below the respiration and CH4 oxidation trends on a graph of O2 versus CO2 indicating the background process of CO2 dissolution and reaction with soil carbonate. In situ processes are further supported by N2 concentrations enriched with respect to the atmosphere. O2/N2 is near atmospheric ratios indicating no CH4 oxidation.
As the anomaly is approached along the transect, soil gas relationships between CO2 and O2 shift systematically toward the CH4 oxidation trend line, then to low O2 concentrations along that line, and finally to the right of the biologic respiration trend in the leakage field (FIG. 4). This progressive transformation represents an increasing magnitude of CH4 oxidation as the anomaly is approached which eventually manifests as an exogenous source plotting in the leakage field. N2 versus CO2 also shifts as the anomaly is approached from a background CO2 dissolution signal to one that signifies input of exogenous gas (N2 concentrations<atmospheric values). N2/O2 ratios much greater than air correctly indicate persistent CH4 oxidation and influx of air.
The present invention provides for the first time a new approach to separate leakage signal in the vadose zone above GCS sites from relatively complex natural CO2 cycling processes without the need for background data. The approach uses three major soil gas concentration relationships (CO2 vs. O2, CO2 vs. N2, and CO2 vs. N2/O2) to identify the vadose zone processes of biologic respiration, CH4 oxidation, soil carbonate and CO2 dissolution, atmospheric mixing, and input of exogenous gas (CO2 and/or CH4). Natural background processes were identified at a CO2-rich playa lake in west Texas and using these techniques that were then successfully applied at an industrial oil field site near Cranfield, Miss., where exogenous gas input from depth reached the surface. At the Cranfield site, gas concentration relationships indicating natural processes shifted systematically to those indicating an exogenous gas source as a surface gas anomaly was approached. Success of the process-based approach to identify deep gas in the vadose zone at an industrial site represents a significant advance in our ability to detect CO2 leakage from depth into the vadose zone at CO2 storage sites.
It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method, kit, reagent, or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.
It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.
All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.
The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.
As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. In certain embodiments, the present invention may also include methods and compositions in which the transition phrase “consisting essentially of” or “consisting of” may also be used.
As used herein, words of approximation such as, without limitation, “about”, “substantial” or “substantially” refers to a condition that when so modified is understood to not necessarily be absolute or perfect but would be considered close enough to those of ordinary skill in the art to warrant designating the condition as being present. The extent to which the description may vary will depend on how great a change can be instituted and still have one of ordinary skilled in the art recognize the modified feature as still having the required characteristics and capabilities of the unmodified feature. In general, but subject to the preceding discussion, a numerical value herein that is modified by a word of approximation such as “about” may vary from the stated value by at least ±1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%.
All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.
REFERENCES


