International Journal of Coal Geology 76 (2008) 7685

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International Journal of Coal Geology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / i j c o a l g e o

Chemical and stable isotopic evidence for water/rock interaction and biogenic origin of coalbed methane, Fort Union Formation, Powder River Basin, Wyoming and Montana U.S.A.
C.A. Rice , R.M. Flores, G.D. Stricker, M.S. Ellis
U. S. Geological Survey, P.O. Box 25046, MS 939, Denver, CO 80225, USA

A R T I C L E

I N F O

A B S T R A C T
Signicant amounts (N 36 million m3/day) of coalbed methane (CBM) are currently being extracted from coal beds in the Paleocene Fort Union Formation of the Powder River Basin of Wyoming and Montana. Information on processes that generate methane in these coalbed reservoirs is important for developing methods that will stimulate additional production. The chemical and isotopic compositions of gas and ground water from CBM wells throughout the basin reect generation processes as well as those that affect water/rock interaction. Our study included analyses of water samples collected from 228 CBM wells. Major cations and anions were measured for all samples, DH2O and 18OH2O were measured for 199 of the samples, and DCH4 of gas coproduced with water was measured for 100 of the samples. Results show that (1) water from Fort Union Formation coal beds is exclusively NaHCO3-type water with low dissolved SO4 content (median b 1 mg/L) and little or no dissolved oxygen (b 0.15 mg/L), whereas shallow groundwater (depth generally b 120 m) is a mixed CaMgNaSO4HCO3 type; (2) water/rock interactions, such as cation exchange on clay minerals and precipitation/dissolution of CaCO3 and SO4 minerals, account for the accumulation of dissolved Na and depletion of Ca and Mg; (3) bacterially-mediated oxidationreduction reactions account for high HCO3 (270 3310 mg/L) and low SO4 (median b 0.15 mg/L) values; (4) fractionation between DCH4 ( 283 to 328 per mil) and DH2O ( 121 to 167 per mil) indicates that the production of methane is primarily by biogenic CO2 reduction; and (5) values of DH2O and 18OH2O ( 16 to 22 per mil) have a wide range of values and plot near or above the global meteoric water line, indicating that the original meteoric water has been inuenced by methanogenesis and by being mixed with surface and shallow groundwater. Published by Elsevier B.V.

Article history: Received 23 March 2008 Received in revised form 1 May 2008 Accepted 5 May 2008 Available online 10 May 2008 Keywords: Coalbed methane Co-produced water Chemical and isotope composition Groundwater Fort Union Formation Powder River Basin

1. Introduction The chemical and isotopic composition of water co-produced with coalbed methane (CBM) can yield valuable information on the geochemical processes that produce the gas, as well as on the hydrogeological controls affecting the movement and storage of the gas. Formation water chemical composition is an indicator of water/rock interactions that include precipitation/dissolution, cation exchange, and oxidationreduction reactions. Isotopes of formation water reect the origin and evolution of the water as well as biogeochemical reactions such as methanogenesis that utilize water as a source of reactants. Studies by Ayers et al. (1991) in the San Juan Basin of New Mexico and Colorado and Rice (2003) in the Uinta Basin of Colorado and Utah utilized the chemical and isotopic composition of CBM formation water to understand the complex hydrogeology of the CBM reservoirs in these basins.
Corresponding author. U.S. Geological Survey, MS 939, Box 25046, Denver Federal Center, Denver CO 80225-0046, USA. Tel.: +1 303 236 1989; fax: +1 303 236 0459. E-mail address: crice@usgs.gov (C.A. Rice). 0166-5162/$ see front matter. Published by Elsevier B.V. doi:10.1016/j.coal.2008.05.002

In the Powder River Basin (PRB) of Wyoming and Montana, previous studies of water associated with the coalbed reservoirs in the Paleocene Fort Union Formation have been either limited in scope (Gorody, 1999; Rice and Flores, 1991; Rice et al., 2002) or have been focused on the properties of the reservoirs as aquifers (Feathers et al., 1981; Bloyd et al., 1986; Martin et al., 1988). The studies by Gorody (1999), Rice and Flores (1991), Rice (1993), and Surdam et al. (2007) attempted to identify the specic methanogenic pathway for biogenic gas formation in the basin, but the interpretations were based on sparse analytical data (b 5 samples for some of the most important relationships), and the samples represented only a small portion of the PRB. In our study, 228 samples of water and 100 samples of gas from CBM wellheads throughout the basin were collected for detailed study. The chemical composition of the water reects the geochemical processes that produced the major ion composition and the stable isotope contents of both water and gas indicate the specic methanogenic pathway that produced the gas. This paper is a further expansion, with new data, of work presented previously in Rice et al. (2000) and Rice et al. (2002), which focused primarily on the chemical composition of CBM water in the PRB.

