Geology topics

Andrew G. Hunt

Publications and source records attributed to Andrew G. Hunt.

At least 37 records · Page 2Linked to original sources

USGS2021

Relative risk of groundwater-quality degradation near California (USA) oil fields estimated from 3H, 14C, and 4He

Relative risks of groundwater-quality degradation near selected California oil fields are estimated by examining spatial and temporal patterns in chemical and isotopic data in the context of groundwater-age categories defined by tritium and carbon-14. In the Coastal basins, western San Joaquin Valley (SJV), and eastern SJV; 82, 76, and 0% of samples are premodern (pre-1953 recharge), respectively; and 3, 0, and 31% are modern (recharged during or after 1953), respectively. Carbon-14 and helium-4 data indicate most premodern samples are 1000 to 10,000 (33%) or >10,000 (50%) years old. Organic chemicals that could be associated with deeper hydrocarbon reservoirs (e.g. thermogenic gases and benzene) occur most frequently in premodern groundwater, suggesting premodern groundwater has a higher risk of degradation from upward migration of hydrocarbons than modern and mixed-age groundwater. Low sulfate concentrations in some premodern groundwater containing high thermogenic-methane concentrations (>28 mg/L) indicate methane attenuation associated with sulfate reduction can be limited in premodern groundwater. The more common occurrence of manufactured compounds, like tetrachloroethene, in modern and mixed-age groundwater than in premodern groundwater indicates modern and mixed-age groundwater has a higher risk of degradation from land-surface sources than premodern groundwater. Time-series data for chloride in groundwater affected by disposal of oil-field water in unlined ponds indicate some modern and mixed-age groundwater are susceptible to chemical migration within 2–3 km of surface sources. Timescales for diluting chloride concentrations in groundwater with fresh recharge once disposal ponds are decommissioned are shorter in mixed-age groundwater with large fractions of modern water (9–14 years in one example) than in mixed-age groundwater with large fractions of premodern water (no evidence of dilution after 12 years of monitoring in one example). The presence of predominantly premodern groundwater in the Coastal basins and western SJV indicates these areas have relatively high risk from upward migration of hydrocarbons, reduced methane attenuation capacity, and long dilution times, whereas predominantly modern- and mixed-age groundwater in the eastern SJV indicates this area has relatively high risk from chemical migration from land-surface sources and subsequent extensive spreading. Age-based characterizations of relative risk could inform the design of groundwater-monitoring programs near oil fields in terms of the spatial distribution of monitoring points relative to source areas and monitoring frequency and duration.

California↗

USGS2021

Noble gas signatures constrain oil-field water as the carrier phase of hydrocarbons occurring in shallow aquifers in the San Joaquin Basin, USA

Noble gases record fluid interactions in multiphase subsurface environments through fractionation processes during fluid equilibration. Water in the presence of hydrocarbons at the subsurface acquires a distinct elemental signature due to the difference in solubility between these two fluids. We find the atmospheric noble gas signature in produced water is partially preserved after hydrocarbons production and water disposal to unlined ponds at the surface. This signature is distinct from meteoric water and can be used to trace oil-field water seepage into groundwater aquifers. We analyse groundwater ( n = 30) and fluid disposal pond ( n = 2) samples from areas overlying or adjacent to the Fruitvale, Lost Hills, and South Belridge Oil Fields in the San Joaquin Basin, California, USA. Methane (2.8 × 10 −7 to 3 × 10 −2 cm 3 STP/cm 3 ) was detected in 27 of 30 groundwater samples. Using atmospheric noble gas signatures, the presence of oil-field water was identified in 3 samples, which had equilibrated with thermogenic hydrocarbons in the reservoir. Two (of the three) samples also had a shallow microbial methane component, acquired when produced water was deposited in a disposal pond at the surface. An additional 6 samples contained benzene and toluene, indicative of interaction with oil-field water; however, the noble gas signatures of these samples are not anomalous. Based on low tritium and 14 C contents (≤ 0.3 TU and 0.87–6.9 pcm, respectively), the source of oil-field water is likely deep, which could include both anthropogenic and natural processes. Incorporating noble gas analytical techniques into the groundwater monitoring programme allows us to 1) differentiate between thermogenic and microbial hydrocarbon gas sources in instances when methane isotope data are unavailable, 2) identify the carrier phase of oil-field constituents in the aquifer (gas, oil-field water, or a combination), and 3) differentiate between leakage from a surface source (disposal ponds) and from the hydrocarbon reservoir (either along natural or anthropogenic pathways such as faulty wells).