    European Commission (2009), Directive 2009/31/EC of the European Parliament and of the Council of 23 Apr. 2009 on the geological storage of carbon dioxide: Official Journal of the European Union L 140/114 EN.
    Fryar, A. E., S. A. Macko, W. F. Mullican, K. D. Romanak, and P. C. Bennett (2000), Nitrate reduction during ground-water recharge, Southern High Plains, Tex.: Journal of Contaminant Hydrology 40, 335-363.
    Furche, M., S. Schlomer, E. Faber, and I. Dumke (2010), One year continuous vadose zone gas monitoring above an EGR test site Geophysical Research Abstracts Vol. 12, EGU2010-3095-1, 2010 7th EGU General Assembly 2010.
    Gustayson, T. C., and D. A. Winkler (1988), Depositional facies of the Miocene-Pliocene Ogallala Formation, northwestern Texas and eastern New Mexico: Geology, 16(3): 203-206.
    Hanson, P. J., N. T. Edwards, C. T. Garten, and J. A. Andrews (2000), Separating root and soil microbial contributions to soil respiration: A review of methods and observations: Biogeochemistry, 48: 115-146.
    Hines, L., (1950), The Cranfield: World Oil, February: 131-146.
    Hovorka, S. D., (1995), Quaternary evolution of playa lakes on the Southern High Plains—a case study from the Amarillo area, Texas: The University of Texas at Austin, Bureau of Economic Geology Report of Investigations No. 236, 52 p.
    Konhauser, K. (2006), Introduction to geomicrobiology: Maldon, Oxford, Carlton: Blackwell Publishing, 425 p.
    Luo, Y., and X. Zhou (2006), Soil respiration and the environment: Elsevier Academic Press Amsterdam, 334 p.
    Mariotti, A., J. Germon, P. Hubert, P. Kaiser, R. Letolle, A. Tardieux, and P. Tardieux (1981), Experimental determination of nitrogen kinetic isotope fractionation: Some principles; illustration for the denitrification and nitrification processes: Plant and Soil 62(3): 413-430.
    Martin, G. E., D. D. Snow, K. Euisik, and R. F. Spalding (1995), Simultaneous determination of Argon and Nitrogen: Ground Water 33(5): 781-785.
    Nicot, J. P., and P. C. Bennett (1998), Gas phase dynamics of playa-wetlands: Journal of Environmental Engineering: 124: 1038-1046.
    Osterkamp, W. R. and W. W. Wood (1987), Playa-lake basins on the Southern High Plains of Texas and New Mexico: Part 1: Hydrologic, geomorphic, and geologic evidence for their development: GSA Bulletin, 99: 215-223.
    Riding, J. B., and C. A. Rochelle, (2009), Subsurface characterisation and geological monitoring of the CO2 injection operation at Weyburn, Saskatchewan, Canada in D. J. Evans and R. A. Chadwick, eds., Underground gas storage: worldwide experiences and future development in the UK and Europe: London, Geological Society, Special Publication 313: 227-256.
    Romanak, K. D. (1997), Vadose-zone geochemistry of playa wetlands, High Plains, Tex.: The University of Texas at Austin, Ph.D. dissertation, 273 p.
    Sherk, G. W., Romanak, K. D., Dale, J., Gilfillan, S. M. V., Haszeldine, R. S., Ringler, E. S., Wolayer, B. D., and Yang, C., (2011), The Kerr investigation: findings of the investigation into the impact of CO2 on the Kerr property: IPAC Research Inc., final report prepared for property owners Cameron and Jean Kerr, 181 p.
    Scanlon, B. R., R. S. Goldsmith, and W. F. Mullican III (1997), Spatial variability in vadose flow beneath playa and adjacent interplaya settings and implications for contaminant transport, Southern High Plains, Tex.: The University of Texas at Austin, Bureau of Economic Geology Report of Investigations No. 243, 56 p.
    Smith, K. A., and J. R. M. Arah, (1991), Gas chromatographic analysis of the soil atmosphere, in K. Smith, ed., Soil analysis: Marcel Dekker, New York, 505-546.
    Strazisar, N. R., A. W. Wells, J. R. Diehl, R. W. Hammack, and G. A. Veloski, (2009), Near-surface monitoring for the ZERT shallow CO2 injection project: International Journal of Greenhouse Gas Control, 3(6): 736-744.
    Striegl, R. G. and D. E. Armstrong, (1990), Carbon dioxide retention and carbon exchange on vadose Quaternary sediments: Geochimica et Cosmochimica Acta, 54(8): 2277-2283.
    USEPA (2010a), General technical support document for injection and geologic sequestration of carbon dioxide: subparts RR and UU.
    USEPA (2010b), Mandatory reporting of greenhouse gases: injection and geologic sequestration of carbon dioxide; final rule, 75 FR 75060.
    Whalen, S. C., W. S. Reeburgh, and K. A. Sandbeck, (1990), Rapid methane oxidation in a landfill cover soil Applied Environmental Microbiology, 56(11): 3405-3411.
    Whiticar, (1999), Carbon and hydrogen isotope systematics of bacterial formation and oxidation of methane: Chemical Geology, 161: 291-314.

## Claims

1. A method of determining a level of deep gas in a near surface formation without a need for background monitoring comprising:
measuring CO2, O2, CH4, and N2 levels in percent by volume from one or more surface or near surface geological samples;
transforming the measured CO2, O2, CH4, and N2 levels by adding water vapor content to the measured CO2, O2, CH4, and N2 levels in percent by volume;
normalizing the CO2, O2, CH4, and N2 levels to 100% by volume or 1 atmosphere total pressure to generate normalized CO2, O2, CH4, and N2 levels;
determining the ratios of:
the normalized O2 level versus the normalized CO2 level to distinguish in-situ vadose zone CO2 from exogenous deep leakage CO2; and
the normalized CO2 level versus the normalized N2 level to distinguish whether CO2 is being removed from the near surface formation or CO2 is added from an exogenous deep leakage input; or the normalized CO2 level versus the normalized N2 level divided by the normalized O2 level to determine a degree of oxygen influx, consumption, or both oxygen influx and consumption; and

evaluating the ratios to determine whether CO2 present in the surface or near surface geological samples is from natural in-situ CO2 or CO2 from exogenous deep leakage without a need for background monitoring, wherein evaluating includes identifying CO2 from exogenous deep leakage if the normalized N2 level is less than 78% under dry conditions, wherein evaluating includes identifying CO2 from natural in-situ CO2 if the normalized N2 level is about 78% under dry conditions, or wherein evaluating includes identifying air influx into the near surface formation if the normalized N2 level divided by the normalized O2 level is greater than a ratio of O2 to N2 in air.