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2. Geologic and hydrogeologic settings The Fort Union Formation in the PRB is described in numerous reports (e.g. Love and Weitz, 1951; Hose, 1955; Curry, 1971; Tschudy, 1976; Law, 1978; Seeland, 1992; Flores and Bader, 1999; Flores, 2004; Flores et al., 1999, 2008-this volume). The PRB, which encompasses about a 57,000-km2 area (Fig. 1), is an asymmetrical structural and sedimentary basin whose axis, near the west margin, trends northwest to southeast. Coalbed methane is currently produced mainly from coal beds in the Tongue River Member of the Paleocene Fort Union Formation. These strata crop out along the margins of the basin and, in much of the basin, are overlain by the Eocene Wasatch Formation (Fig. 1). Fort Union rocks dip an average of 20 to 25 to the east along the west margin of the PRB and an average of 2 to 5 to the west along the east margin; maximum thickness is 1,830 m in the deep axial part of the basin. The formation contains conglomerate, sandstone, siltstone, and mudstone, with lesser amounts of limestone, coal, and carbonaceous shale. Coal beds range from several centimeters to more than 61m thick; average is 7.6 m. The stratigraphic relation of coal beds within the Fort Union Formation is complex (e.g. some beds merge, split and pinch out within distances as short as 400 m; Flores et al., 2008-this volume). The nomenclature of individual coal beds also varies across the basin, particularly between localities near Gillette, Wyoming, and those farther northwest in Wyoming and southeastern Montana (Fig. 2; Flores et al.,

2005). Although the Wasatch Formation is considered to overlie the Fort Union Formation unconformably along most of the basin margin, in some areas the lithologies of the two formations are so similar that no distinction can be made except by detailed mineralogical or palynological studies (Denson et al., 1989a,b; Tschudy, 1976). Most of the CBM development is concentrated in the WyodakAnderson coal zone of the Fort Union Formation, but other beds and zones also are locally being targeted, such as the Felix coals (Fig. 2) of the Wasatch Formation near Buffalo, Wyoming. Coal beds in the Fort Union Formation are some of the most important local aquifers in the PRB. The WyodakAnderson coal zone and other thick coal beds, for example, are the most continuous aquifers in lower Tertiary strata throughout much of the basin (Martin et al.,1988). At a basinwide scale, members of the Fort Union Formation are assigned to relatively large aquifer systems along with members of other formations (Feathers et al., 1981; Lewis and Hotchkiss, 1981). At sub-basin and local scales, however, the Fort Union Formation is considered a separate aquifer, with members further divided into distinct hydrogeologic units (Feathers et al., 1981; Bloyd et al., 1986; Martin et al., 1988). A detailed discussion of these and other characteristics of the hydrogeologic units in the Wasatch and Fort Union Formations is beyond the scope of this paper, but the reader is referred to Martin et al. (1988), Lindner-Lunsford and Wilson (1992), and Bartos and Ogle (2002) for more information. Groundwater ow, recharge, and discharge in the Fort Union Formation in the PRB is not well understood, especially the relative

Fig. 1. Map of the Powder River Basin, Wyoming and Montana, showing distribution of uppermost Cretaceous, Paleocene, and lower Eocene rocks.

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Fig. 2. Generalized stratigraphic column for the Powder River Basin, showing coal and uvial channel sandstone beds in the Upper Cretaceous Lance, Paleocene Fort Union, and Eocene Wasatch Formations; older Cretaceous formations are shown in the inset column. Coalbed methane reservoirs in the Fort Union and Wasatch Formations are identied using U.S. Geological Survey names; names in parenthesis are equivalent names in different portions of the basin. Modied from Flores and Bader (1999).

amounts and importance of regional versus local ow systems and vertical versus horizontal ow components (Lindner-Lundsford and Wilson, 1992). Groundwater ow at shallow depths (b 60 to 150 m) in the formation is believed to be primarily local and related to topography, with discharge occurring primarily along streams adjacent to local recharge areas (sandstone and clinker outcrops), although some investigators report little evidence of discharge from these deposits to local streams (Rankl and Lowry, 1990). Clinker in the areally extensive Rochelle Hills escarpment on the eastern margin of the basin near Gillette and Wright, has been speculated to provide considerable recharge to coalbed aquifers (Davis, 1976; Daddow, 1986; Lowry et al., 1986; Martin et al., 1988; Heffern et al., 1996; U.S. Bureau of Land Management, 1999; Heffern and Coates, 1999). Regionally, groundwater in the aquifers of the Fort Union Formation is believed to move generally northward and northeastward (Lobmeyer, 1985), and discharge is postulated to occur to the north and in topographic valleys. A potentiometric surface map prepared by Daddow (1986) indicates that groundwater in the WyodakAnderson coalbed aquifer moves to the north and northwest. The amount of hydraulic connection under natural conditions among the different aquifers is subject to interpretation, but some leakage probably occurs where the hydraulic gradient allows for downward vertical groundwater ow and where sandstone beds are stacked or directly overlie coal beds (Bartos and Ogle, 2002).