California↗

USGS2021

Groundwater quality of aquifers overlying the Oxnard Oil Field, Ventura County, California

Groundwater samples collected from irrigation, monitoring, and municipal supply wells near the Oxnard Oil Field were analyzed for chemical and isotopic tracers to evaluate if thermogenic gas or water from hydrocarbon-bearing formations have mixed with surrounding groundwater. New and historical data show no evidence of water from hydrocarbon-bearing formations in groundwater overlying the field. However, thermogenic gas mixed with microbial methane was detected in 5 wells at concentrations ranging from 0.011–9.1 mg/L. The presence of these gases at concentrations <10 mg/L do not indicate degraded water quality posing a known health risk. Analysis of carbon isotopes (δ 13 C-CH 4 ) and hydrogen isotopes (δ 2 H-CH 4 ) of methane and ratios of methane to heavier hydrocarbon gases were used to differentiate sources of methane between a) microbial, b) thermogenic or c) mixed sources. Results indicate that microbial-sourced methane is widespread in the study area, and concentrations overlap with those from thermogenic sources. The highest concentrations of thermogenic gas were observed in proximity to relatively high density of oil wells, large injection volumes of water disposal and cyclic steam, shallow oil development, and hydrocarbon shows in sediments overlying the producing oil reservoirs. Depths of water wells containing thermogenic gas were within approximately 200 m of the top of the Vaca Tar Sand production zone (approximately 600 m below land surface). Due to the limited sampling density, the source and pathways of thermogenic gas detected in groundwater could not be conclusively determined. Thermogenic gas detected in the absence of co-occurring water from hydrocarbon-bearing formations may result from natural gas migration over geologic time from the Vaca Tar Sand or deeper formations, hydrocarbon shows in sediments overlying producing zones, and/or gas leaking from oil-field infrastructure. Denser sampling of groundwater, potential end-members, and pressure monitoring could help better distinguish pathways of thermogenic gases.

California↗

USGS2020

Hydrothermal activity in the southwest Yellowstone Plateau Volcanic Field

In the past two decades, the U.S. Geological Survey and the National Park Service have studied hydrothermal activity across the Yellowstone Plateau Volcanic Field (YPVF) to improve the understanding of the magmatic-hydrothermal system and to provide a baseline for detecting future anomalous activity. In 2017 and 2018 we sampled water and gas over a large area in the southwest YPVF and used Landsat 8 thermal infrared data to estimate radiative heat flow. Most of the thermal activity in this region is in close proximity to the Yellowstone Caldera boundary. Springs and fumaroles discharge from a variety of lithologies including some of the youngest rhyolites in the YPVF. Gas compositions and helium isotope ratios of most samples resemble those in other parts of the YPVF. The waters have meteoric origins and tritium was detected in several samples. Thermal waters from some areas have compositions that plot along a line connecting thermal and non-thermal water endmember compositions. The thermal water endmember equilibrated at 160-170 °C, lower than waters in Yellowstone’s geyser basins. Heat discharged by springs and fumaroles originates from within the Yellowstone Caldera and is transported laterally by advection, mainly along the base of rhyolite flows that cover the inferred caldera boundaries.

Yellowstone National Park↗

USGS2020

Geochemistry and age of groundwater in the Williston Basin, USA: Assessing potential effects of shale-oil production on groundwater quality

