Chemical analyses of ground-water samples were evaluated as part of an investigation of lower Tertiary aquifers in the eastern Powder River Basin where coalbed methane is being developed. Ground-water samples were collected from two springs discharging from clinker, eight monitoring wells completed in the Wasatch aquifer, and 13 monitoring or coalbed methane production wells completed in coalbed aquifers. The ground-water samples were analyzed for major ions and environmental isotopes (tritium and stable isotopes of hydrogen and oxygen) to characterize the composition of waters in these aquifers, to relate these characteristics to geochemical processes, and to evaluate recharge and ground-water flow within and between these aquifers. This investigation was conducted in cooperation with the Wyoming State Engineer's Office and the Bureau of Land Management.

Water quality in the different aquifers was characterized by major-ion composition. Samples collected from the two springs were classified as calcium-sulfate-type and calcium-bicarbonate-type waters. All ground-water samples from the coalbed aquifers were sodium-bicarbonate-type waters as were five of eight samples collected from the overlying Wasatch aquifer.

Potential areal patterns in ionic composition were examined. Ground-water samples collected during this and another investigation suggest that dissolved-solids concentrations in the coalbed aquifers may be lower south of the Belle Fourche River (generally less than 600 milligrams per liter). As ground water in coalbed aquifers flows to the north and northwest away from an inferred source of recharge (clinker in the study area), dissolved-solids concentrations appear to increase.

Variation in ionic composition in the vertical dimension was examined qualitatively and statistically within and between aquifers. A relationship between ionic composition and well depth was noted and corroborates similar observations by earlier investigators in the Powder River Basin in both Wyoming and Montana. This relationship results in two different water-quality zones with different characteristics - a shallow zone, comprising the upper part of the Wasatch aquifer, characterized by mixed cation composition and either sulfate or bicarbonate as the dominant anion; and a deeper zone, comprising the lower (deeper) part of the Wasatch aquifer and the underlying coalbed aquifers, characterized by sodium-bicarbonate-type waters. The zonation appears to be related to geochemical processes described by earlier investigators such as dissolution and precipitation of minerals, ion exchange, sulfate reduction, and mixing of waters. Qualitative and statistically significant differences were observed in sulfate concentrations between the coalbed aquifers and the overlying Wasatch aquifer. Ionic composition suggests that bacterially mediated redox processes such as sulfate reduction were probably the dominant geochemical processes in the anaerobic coalbed aquifers.

Tritium was used to qualitatively estimate the time of ground-water recharge. Tritium concentrations in both springs suggests that both were recharged after 1952 and contain modern water. Tritium was not detected at concentrations suggestive of modern water in any ground-water samples collected from the coalbed aquifers or in six of eight ground-water samples collected from the overlying Wasatch aquifer. Tritium concentrations in the remaining two wells from the Wasatch aquifer suggest a mixture between submodern (recharged before 1952) and modern water, although the low concentrations suggest that ground water in these two wells have very little modern water. The relative absence of modern water in all aquifers in the study area suggests that recharge processes to these aquifers are probably very slow.

Paired d²H (deuterium/hydrogen isotopic ratio) and d¹⁸O (oxygen-18/oxygen-16 isotopic ratio) values for samples collected from the springs and all aquifers are close to the Global Meteoric Water Line, a meteoric water line for North American continental precipitation, and an estimated local meteoric water line, suggesting the water in the aquifers is of meteoric origin. The d²H and d¹⁸O values suggest that the waters were recharged in a colder climate or temperature, mid-latitudes, and mid-continent. In general, the samples do not form separate groups based on aquifer origin; this suggests either intermixing of the waters in the aquifers or that the different aquifers are subject to similar recharge and/or evolutional paths for the water. However, examination of the differences in the values of d²H and d¹⁸O, in combination with major-ion chemistry at three monitoring-well clusters, suggest that changes in the values with depth may represent different timing or sources of recharge to the different aquifers.

The areal distribution of d²H was examined and an apparent break in the d²H along a northwest to southeast trend was observed. In the coalbed aquifers, all but one ground-water sample (collected from the Big George coal bed), show a pattern where the d²H values become more negative towards the center of the Powder River Basin and values greater (less negative) than an arbitrary reference value of -140 ‰ (per mil or parts per thousand) were observed near the outcrop area of the Wyodak-Anderson coal zone. In the overlying Wasatch aquifer, the d²H values became less negative towards the center of the basin. The values more negative than -140 ‰ are near the outcrop area and the values that are less negative than -140 ‰ are closer to the basin center. It is unclear if this pattern is a result of sample size, different recharge mechanisms, geochemical processes, or if the processes producing these differences are independent or unrecognized.

Results of water-quality sampling were compared with selected regulatory and non-regulatory standards as well as commonly-used guidelines for proposed water uses. Dissolved solids was the measure that most frequently exceeded U.S. Environmental Protection Agency public water-supply standards and State of Wyoming domestic-use standards in ground-water samples collected from the Wasatch aquifer and coalbed aquifers. The State of Wyoming agricultural standards (irrigation) for sulfate and dissolved solids were exceeded in some samples collected from the Wasatch aquifer and coalbed aquifers. The State of Wyoming livestock standard for pH was exceeded in some samples collected from the Wasatch aquifer. Water from the Wasatch aquifer ranged from soft to very hard, and water from the coalbed aquifers ranged from moderately hard to very hard. Samples collected from wells completed in both the Wasatch aquifer and coalbed aquifers plotted in a wide range of both sodium- and salinity-hazard classes, but most samples clustered in or near the combined medium-sodium-hazard—high-salinity-hazard classes.