3. Methods Between 1999 and 2004, water samples were collected from 228 wells completed in coal beds in the Fort Union Formation (Fig. 3). Major dissolved-ion chemistry was obtained using inductively coupled plasma mass spectrometry and ion chromatography for all samples. Details of methods for water collection, preservation, and analysis are in Rice et al. (2000) and Bartos and Ogle (2002). Deuterium and oxygen stable isotopes (D and 18O) were obtained for 199 of the 228 samples. In addition, gas samples were obtained from 100 of the wells and analyzed for D of the methane. Gas samples were collected at the well sites by collection through displacement of water in inverted bottles. Gas analyses and results are described in Flores et al. (2008-this volume). 4. Results and discussion 4.1. Chemical composition Groundwater associated with recharge in the PRB is represented by oxygenated water dominant in Ca, Mg, bicarbonate, and SO4, with lesser amounts of Na (Hagmaier, 1971; Lee, 1981; Woessner et al., 1981). An examination of groundwater from sandstones of the Fort Union Formation (Table 1; Larson and Daddow, 1984), indicates that samples having SO4 values N 100 mg/L are at a median depth of 73 m,

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Fig. 3. Areal distribution of total dissolved solids in water from Fort Union Formation coal beds.

have a total dissolved solids (TDS) value of 1,550 mg/L, and are comprised of mixed cations and mixed anions. Groundwater in deeper sandstones (median depth, 160 m) has SO4 concentrations b 100 mg/L, and median TDS of 1,010 mg/L, is of a NaHCO3 type, and is depleted in Ca, Mg, and SO4 relative to that in the shallower sandstones. The chemical composition of formation water in coal beds of the Fort Union Formation, as determined in this study (summarized in Table 2), is closely similar to that reported by Larson and Daddow (1984) for water in deeper sandstones. The coalbed water samples are from a median depth of 254 m, have a median TDS of 980 mg/L, exhibit a NaHCO3 type water with very low SO4 (median value of 0.15 mg/L), and contain slightly higher Ca and Mg than the deeper sandstone water. TDS concentrations typically are low near recharge sources, where groundwater residence times (time in contact with aquifer materials) are relatively short, however, their concentrations increase as groundwater ows away from the source of recharge and residence times increase. An areal plot (Fig. 3) indicates that TDS increases, which trend from south to north and from east to west, are due to increases in

Na and bicarbonate. These trends coincide with the potentiometric surface map of Daddow (1986), which indicates that regional groundwater ow in the WyodakAnderson coalbed aquifer is directed

Table 1 Median values of composition of water from wells penetrating sandstones in the Fort Union Formation, Powder River Basin, Wyoming. Data from Larson and Daddow (1984). Shallow, sulfate N 100 mg/L; Deep, sulfate b 100 mg/L Shallow sandstone N Depth (m) TDS (mg/L) Calcium (mg/L) Magnesium (mg/L) Sodium (mg/L) Bicarbonate (mg/L) Sulfate (mg/L) Chloride (mg/L) 28 73 1550 86 51 306 477 706 8 Deep sandstone 26 160 1010 12 3 395 1129 2 11

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Table 2 Median values of composition of water from wells penetrating coal beds in the Fort Union Formation, Powder River Basin, Wyoming and Montana Median N Depth (m) TDS (mg/L) Calcium (mg/L) Magnesium (mg/L) Sodium (mg/L) Bicarbonate (mg/L) Sulfate (mg/L) Chloride (mg/L)
a

Minimum 68 230 1.8 0.64 81 270 b 0.3 1.8

Maximum 692 2900 78 46 1160 3310 530 130

228 254 980 30 13 350 1110 0.15a 9.5

Less than values assigned value of 0.15 to calculate median.

westward and northwestward from the southeastern clinker areas where most recharge is thought to occur. The trends also agree with the conclusion of Lobmeyer (1985) that regional ow in lower Tertiary aquifers of the PRB is to the north, but the northeast ow trend he noted in northern Wyoming is not observed in this study. As groundwater ows away from sources of recharge, interactions among water, aquifer minerals, and bacteria along vertical and horizontal ow paths change the relative abundance and importance of individual cations or anions. The relation between well depth and a change in major ion composition as a result of these interactions was noted previously by many investigators (e.g. Riffenburg, 1925; Lowry and Cummings, 1966; Whitcomb et al., 1966; Hagmaier, 1971; Dockins et al., 1980; Lee, 1981; Woessner et al., 1981; Slagle et al., 1985; Lowry et al., 1986; Van Voast and Reiten, 1988; Rankl and Lowry,1990; Bartos and Ogle, 2002; Rice et al., 2002). Minerals (reactants or products created during water/rock interactions) that were identied in drill cores of the Tongue River Member of the Fort Union Formation from southeastern Montana (Lee, 1981; Davis, 1984) are similar to those described by Martin et al. (1988) in mine spoil in the eastern PRB. They include quartz, oligoclase and adularia (plagioclases), calcite, dolomite, aragonite, pyrite, siderite, gypsum, chlorite, and clay minerals (smectite, illite, and kaolinite). Sodium enrichment of our water samples likely occurs through the dissolution of plagioclases in the Tongue River Member, cation exchange of Ca and Mg for Na on the clay minerals, and (or) from removal of Ca and Mg by carbonate precipitation. Oxidation of pyrite by oxygenated recharge water initially provides additional SO4 to the water as it moves along ow paths, increasing the relative abundance of SO4 over bicarbonate. However, as the water moves farther from sources of oxygenated recharge, evidence (Dockins et al., 1980; Lee, 1981; Martin et al., 1988) indicates that bacterial sulfate reduction occurs, resulting in depletion of SO4 and enrichment in bicarbonate. Sulfate also may be removed by precipitation of gypsum, which also removes Ca from solution. As recorded in our analyses, the net result of the water/rock interactions along the ow path is a decrease in Ca, Mg and SO4 and a corresponding increase in Na and bicarbonate. In Fort Union coal beds, processes associated with coalication also inuence water composition. Coalbed methane in the PRB is believed to be biological in origin (methanogenic) (Law et al., 1991; Rice, 1993; Gorody, 1999; Flores et al., 2008-this volume). A series of bacteriallymediated redox reactions (Stumm and Morgan, 1981; Rice, 1993) occurs in reducing environments, progressing in stages from a reduction of NO3 rst, to manganese and iron oxides, then to SO4, and nally to CO2 (methanogenesis). The net effect of these redox processes is to generate 2+ 2+ species such as NH+ 4, Mn , Fe , HS , CO2, and CH4, many of which are present in CBM co-produced water in the PRB (Rice et al., 2000). Some of the products may engage in further reactions, for example, Mn2+ and Fe2 + may react with HS to form sulde minerals and CO2 may be produced or consumed depending on the particular bacterial pathway and on the specic bacteria that produce methane (Scott, 1999). The overall effect on water composition of reduction reactions on the path to methano-