Thirty water wells were sampled in 2018 to understand the geochemistry and age of groundwater in the Williston Basin and assess potential effects of shale-oil production from the Three Forks-Bakken petroleum system (TBPS) on groundwater quality. Two geochemical groups are identified using hierarchical cluster analysis. Group 1 represents the younger (median 4 He = 21.49 × 10 −8 cm 3 STP/g), less chemically evolved water. Group 2 represents the older (median 4 He = 1389 × 10 −8 cm 3 STP/g), more chemically evolved water. At least two samples from each group contain elevated Cl concentrations (>70 mg/L). Br/Cl, B/Cl, and Li/Cl ratios indicate multiple sources account for the elevated Cl concentrations: septic-system leachate/road deicing salt, lignite beds in the aquifers, Pierre Shale beneath the aquifers, and water associated with the TBPS (one sample). 3 H and 14 C data indicate that 10.8, 21.6, and 67.6% of the samples are modern (post-1952), mixed age, and premodern (pre-1953), respectively. Lumped-parameter modeling of 3 H, SF 6 , 3 He, and 14 C concentrations indicates mean ages of the modern and premodern fractions range from ~1 to 30 years and 1300 to >30,000 years, respectively. Group 2 contains the highest CH 4 concentrations (0.0018–32 mg/L). δ 13 C–CH 4 and C 1 /C 2 +C 3 data in groundwater (−91.7 to −70.0‰ and 1280 to 13,600) indicate groundwater CH 4 is biogenic in origin and not from thermogenic shale gas. Four volatile organic compounds (VOCs) were detected in two samples. One mixed-age sample contains chloroform (0.25 μg/L) and dichloromethane (0.05 μg/L), which are probably associated with septic leachate. One premodern sample contains butane (0.082 μg/L) and n-pentane (0.032 μg/L), which are probably associated with thermogenic gas from a nearby oil well. The data indicate hydrocarbon production activities do not currently (2018) widely affect Cl, CH 4 , and VOC concentrations in groundwater. The predominance of premodern recharge in the aquifers indicates the groundwater moves relatively slowly, which could inhibit widespread chemical movement in groundwater overlying the TBPS. Comparison of groundwater-age data from five major unconventional hydrocarbon-production areas indicates aquifer zones used for water supply in the TBPS area have a lower risk of widespread chemical movement in groundwater than similar aquifer zones in the Fayetteville (Arkansas) and Marcellus (Pennsylvania) Shale production areas, but have a higher risk than similar aquifer zones in the Eagle Ford (Texas) and Haynesville (Texas, Louisiana) Shale production areas.

Montana, North Dakota, South Dakota↗

USGS2020

A post-eruption study of gases and thermal waters at Okmok Volcano, Alaska

We report here on the first focused study of gas discharges and thermal spring waters at Okmok Volcano since the 2008 phreatomagmatic eruptions. Results include the first compositional gas data from Okmok with minimal air contamination and the first data on magmatic carbon in Okmok spring waters. Chemical and isotopic analyses of the waters and gases are used to assess the character of Okmok fluids eight years after the eruptions ceased. Gases from vents on intracaldera Cone C have high concentrations of H2 and contain H2S rather than SO2, demonstrating the influence of a hydrothermal system, while isotope values of carbon ( 10.2 to 8.9‰) and helium (~8 RA) confirm the presence of magma-derived volatiles. Estimates of equilibrium temperatures for the Cone C gas are ~230 ± 30 ºC. A much cooler reservoir with a maximum temperature of ~55 ºC feeds the intracaldera warm springs. Based on discharge measurements of creeks draining the caldera, the total heat output of the warm springs is estimated to be about 32 MW. Gas data from a single location of steaming ground at the Geyser Bight geothermal area southwest of the Okmok Caldera are given. The gas is typical of geothermal gases with high concentrations of H2S and an air-corrected helium isotope ratio of 7.15 RA.

Alaska↗

USGS2020

Noble gases fingerprint the source and evolution of ore-forming fluids of Carlin-type gold deposits in the Golden Triangle, south China

