Andrew G. Hunt

Source of radiogenic helium 4 in shallow aquifers: Implications for dating young groundwater

Radiogenic helium 4 (4Herad) has been used in numerous studies as a tracer of groundwater age in the range of 103–108 years. We have measured 4Herad along shallow groundwater flow paths at a variety of hydrogeologically distinct sites and postulate its use for dating groundwater as young as 101 years. Groundwater travel times and fluid velocities are particularly well documented at one site in northern Ontario because of detailed profiling of tritium, 3H/3He ratios, and chlorofluorocarbons (CFCs). Metamorphic rocks of the Canadian Shield (>1 Ga) that contain large quantities of 4He are the protolith of this unconsolidated aquifer and observed 4Herad values increase linearly with distance along a flow path and with increasing groundwater age. A solute transport model suggests that the aquifer solids are the source of 4Herad as vertical fluid velocities are too great to allow upward diffusion of 4Herad from the underlying shield rocks. The apparent rate of 4Herad release is 130 μcm3 m−3 yr−1 and is 300 times greater than can be supported by the in situ decay of U and Th series nuclides (i.e., the “steady state” approximation). Laboratory release experiments (conducted by sequentially heating the aquifer solids, measuring the amount of 4He released, and then extrapolating release rates to the in situ temperature) agree well with the field results and suggest that diffusion from aquifer solids is the source of 4Herad. The combined laboratory and field release data yield 4He diffusion coefficients that exhibit an Arrhenius temperature dependence that is similar to4Herad diffusion in quartz reported by other researchers. The 4Herad release rate at the Ontario site is extraordinarily similar to sites in Tennessee, Nebraska, and Germany in spite of major hydrogeologic differences. A model of 4He diffusion from spherical grains suggests that aquifer solids derived from old protoliths will release 4He at rates greater than supported by U/Th production for up to 50 million years in fine sands that have typical U/Th concentrations. Both observations and modeling suggest that 4He may be useful as a groundwater dating tool over a range of tens to hundreds of years. The latter is particularly important because no other groundwater dating techniques are accurate for waters ranging from 40 to about 500 years old.

Determining the source and genetic fingerprint of natural gases using noble gas geochemistry: A northern Appalachian Basin case study

Silurian and Devonian natural gas reservoirs present within New York state represent an example of unconventional gas accumulations within the northern Appalachian Basin. These unconventional energy resources, previously thought to be noneconomically viable, have come into play following advances in drilling (i.e., horizontal drilling) and extraction (i.e., hydraulic fracturing) capabilities. Therefore, efforts to understand these and other domestic and global natural gas reserves have recently increased. The suspicion of fugitive mass migration issues within current Appalachian production fields has catalyzed the need to develop a greater understanding of the genetic grouping (source) and migrational history of natural gases in this area. We introduce new noble gas data in the context of published hydrocarbon carbon (C1,C2+) (13C) data to explore the genesis of thermogenic gases in the Appalachian Basin. This study includes natural gases from two distinct genetic groups: group 1, Upper Devonian (Marcellus shale and Canadaway Group) gases generated in situ, characterized by early mature (13C[C1 C2][13C113C2]: –9), isotopically light methane, with low (4He) (average, 1 103 cc/cc) elevated 4He/40Ar and 21Ne/40Ar (where the asterisk denotes excess radiogenic or nucleogenic production beyond the atmospheric ratio), and a variable, atmospherically (air-saturated–water) derived noble gas component; and group 2, a migratory natural gas that emanated from Lower Ordovician source rocks (i.e., most likely, Middle Ordovician Trenton or Black River group) that is currently hosted primarily in Lower Silurian sands (i.e., Medina or Clinton group) characterized by isotopically heavy, mature methane (13C[C1 – C2] [13C113C2]: 3), with high (4He) (average, 1.85 103 cc/cc) 4He/40Ar and 21Ne/40Ar near crustal production levels and elevated crustal noble gas content (enriched 4He, 21Ne, 40Ar). Because the release of each crustal noble gas (i.e., He, Ne, Ar) from mineral grains in the shale matrix is regulated by temperature, natural gases obtain and retain a record of the thermal conditions of the source rock. Therefore, noble gases constitute a valuable technique for distinguishing the genetic source and post-genetic processes of natural gases.