Fig. 4. DH2O versus 18OH2O for Fort Union Formation coal beds(determined in Gorody, 1999; Bartos and Ogle, 2002; this study) and for Powder River Basin surface water and springs (from Gorody, 1999; Bartos and Ogle, 2002). The line is the Global Meteoric Water Line as dened by Craig (1961).

genesis is to deplete SO4, increase bicarbonate, and establish a reducing environment, all of which are representative of CBM co-produced water samples. 4.2. Isotopic composition The DH2O and 18OH2O values of CBM formation water in the Fort Union coal beds vary widely, with values of DH2O ranging from 121 to 167 per mil and values of 18OH2O ranging from 16 to 22 per mil; many results are spread along the Global Meteoric Water Line (GMWL; Craig, 1961). A plot of DH2O vs 18OH2O (Fig. 4) for the water samples we studied indicates that many Fort Union coalbed waters cluster along or above the GMWL (Craig, 1961). Values for DH2O and 18OH2O that fall on the lower portion of the GMWL (lighter DH2O and 18OH2O) indicate that some of the water in portions of the basin may be older, with an isotopic signature more representative of a cooler climate. Samples that fall above the GMWL have been affected by methanogenesis and those below the line have likely mixed with near-surface water that has undergone varying degrees of evaporation (see shallow aquifer/surface water and spring samples in Fig. 4). Because methanogenic bacteria preferentially utilize hydrogen from water molecules (Whiticar, 1999), the isotopic signature of the formation water will shift to heavier deuterium values during methanogenesis. This results in the samples plotting above the GMWL, which is where the bulk of our samples plot. The enrichment in deuterium trend was also noted in many of Gorody's (1999) and Bartos and Ogle's (2002) Fort Union Formation waters as well (Fig. 4). The water samples on or slightly below (12 per mil) the GMWL are consistent with the isotopic signature of modern meteoric water in

Fig. 5. DH2O versus 18OH2O from Fort Union Formation coal beds. The line is the Global Meteoric Water Line as dened by Craig (1961).

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Fig. 6. Areal distribution of 18OH2O in Fort Union Formation coal beds.

the PRB (the local meteoric water line is believed to be displaced below the GMWL). Some of the samples below the GMWL indicate they may have mixed with water that has evolved away from the GMWL as a result of evaporation (Gorody, 1999's shallow coal seams and surface waters). The DH2O and 18OH2O of the formation water determined in this study are plotted in Fig. 5 by groups of individual Tongue River Member coal beds. The groupings represent equivalent coal beds that have different names in different parts of the basin (e.g. the Dietz coal bed from the Sheridan, Wyoming area is the equivalent of the Anderson coal bed from the eastern portion of the basin). It is apparent that within specic coal beds, the isotopic values vary along the meteoric water line over fairly large ranges rather than clumping together. In fact, the DH2O and 18OH2O within a coal bed trends from heavier (enriched in deuterium) to lighter (depleted in deuterium) values along a north-to-northwest trend across the basin, away from recharge areas to the south-southeast (Figs. 6 and 7). This trend may represent mixing of more recent water with older basinal water along recharge ow paths. The lightest isotopes of DH2O and 18OH2O are located in the northwesternmost portion of the basin and along a south-to-north trend to the east of the basin axis.