2. The method of claim 1, wherein an in-situ vadose zone background level of carbon comprises at least one of biologic respiration, methane oxidation, or CO2 dissolution.

3. The method of claim 1, wherein a presence of a deep gas source of carbon is indicated if the normalized N2 level under water saturated conditions is less than 76.4%.

4. The method of claim 1, wherein if the normalized O2 level is determined by gas chromatography without separation of O2 and Argon peaks, the method further comprises subtracting an amount of Argon from the normalized O2 level to determine an actual O2 level.

5. The method of claim 4, wherein the amount of Argon is calculated equal to 1/63× the normalized N2 level.

6. The method of claim 1, wherein the water vapor content corresponds to water saturated conditions.

7. The method of claim 1, wherein an amount of the water vapor content is 2.1 to 2.4%.

8. The method of claim 1, further comprising installing gas probes into the near surface formation for measuring the CO2, O2, CH4, and N2 levels.

9. The method of claim 1, wherein the water vapor content is measured or estimated.

10. The method of claim 1, wherein the one or more surface or near surface geological samples are collected in a sealed container and later analyzed in a laboratory.

11. A method of determining a level of deep gas in a near surface formation without a need for background monitoring comprising:
measuring CO2, O2, CH4, and N2 levels in percent by volume from one or more surface or near surface geological samples;
transforming the measured CO2, O2, CH4, and N2 levels by adding water vapor content to the measured CO2, O2, CH4, and N2 levels in percent by volume;
normalizing the CO2, O2, CH4 and N2 levels to 100% by volume or 1 atmosphere total pressure to generate normalized CO2, O2, CH4 and N2 levels;
determining the ratios of:
the normalized O2 level versus the normalized CO2 level to distinguish in-situ vadose zone CO2 from exogenous deep leakage CO2;
the normalized CO2 level versus the normalized N2 level to distinguish whether CO2 is being removed from the near surface formation or CO2 is added from an exogenous deep leakage input; and
the normalized CO2 level versus the normalized N2 level divided by the normalized O2 level to determine a degree of oxygen influx, consumption, or both oxygen influx and consumption; and

evaluating the ratios to determine whether CO2 present in the surface or near surface geological samples is from natural in-situ CO2 or CO2 from exogenous deep leakage without a need for background monitoring, wherein evaluating includes identifying CO2 from exogenous deep leakage if the normalized N2 level is less than 78% under dry conditions, wherein evaluating includes identifying CO2 from natural in-situ CO2 if the normalized N2 level is about 78% under dry conditions and wherein evaluating includes identifying air influx into the near surface formation if the normalized N2 level divided by the normalized O2 level is greater than a ratio of O2 to N2 in air.

12. The method of claim 11, wherein an in-situ vadose zone background level of carbon comprises at least one of biologic respiration, methane oxidation, or CO2 dissolution.

13. The method of claim 11, wherein the presence of a deep gas source of carbon is indicated if the normalized N2 level under water saturated conditions is less than 76.4%.

14. The method of claim 11, wherein if the normalized O2 level is determined by gas chromatography without separation of O2 and Argon peaks, the method further comprises subtracting an amount of Argon from the normalized O2 level to determine an actual O2 level.

15. The method of claim 14, wherein the amount of Argon is calculated equal to 1/63× the normalized N2 level.

16. The method of claim 11, wherein the water vapor content corresponds to water saturated conditions.

17. The method of claim 11, wherein an amount of the water vapor content is 2.1 to 2.4%.

18. The method of claim 11, further comprising installing probes into the near surface formation for measuring the CO2, O2, CH4, and N2 levels.

19. The method of claim 11, wherein the water vapor content is measured or estimated.

20. The method of claim 11, wherein the one or more surface or near surface geological samples are collected in a sealed container and later analyzed in a laboratory.