Vulnerability of a Public Supply Well in a Karstic Aquifer to Contamination

To assess the vulnerability of ground water to contamination in the karstic Upper Floridan aquifer (UFA), age-dating tracers and selected anthropogenic and naturally occurring compounds were analyzed in multiple water samples from a public supply well (PSW) near Tampa, Florida. Samples also were collected from 28 monitoring wells in the UFA and the overlying surficial aquifer system (SAS) and intermediate confining unit located within the contributing recharge area to the PSW. Age tracer and geochemical data from the earlier stage of the study (2003 through 2005) were combined with new data (2006) on concentrations of sulfur hexafluoride (SF(6)), tritium ((3)H), and helium-3, which were consistent with binary mixtures of water for the PSW dominated by young water (less than 7 years). Water samples from the SAS also indicated mostly young water (less than 7 years); however, most water samples from monitoring wells in the UFA had lower SF(6) and (3)H concentrations than the PSW and SAS, indicating mixtures containing high proportions of older water (more than 60 years). Vulnerability of the PSW to contamination was indicated by predominantly young water and elevated nitrate-N and volatile organic compound concentrations that were similar to those in the SAS. Elevated arsenic (As) concentrations (3 to 19 microg/L) and higher As(V)/As(III) ratios in the PSW than in water from UFA monitoring wells indicate that oxic water from the SAS likely mobilizes As from pyrite in the UFA matrix. Young water found in the PSW also was present in UFA monitoring wells that tap a highly transmissive zone (43- to 53-m depth) in the UFA.

Quality and Age of Shallow Groundwater in the Bakken Formation Production Area, Williston Basin, Montana and North Dakota

The quality and age of shallow groundwater in the Bakken Formation production area were characterized using data from 30 randomly distributed domestic wells screened in the upper Fort Union Formation. Comparison of inorganic and organic chemical concentrations to health based drinking-water standards, correlation analysis of concentrations with oil and gas well locations, and isotopic data give no indication that energy-development activities affected groundwater quality. It is important, however, to consider these results in the context of groundwater age. Most samples were recharged before the early 1950s and had 14C ages ranging from <1000 to >30,000 years. Thus, domestic wells may not be as well suited for detecting contamination associated with recent surface spills as shallower wells screened near the water table. Old groundwater could be contaminated directly by recent subsurface leaks from imperfectly cemented oil and gas wells, but horizontal groundwater velocities calculated from 14C ages imply that the contaminants would still be less than 0.5 km from their source. For the wells sampled in this study, the median distance to the nearest oil and gas well was 4.6 km. Because of the slow velocities, a long-term commitment to groundwater monitoring in the upper Fort Union Formation is needed to assess the effects of energy development on groundwater quality. In conjunction with that effort, monitoring could be done closer to energy-development activities to increase the likelihood of early detection of groundwater contamination if it did occur.

Dissolved gases in hydrothermal (phreatic) and geyser eruptions at Yellowstone National Park, USA

Multiphase and multicomponent fluid flow in the shallow continental crust plays a significant role in a variety of processes over a broad range of temperatures and pressures. The presence of dissolved gases in aqueous fluids reduces the liquid stability field toward lower temperatures and enhances the explosivity potential with respect to pure water. Therefore, in areas where magma is actively degassing into a hydrothermal system, gas-rich aqueous fluids can exert a major control on geothermal energy production, can be propellants in hazardous hydrothermal (phreatic) eruptions, and can modulate the dynamics of geyser eruptions. We collected pressurized samples of thermal water that preserved dissolved gases in conjunction with precise temperature measurements with depth in research well Y-7 (maximum depth of 70.1 m; casing to 31 m) and five thermal pools (maximum depth of 11.3 m) in the Upper Geyser Basin of Yellowstone National Park, USA. Based on the dissolved gas concentrations, we demonstrate that CO 2 mainly derived from magma and N 2 from air-saturated meteoric water reduce the near-surface saturation temperature, consistent with some previous observations in geyser conduits. Thermodynamic calculations suggest that the dissolved CO 2 and N 2 modulate the dynamics of geyser eruptions and are likely triggers of hydrothermal eruptions when recharged into shallow reservoirs at high concentrations. Therefore, monitoring changes in gas emission rate and composition in areas with neutral and alkaline chlorine thermal features could provide important information on the natural resources (geysers) and hazards (eruptions) in these areas.