The heaviest isotopes appear on the east edge of the WyodakAnderson coal zone near areas of recharge and have values similar to those for modern surface waters as reported by Gorody (1999), indicating mixing of older basinal water with more modern recharge. Another contour of heavier isotopes appears to be in the western part of the basin, but this might be an artifact of the contouring program, which is based on sparse data in that part of the basin. The data in Figs. 6 and 7 are not separated according to individual coal beds or groups of coal beds as are the data for the scatter plot in Fig. 5, but rather they represent an overview of all the formation water in the Fort Union Formation across the PRB. The trends in the isotopes probably represent methane formed by both thermogenesis and methanogenesis (Flores et al., 2008-this volume), which is then altered by mixing; the mixing is controlled largely by the complex geology initiated during deposition and from post-depositional tectonics. Fig. 8 is a coal thickness map of the WyodakAnderson coal zone showing the location and number of coal beds more than 6-m thick. The coal zone is split by uvial channel sandstones, an indication of the location of paleochannels within the riverine complex during the

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Fig. 7. Areal distribution of DH2O in Fort Union Formation coal beds.

time of peat deposition (Flores et al., 2005). The trends observed in Fig. 8 are similar to the trends observed in the isotopic values of Fort Union Formation water in Figs. 6 and 7 where light isotopic values form a line from south to north in the middle part of the basin. The water with these values is probably among the oldest in the basin and represents the isotopic signature of the original formation water after methanogenic and/or thermogenic processes have altered the isotopic signature. Interestingly, the areal distribution of TDS shown in Fig. 3 also has a south-to-north trend of higher TDS values, but the trend in TDS is displaced to the west of the main thick coal zones shown in Fig. 8. The trend in TDS reects increased water/rock interaction with greater depth in the basin, which would not affect the isotopic signature of the water unless isotopic exchange with formation materials occurred. It is unlikely that the isotopic exchange has occurred because of the types of water/rock interactions that took place and the relatively shallow depths of burial. The isotopically lightest water in the northwesternmost part of the basin is somewhat problematic to explain because of its relatively shallow depth and proximity to clinker deposits that are presumed to be

potential recharge areas. This portion of the basin was signicantly uplifted after deposition and the coal beds are steeply sloping on the basin margin (Flores and Bader, 1999; Flores et al., 1999). This uplift may have sufced to (1) isolate and preserve older formation water that has an isotopic signature reective of a colder climate, and (2) prevent signicant mixing with more modern water. The possibility also exists that water from the northwestern portion of the basin is not connected to the regional ow system (e.g. from southeast to northwest ow) in the basin as a whole and that local processes are affecting the isotopic signature of the water (Flores et al., 2008-this volume). In addition to indicating the geologic and hydrogeologic controls exerted on water in Fort Union Formation coal beds, the stable isotopes of water can be used in conjunction with the stable isotopes of associated gas to understand the origin of methane in the Fort Union coal beds. Methane from the PRB has been shown by Rice and Flores (1991), Rice, 1993, Gorody (1999), Surdam et al. (2007), and Flores et al. (2008this volume) to be biogenic in origin. Before our study and that of Flores et al. (2008-this volume), however, the specic pathway for the biogenic gas was unclear, based on limited data from only a few areas of

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Fig. 8. Map showing distribution of the WyodakAnderson coal zone in the Powder River Basin in Wyoming, and the number of individual beds in the zone thicker than 6 m. Direction and size of arrows show uvial-channel ow and trunk-tributary uvial system, respectively (adopted from Flores et al., 2005).

the basin, or examined only limited relationships between isotopes. Methanogenesis can occur by either methyl-type fermentation: CH3 COOHCH4 CO2 ; or by CO2-reduction: CO2 4H2 CH4 2H2 O 2 1

In CO2-reduction, the hydrogen in methane is derived solely from the formation water producing CH4 fractionated with respect to formation water as follows (Whiticar, 1999): DCH4 YDH2O 16010 4

as denoted in these simplied equations (Whiticar et al., 1986; Whiticar, 1999). Each pathway produces a distinct isotopic signature for the produced gas and for associated formation water, depending on the isotopic signature and concentration of the reactants. For methyl-type fermentation, 75% of the hydrogen in CH4 is derived from the original organic matter and only 25% from formation water, producing a fractionation of the isotopes between CH4 and H2O (Whiticar, 1999): DCH4 Y0:25DH2O 33510 3

In a plot of DCH4 versus DH2O, the areas for methyl-type fermentation and CO2-reduction are readily distinguishable. For our study, values of DCH4 and DH2O obtained for 100 samples of gas and water in Fort Union Formation coal beds are plotted in Fig. 9, with the eld for CO2-reduction bounded by dashed lines. The eld for methyl-type fermentation based on the results of Whiticar (1999) is not shown in the gure, but would plot below the eld for CO2-reduction if the plot were extended to isotopically lighter values of DCH4. Most of our samples plot within the eld of CO2-reduction, with some samples falling below, but not to, the methyl-type fermentation eld, indicating that CO2-reduction is the predominant metabolic pathway for methanogenesis in the Fort Union Formation. The