Precise constraints on the source and evolution of ore-forming fluids of Carlin-type gold deposits in the Golden Triangle (south China) are of critical importance for a better understanding of the ore genesis and a refined genetic model for gold mineralization. However, constraints on the source of ore fluid components have long been a challenge due to the very fine grained nature of the ore and gangue minerals in the deposits. Here we present He, Ne, and Ar isotope data of fluid inclusion extracts from a variety of ore and gangue minerals (arsenian pyrite, realgar, quartz, calcite, and fluorite) representing the main and late ore stages of three well-characterized major gold deposits (Shuiyindong, Nibao, and Yata) to provide significant new insights into the source and evolution of ore-forming fluids of this important gold province. Measured He isotopes have R/R A ratios ranging from 0.01 to 0.4 that suggest a maximum of 5% mantle helium with an R/R A of 8. The Ne and Ar isotope compositions are broadly comparable to air-saturated water, with a few analyses indicating the presence of an external fluid containing nucleogenic 38 Ar and radiogenic 40 Ar. Plotted on the 20 Ne/ 4 He vs. helium R/R A and 3 He/ 20 Ne vs. 4 He/ 20 Ne diagrams, the results define two distinct arrays that emanate from a common sedimentary pore fluid or deeply sourced metamorphic fluid end-member containing crustal He. The main ore-stage fluids are interpreted as a mixture of magmatic fluid containing mantle He and sedimentary pore fluid or deeply sourced metamorphic fluid with predominantly crustal He, whereas the late ore-stage fluids are a mixture of sedimentary pore fluid or deeply sourced metamorphic fluid bearing crustal He and shallow meteoric groundwater containing atmospheric He. Results presented here, when combined with independent evidence, support a magmatic origin for the ore-forming fluids. The ascending magmatic fluid mixed with sedimentary pore fluid or deeply sourced metamorphic fluid in the ore stage and subsequently mixed with the meteoric groundwater in the late ore stage, eventually producing the Carlin-type gold deposits in the Golden Triangle.

Golden Triangle, south China↗

USGS2019

A novel method for the extraction, purification and characterization of noble gases in produced fluids

Hydrocarbon systems with declining or viscous oil production are often stimulated using enhanced oil recovery (EOR) techniques, such as the injection of water, steam and CO2, in order to increase oil and gas production. As EOR and other methods of enhancing production such as hydraulic fracturing have become more prevalent, environmental concerns about the impact of both new and historical hydrocarbon production on overlying shallow aquifers have increased. Noble gas isotopes are powerful tracers of subsurface fluid provenance and can be used to understand the impact of EOR on hydrocarbon systems and potentially overlying aquifers. In oil systems, produced fluids can consist of a mixture of oil, water and gas. Noble gases are typically measured in the gas phase; however, it is not always possible to collect gases and therefore produced fluids (which are water, oil and gas mixtures) must be analyzed. We outline a new technique to separate and analyze noble gases in multi-phase hydrocarbon-associated fluid samples. An offline double capillary method has been developed to quantitatively isolate noble gases into a transfer vessel, while effectively removing all water, oil, and less volatile hydrocarbons. The gases are then cleaned and analyzed using standard techniques. Air-saturated water reference materials (n=24) were analyzed and results show a method reproducibility of 2.9% for 4He, 3.8% for 20Ne, 4.5% for 36Ar, 5.3% for 84Kr and 5.7% for 132Xe. This new technique was used to measure the noble gas isotopic compositions in six produced fluid samples from the Fruitvale Oil Field, Bakersfield, California.

Geochemistry, Geophysics, Geosystems↗

USGS2019

Occurrence and sources of radium in groundwater associated with oil fields in the southern San Joaquin Valley, California

Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range=0.010-0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p<0.001, ρ=0.90, range=145-15,900 mg/L), Mn+Fe concentrations (p<0.001, ρ=0.82, range=<0.005-18.5 mg/L), and pH (p<0.001, ρ=-0.67, range=6.2-9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median=3.1) differed from those in oil-field water (median=0.51). PHREEQC mixing calculations and spatial geochemical variations suggest the Ra in oil-field water was removed by co-precipitation with secondary barite and adsorption on Mn-Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

California↗

USGS2019

Hydrocarbons in upland groundwater, Marcellus Shale Region, Northeastern Pennsylvania and Southern New York, USA

Water samples from 50 domestic wells located <1 km (proximal) and >1 km (distal) from shale-gas wells in upland areas of the Marcellus Shale region were analyzed for chemical, isotopic, and groundwater-age tracers. Uplands were targeted because natural mixing with brine and hydrocarbons from deep formations is less common in those areas compared to valleys. CH 4 -isotope, predrill CH 4 -concentration, and other data indicate that one proximal sample (5% of proximal samples) contains thermogenic CH 4 (2.6 mg/L) from a relatively shallow source (Catskill/Lock Haven Formations) that appears to have been mobilized by shale-gas production activities. Another proximal sample contains five other volatile hydrocarbons (0.03–0.4 μg/L), including benzene, more hydrocarbons than in any other sample. Modeled groundwater-age distributions, calibrated to 3 H, SF 6 , and 14 C concentrations, indicate that water in that sample recharged prior to shale-gas development, suggesting that land-surface releases associated with shale-gas production were not the source of those hydrocarbons, although subsurface leakage from a nearby gas well directly into the groundwater cannot be ruled out. Age distributions in the samples span ∼20 to >10000 years and have implications for relating occurrences of hydrocarbons in groundwater to land-surface releases associated with recent shale-gas production and for the time required to flush contaminants from the system.