Using geochemistry to identify the source of groundwater to Montezuma Well, a natural spring in Central Arizona, USA: part 2

Montezuma Well is a natural spring located within a “sinkhole” in the desert environment of the Verde Valley in Central Arizona. It is managed by the National Park Service as part of Montezuma Castle National Monument. Because of increasing development of groundwater in the area, this research was undertaken to better understand the sources of groundwater to Montezuma Well. The use of well logs and geophysics provides details on the geology in the area around Montezuma Well. This includes characterizing the extent and position of a basalt dike that intruded a deep fracture zone. This low permeability barrier forces groundwater to the surface at the Montezuma Well “pool” with sufficient velocity to entrain sand-sized particles from underlying bedrock. Permeable fractures along and above the basalt dike provide conduits that carry deep sourced carbon dioxide to the surface, which can dissolve carbonate minerals along the transport path in response to the added carbon dioxide. At the ground surface, CO2 degasses, depositing travertine. Geologic cross sections, rock geochemistry, and semi-quantitative groundwater flow modeling provide a hydrogeologic framework that indicates groundwater flow through a karstic limestone at depth (Redwall Limestone) as the most significant source of groundwater to Montezuma Well. Additional groundwater flow from the overlying formations (Verde Formation and Permian Sandstones) is a possibility, but significant flow from these units is not indicated.

A landslide in Tertiary marine shale with superheated fumaroles, Coast Ranges, California

In August 2004, a National Forest fire crew extinguished a 1.2 ha fire in a wilderness area ~40 km northeast of Santa Barbara, California. Examination revealed that the fire originated on a landslide dotted with superheated fumaroles. A 4 m borehole punched near the hottest (262 °C) fumarole had a maximum temperature of 307 °C. Temperatures in this borehole have been decreasing by ~0.1 °C/d, although the cooling rate is higher when the slide is dry. Gas from the fumaroles and boreholes is mostly air with 3–8 vol% carbon dioxide and trace amounts of carbon monoxide, methane, ethane, and propane. The carbon dioxide is 14 C-dead. The ratios of methane to ethane plus propane [C 1 /(C 2 + C 3 )] range from 3.6 to 14. Carbon isotope values for the CO 2 range from −14‰ to −23‰ δ 13 C. 3 He/ 4 He values range from 0.96 to 0.97 times that of air. The anomalous heat is interpreted to be due to rapid oxidation of iron sulfide augmented by combustion of carbonaceous matter within the formation.

Methane in groundwater from a leaking gas well, Piceance Basin, Colorado, USA

Site-specific and regional analysis of time-series hydrologic and geochemical data collected from 15 monitoring wells in the Piceance Basin indicated that a leaking gas well contaminated shallow groundwater with thermogenic methane. The gas well was drilled in 1956 and plugged and abandoned in 1990. Chemical and isotopic data showed the thermogenic methane was not from mixing of gas-rich formation water with shallow groundwater or natural migration of a free-gas phase. Water-level and methane-isotopic data, and video logs from a deep monitoring well, indicated that a shale confining layer ~125m below the zone of contamination was an effective barrier to upward migration of water and gas. The gas well, located 27m from the contaminated monitoring well, had ~1000m of uncemented annular space behind production casing that was the likely pathway through which deep gas migrated into the shallow aquifer. Measurements of soil gas near the gas well showed no evidence of methane emissions from the soil to the atmosphere even though methane concentrations in shallow groundwater (16 to 20mg/L) were above air-saturation levels. Methane degassing from the water table was likely oxidized in the relatively thick unsaturated zone (~18m), thus rendering the leak undetectable at land surface. Drilling and plugging records for oil and gas wells in Colorado and proxies for depth to groundwater indicated thousands of oil and gas wells were drilled and plugged in the same timeframe as the implicated gas well, and the majority of those wells were in areas with relatively large depths to groundwater. This study represents one of the few detailed subsurface investigations of methane leakage from a plugged and abandoned gas well. As such, it could provide a useful template for prioritizing and assessing potentially leaking wells, particularly in cases where the leakage does not manifest itself at land surface.

Aleutian Arc Fluid Geochemical Data

This report contains the chemical and isotopic data from thermal waters and gases collected from the Aleutian Arc over the past 20 years, where such data remain unpublished or only published in part.