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uplift. The trend in the water isotopes is remarkably similar to a plot of coal beds in the WyodakAnderson coal zone that is indicative of paleo-riverine channels. Stable isotopes of CBM formation water in the PRB support the production of biogenic methane in the basin by the CO2-reduction metabolic pathway, with a few samples having been overprinted or inuenced by methyl-type fermentation. These samples are from the south and southeast parts of the basin and may have been affected by late stage methyl-type fermentation close to areas of recharge. References
Ayers, W.B., Kaiser, W.R., Laubach, S.A., Ambrose, W.A., Baumgardner Jr., R.W., Scott, A.R., Tyler, R., Yeh, J., Hawkins, G.J., Swartz, T.E., Schultz-Ela, D.D., Zellers, S.D., 1991. Geologic and hydrologic controls on the occurrence and producibility of coalbed methane. Fruitland Formation, San Juan basin. Gas Research Institute Topical Rept. GRI-91/0072. 314 pp. http://www.gastechnology.org/webroot/app/xn/xd.aspx? it=enweb&xd=10AbstractPage/5426.xml. Bartos, T.T., Ogle, K.M., 2002. Water quality and environmental isotopic analyses of ground-water samples collected from the Wasatch and Fort Union Formations in areas of coalbed methane development implications to recharge and groundwater ow, eastern Powder River Basin, Wyoming. U.S. Geological Survey Water Resources Investigation Report. Bloyd, R.M., Daddow, P.B., Jordan, P.R., Lowham, H.W., 1986. Investigation of possible effects of surface coal mining on hydrology and landscape stability in part of the Powder River structural basin, northeastern Wyoming. U.S. Geological Survey Water Resources Investigations Report 86-4329. 101 pp. Craig, H., 1961. Isotopic variations in meteoric waters. Science 133 (3465), 17021703. Curry, W.H., 1971. Laramide structural history of the Powder River basin, Wyoming. Symposium on Wyoming Tectonics and Their Economic Signicance. Wyoming Geological Association, 23rd Annual Field Conference Guidebook, pp. 4960. Daddow, P.B., 1986. Potentiometric-surface map of the WyodakAnderson coal bed, Powder River structural basin, Wyoming, 1973-84. U.S. Geological Survey WaterResources Investigations Report 85-4305, scale 1:250,000. Davis, R.W., 1976. Hydrologic factors related to coal development in the eastern Powder River Basin. In: Laudon, R.B. (Ed.), Geology and Energy Resources of the Powder River Basin. Wyoming Geological Association, 28th Annual Field Conference Guidebook, pp. 203207. Davis, R.E., 1984. Geochemistry and geohydrology of the west Decker and Big Sky coalmining areas, southeastern Montana. U.S. Geological Survey Water Resources Investigations Report 83-4225. 109 pp. Denson, N.M., Macke, D.I., Schumann, R.R., 1989a. Geologic map and distribution of heavy minerals in Tertiary rocks of the Gillette 30' x 60' quadrangle, Campbell, Crook, and Weston Counties, Wyoming. U.S. Geological Survey, Miscellaneous Investigations Series Map I-2023, scale 1:125,000. Denson, N.M., Macke, D.I., Schumann, R.R., 1989b. Geologic map and distribution of heavy minerals in Tertiary rocks of the Gillette 30' x 60' quadrangle, Campbell, Crook, and Weston Counties, Wyoming. U.S. Geological Survey, Miscellaneous Investigations Series Map I-2025, scale 1:125,000. Dockins, W.S., Olson, G.J., McFeters, G.A., Turbak, S.C., Lee, R.W., 1980. Sulfate reduction in ground water of southeastern Montana. U.S. Geological Survey Water Resources Investigations Report 80-9. 13 pp. Feathers, K.R., Robert, L., Stephenson, T.R., 1981. Occurrence and characteristics of ground water in the Powder River Basin, Wyoming. University of Wyoming, Water Resources Research Institute Report I-1. 168 pp., 4 app., IV, 8 pl. Flores, R.M., 2004. Coalbed methane in the Powder River Basin, Wyoming and Montana: an assessment of the TertiaryUpper Cretaceous coalbed methane Total Petroleum System. U.S. Geological Survey Digital Data Series DDS-69-C. 56 pp. Flores, R.M., Bader, L.R., 1999. Fort Union coal in the Powder River Basin, Wyoming and Montana a synthesis. U.S. Geological Survey Professional Paper 1625-A, CD-ROM disks 1 and 2, Chapter PS, PS1PS75. Flores, R.M., Ochs, A.M., Bader, L.R., Johnson, R.C., Vogler, D., 1999. Framework geology of the Fort Union coal in the Powder River Basin. U.S. Geological Survey Professional Paper 1625-A, Chapter PF, CD-ROM disks 1 and 2, PF1PF37. Flores, R.M., McGarry, D.E., Stricker, G.D., 2005. CBNG development: confusing coal stratigraphy and gas production in the Powder River Basin. Canadian Society of Petroleum Geologist Gussow Conference, Canmore, Canada, Abstracts with Programs 13. Flores, R.M., Rice, C.A., Stricker, G.D., Warden, A., Ellis, M.S., 2008. Methanogenic pathways of coalbed gas in eth Powder River Basin, United States: The geologic factor. In: Flores, R.M. (Ed.), Microbes, Methanogenesis, and Microbial Gas in Coal. International Journal of Coal Geology Special Issue, pp. 5275 (this volume). Gorody, A.W., 1999. The origin of natural gas in the Tertiary coal seams on the eastern margin of the Powder River Basin. In: Miller, W.R. (Ed.), Coalbed Methane and the Tertiary Geology of the Powder River Basin. Wyoming Geological Association, 50th Annual Field Conference Guidebook, pp. 89101. Hagmaier, J.L., 1971. Groundwater ow, hydrogeochemistry, and uranium deposition in the Powder River Basin, Wyoming. University of North Dakota, Grand Forks, Ph.D. Thesis, 166 pp. Heffern, E.L., Coates, D.A., 1999. Hydrogeology and ecology of clinker in the Powder River Basin, Wyoming and Montana. In: Miller, W.R. (Ed.), Coalbed Methane and the Tertiary Geology of the Powder River Basin. Wyoming Geological Association, 50th Annual Field Conference Guidebook, pp. 231252.