New York, Pennsylvania↗

USGS2019

Rate of magma supply beneath Mammoth Mountain, California based on helium isotopes and CO2 emissions

Mammoth Mountain, California, has exhibited unrest over the past ~30 years, characterized by seismicity over a broad range of depths, elevated 3 He/ 4 He ratios in fumarolic gas, and large-scale diffuse CO 2 emissions. This activity has been attributed to magmatic intrusion, but minimal ground deformation and the presence of a shallow crustal gas reservoir beneath Mammoth Mountain pose a challenge for estimating magma supply rate. Here, we use the record of fumarolic 3 He/ 4 He ratios and CO 2 emissions to estimate that of the ~5.2 Mt of CO 2 released from Mammoth Mountain between 1989 and 2016, 1.6 Mt was associated with active intrusion and degassing of ~0.05–0.07 km 3 of basaltic magma. Intrusion at an average rate of ~0.002–0.003 km 3 /year into a postulated zone of partial melt at ~15-km depth could occur without detection by local Global Navigation Satellite System stations.

California↗

USGS2018

Geochemical characterization and modeling of regional groundwater contributing to the Verde River, Arizona between Mormon Pocket and the USGS Clarkdale gage

We use synoptic surveys of stream discharge, stable isotopes, and dissolved noble gases to identify the source of groundwater discharge to the Verde River in central Arizona. The Verde River more than doubles in discharge in Mormon Pocket over a 1.4 km distance that includes three discrete locations of visible spring input to the river and other diffuse groundwater inputs. A detailed study of the Verde River between Mormon Pocket and the USGS Clarkdale Gage was conducted to better constrain the location of groundwater inputs, the geochemical signature and constrain the source of groundwater input. Discharge, water quality parameters (temperature, pH, specific conductance, and dissolved oxygen), stable isotopes (δ18O and δ2H), noble gases (He, Ne, Ar, Kr and Xe), and radon (222Rn) from river water were collected. Groundwater samples from springs and wells in the area were collected and analyzed for tracers measured in the stream along with some additional analytes (major ions, strontium isotopes (87Sr/86Sr), carbon-14, δ13C, and tritium). Groundwater isotopic signature is consistent with a regional groundwater source. Groundwater springs discharging to the river have a depleted stable isotopic signature indicating recharge source up to 1000 m higher than the discharge location in the Verde River and are significantly fresher than stream water. Spring water has a radiocarbon age of several thousand years and some areas have tritium less than the laboratory reporting level or low concentrations of tritium (1.5 TU). The strontium isotopes indicate groundwater interaction with tertiary volcanic rock and Paleozoic sedimentary rocks. Along the study reach with distance downstream, Verde stream water chemistry shows increased 222Rn, freshening, increased 4He, and isotopic depletion with distance downstream. We estimated total groundwater discharge by inverting a stream transport model against 222Rn and discharge measured in the stream. The salinity, 4He, and stable isotope composition of discharging groundwater was then estimated by fitting modeled values to observed in-stream values. Estimated groundwater inflow to the stream was well within the ranges observed in springs, indicating that the main source of streamflow is deep, regional groundwater. These results show that synoptic surveys of environmental tracers in streams can be used to estimate the isotopic composition and constrain the source of groundwater discharging to streams. Our data provide direct field evidence that deep, regional groundwater discharge can be a significant source of streamflow generation in arid, topographically complex watersheds.

Arizona↗

USGS2018

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 ~125 m below the zone of contamination was an effective barrier to upward migration of water and gas. The gas well, located 27 m from the contaminated monitoring well, had ~1000 m 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 20 mg/L) were above air-saturation levels. Methane degassing from the water table was likely oxidized in the relatively thick unsaturated zone (~18 m), 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.