Fig. 9. DCH4 versus DH2O of Fort Union Formation gas and associated water samples by equivalent individual coal beds. The dashed lines represent the range in values for methanogenesis by CO2-reduction (Whiticar, 1999).

isotopic signature of methane in samples below the CO2-reduction eld have either been overprinted or in some way were inuenced by methyl-type fermentation (Flores et al., 2008-this volume). If overprinted, it may be recent or it may have occurred at the time of primary methanogenesis. (Note: An analysis of each sample and its relative location to recharge areas or other zones of inuence in the basin is needed to clarify the timing.) Samples furthest below the CO2reduction eld are all from localities in the south-southeastern part of the basin, close to WyodakAnderson coal zone outcrops. These samples are likely inuenced by modern generation of methane by late stage methyl-type fermentation. Although there is wide variation in values of the isotopes of gas and water for individual coal beds (Fig. 9), the variations are not correlated within a coal bed. Isotopes of gas and water were correlated between coal beds by Flores et al. (2008-this volume). 5. Summary The composition of water co-produced with CBM reects the geochemical and biogeochemical processes that occur over time in the Fort Union Formation and provides important clues to an understanding of the geologic and hydrologic controls on the generation and storage of coalbed methane. Water/rock interaction, mixing, and biogeochemical reactions alter the chemical and isotopic signature of the water along vertical and horizontal ow paths, with the regional ow path being south-southeast to north-northwest and the primary source of recharge in clinker areas in the eastern and southern portions of the basin. Shallow surface water in the PRB, a mixed cation (Ca, Mg, Na) and mixed anion (HCO3, SO4) type water, was altered to a NaHCO3 type water by (1) the precipitation and dissolution of calcite, dolomite, and gypsum; (2) exchange of Ca and Mg for Na on abundant smectites; and (3) sulfate reduction and methanogenesis. The trend in the isotopic signature of the co-produced water in Fort Union Formation coals in the PRB indicates that the complex depositional history of the lower Tertiary strata play an important role in the generation and storage of methane. The areal distribution of DH2O and 18OH2O shows a south-to-north trend of isotopically light values in the center of the basin, with the heaviest values located along the south-to-southeast recharge areas. An exception is the area in the northwesternmost portion of the basin that was subjected to

C.A. Rice et al. / International Journal of Coal Geology 76 (2008) 7685 Heffern, E.L., Coates, D.A., Peacock, K.T., Oakleaf, J.R., Ogle, K.R., 1996. Recharge from clinker, Powder River Basin, Wyoming and Montana. Geological Society of America, Abstracts with Programs, vol. 28(7), p. 354. Hose, R.K., 1955. Geology of the Crazy Woman Creek area, Johnson County, Wyoming. U.S. Geological Survey Bulletin 1027-B, B33B118. Larson, L.R., Daddow, R.L., 1984. Ground-water quality data from the Powder River structural basin and adjacent areas, northeastern Wyoming. U.S. Geological Survey Open-File Report 83939. 56 pp. Law, B.E., 1978. Geologic map and coal deposits of the Gillette West quadrangle, Campbell County, Wyoming. U.S. Geological Survey Miscellaneous Field Studies Map MF-974, scale 1:24,000. Law, B.E., Rice, D.A., Flores, R.M., 1991. Coalbed gas accumulations in the Paleocene Fort Union Formation, Powder River Basin, Wyoming. In: Schwochow, S.D., Murray, D.K., Fahy, M.F. (Eds.), Coalbed Methane of Western North America. Rocky Mountain Association of Geologists, pp. 179190. Lee, R.W., 1981. Geochemistry of water in the Fort Union Formation of the northern Powder River Basin, southeastern Montana. U.S. Geological Survey Water Supply Paper 2076. 17 pp. Lewis, B.D., Hotchkiss, W.R., 1981. Thickness, percent sand, and conguration of shallow hydrogeologic units in the Powder River Basin, Montana and Wyoming: U.S. Geological Survey Miscellaneous Geologic Investigations Map I1317, scale 1:1,000,000. Lindner-Lunsford, J.B., Wilson Jr., J.F., 1992. Shallow ground water in the Powder River Basin, northeastern Wyoming description of selected publications, 195091, and indications for further study. U.S. Geological Survey Water Resources Investigations Report 914067. 71 pp. Lobmeyer, D.H., 1985. Freshwater heads and ground-water temperatures in aquifers of the Northern Great Plains in parts of Montana, North Dakota, South Dakota, and Wyoming. U.S. Geological Survey Professional Paper 1402-D, D1D11. Love, J.D., Weitz, J.L., 1951. Geologic map of the Powder River basin and adjacent areas, Wyoming. U.S. Geological Survey Oil and Gas Investigations Map OM-122. Lowry, M.E., Cummings, T.R., 1966. Ground-water resources of Sheridan County, Wyoming. U.S. Geological Survey Water Supply Paper 1807. 77 pp. Lowry, M.E., Wilson Jr., J.F., et al., 1986. Hydrology of Area 50, Northern Great Plains and Rocky Mountain coal provinces, Wyoming and Montana. U.S. Geological Survey Water-Resources Investigations Open-File Report 83545. 137 pp. Martin, L.J., Naftz, D.L., Lowham, H.W., Rankl, J.G., 1988. Cumulative potential hydrologic impacts of surface coal mining in the eastern Powder River Structural Basin, northeastern Wyoming. U.S. Geological Survey Water Resources Investigations Rept. 884046. 201 pp. Rankl, J.G., Lowry, M.E., 1990. Ground-water ow systems in the Powder River structural basin, Wyoming and Montana. U.S. Geological Survey Water Resources Investigations Report 854229. 39 pp. Rice, D.D., 1993. Composition and origins of coalbed gas. In: Law, B.E., Rice, D.D. (Eds.), Hydrocarbons from Coal. American Association of Petroleum Geologists Studies in Geology, vol. 38, pp. 159184. Rice, C.A., 2003. Production waters associated with the Ferro coaled methane elds, central Utah: chemical and isotopic composition and volumes. International Journal of Coal Geology 56, 141169.

85

Rice, D.D., Flores, R.M., 1991. Controls of bacterial gas accumulations in thick Tertiary coal beds and adjacent channel sandstones, Powder River Basin, Wyoming and Montana. American Association of Petroleum Geologists Bulletin, vol. 75(3), p. 661. Rice, C.A., Ellis, M.S., Bullock Jr., J.K., 2000. Water co-produced with coalbed methane in the Powder River Basin, Wyoming preliminary compositional data. U.S. Geological Survey Open-File Report 00372 (20 pp). Rice, C.A., Bartos, T.T., Ellis, M.S., 2002. Chemical and isotopic composition of water in the Fort. In: Chowchow, S.D., Nuncio, V.F. (Eds.), Union and Wasatch Formations of the Powder River basin, Wyoming and Montana: implications for coaled methane development. Coaled methane of North America, II. Rocky Mountain Association of Geologists Guidebook, pp. 5370. Riffenburg, H.B., 1925. Chemical character of ground water of the northern Great Plains. U. S. Geological Survey Water-Supply Paper 560-B, pp. 3152. Scott, A.R., 1999. Improving coal gas recovery with microbially enhanced coalbed methane. In: Mastalery, M., Glikson, M.V., Golding, S.D. (Eds.), Coalbed Methane: Scientic, Environmental and Economic Evaluation. Kluwer Academics, pp. 89110. Seeland, D.A., 1992. Depositional systems of a synorogenic continental deposit the upper Paleocene and lower Eocene Wasatch Formation of the Powder River basin, northeast Wyoming. U.S. Geological Survey Bulletin 1917-H, H1H20. Slagle, S.E., Lewis, B.D., Lee, R.E., 1985. Ground-water resources and potential hydrologic effects of surface coal mining in the northern Powder River Basin, southeastern Montana. U.S. Geological Survey Water Supply Paper 2239. 34 pp. Stumm, W., Morgan, J.J., 1981. Aquatic Chemistry. Wiley and Sons, New York, pp. 453461. Surdam, R.C., Jiao, Z., Heasler, H.P., 2007. Origin of thermogenic and biogenic natural gas in the Tongue River Member coals of the Fort Union Formation, Northeastern Powder River Basin, Wyoming. Wyoming State Geological Survey Report of Investigations, vol. 58. 43 pp. Tschudy, R.H., 1976. Pollen changes near the Fort UnionWasatch boundary, Powder River Basin. In: Laudon, R.B. (Ed.), Geology and energy resources of the Powder River basin. Wyoming Geological Association, 28th Annual Field Conference Guidebook, pp. 7381. U.S. Bureau of Land Management, 1999. Wyodak coal bed methane project, draft environmental impact statement. U.S. Bureau of Land Management, Buffalo (Wyoming) Field Ofce, May 1999, variable pagination. Van Voast, W.A., Reiten, J.C., 1988. Hydrogeologic responses: twenty years of surface coal mining in southeastern Montana. Montana Bureau of Mines and Geology Memoir, vol. 62. 30 pp. Whitcomb, H.A., Cummings, T.R., McCullough, R.A., 1966. Ground-water resources and geology of northern and central Johnson County, Wyoming. U.S. Geological Survey Water Supply Paper, vol. 1806. 99 pp. Whiticar, M.J., 1999. Carbon and hydrogen isotope systematics of bacterial formation and oxidation of methane. Chemical Geology 161, 291314. Whiticar, M.J., Faber, E., Schoell, M., 1986. Biogenic methane formation in marine and freshwater environments: CO2 reduction vs. acetate fermentation isotope evidence. Geochimica et Cosmochimica Acta 50, 693709. Woessner, W.W., Osborne, T.J., Heffner, E.L., Andrews, C.J., Whiteman, J., Spotted Elk, W., Morales-Brink, D., 1981. Hydrologic impact from potential coal strip mining, Northern Cheyenne Reservation. U.S. Environmental Protection Agency Research and Development Report EPA-600/S7-81-004. 302 pp.