Colorado↗

USGS2017

Methane and benzene in drinking-water wells overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas

Water wells ( n = 116) overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas were sampled for chemical, isotopic, and groundwater-age tracers to investigate the occurrence and sources of selected hydrocarbons in groundwater. Methane isotopes and hydrocarbon gas compositions indicate most of the methane in the wells was biogenic and produced by the CO 2 reduction pathway, not from thermogenic shale gas. Two samples contained methane from the fermentation pathway that could be associated with hydrocarbon degradation based on their co-occurrence with hydrocarbons such as ethylbenzene and butane. Benzene was detected at low concentrations (<0.15 μg/L), but relatively high frequencies (2.4–13.3% of samples), in the study areas. Eight of nine samples containing benzene had groundwater ages >2500 years, indicating the benzene was from subsurface sources such as natural hydrocarbon migration or leaking hydrocarbon wells. One sample contained benzene that could be from a surface release associated with hydrocarbon production activities based on its age (10 ± 2.4 years) and proximity to hydrocarbon wells. Groundwater travel times inferred from the age-data indicate decades or longer may be needed to fully assess the effects of potential subsurface and surface releases of hydrocarbons on the wells.

Environmental Science & Technology↗

USGS2017

Noble gas isotopes in mineral springs and wells within the Cascadia forearc, Washington, Oregon, and California

Introduction This U.S. Geological Survey report presents laboratory analyses along with field notes for an exploratory study to document the relative abundance of noble gases in mineral springs and water wells within the Cascadia forearc of Washington, Oregon, and California (fig. 1). This report describes 14 samples collected in 2014 and 2015 and complements a previous report that describes 9 samples collected in 2012 and 2013 (McCrory and others, 2014b). Estimates of the depth to the underlying Juan de Fuca oceanic plate beneath sample sites are derived from the McCrory and others (2012) slab model. Some of the springs have been previously sampled for chemical analyses (Mariner and others, 2006), but none of the springs or wells currently has publicly available noble gas data. The helium and neon isotope values and ratios presented below are used to determine the sources and mixing history of these mineral and well waters (for example, McCrory and others, 2016).

California, Oregon, Washington↗

USGS2017

Mantle and crustal gases of the Colorado Plateau: Geochemistry, sources, and migration pathways

The Colorado Plateau hosts several large accumulations of naturally occurring, non-hydrocarbon gases, including CO 2 , N 2 , and the noble gases, making it a good field location to study the fluxes of these gases within the crust and to the atmosphere. In this study, we present a compilation of 1252 published gas-composition measurements. The data reveal at least three natural gas associations in the field area, which are dominated by hydrocarbons, CO 2, and N 2 + He + Ar, respectively. Most gas accumulations of the region exhibit compositions that are intermediate between the three end members. The first non-hydrocarbon gas association is characterized by very high-purity CO 2 , in excess of 75 mol% (hereafter, %). Many of these high-purity CO 2 fields have recently been well described and interpreted as magmatic in origin. The second non-hydrocarbon gas association is less well described on the Colorado Plateau. It exhibits He concentrations on the order of 1–10%, and centered log ratio biplots show that He occurs proportionally to both N 2 and Ar. Overall ratios of N 2 to He to Ar are ≈100:10:1 and correlation in concentrations of these gases suggests that they have been sourced from the same reservoir and/or by a common process. To complement the analysis of the gas-composition data, stable isotope and noble-gas isotope measurements are compiled or newly reported from 11 representative fields (previously published data from 4 fields and new data from 7 fields). Gas sampled from the Harley Dome gas field in Utah contains nearly pure N 2 + He + Ar. The various compositional and stable and noble gas isotopic data for this gas indicate that noble gas molecule/isotope ratios are near crustal radiogenic production values and also suggest a crustal N 2 source. Across the field area, most of the high-purity N 2 + He + Ar gas accumulations are associated with the mapped surface trace of structures or sutures in the Precambrian basement and are often accumulated in lower parts of the overlying Phanerozoic sedimentary cover. The high-purity gas association mostly occurs in areas interior to the plateau that are characterized by a narrow range of elevated, moderate heat flow values (53–74 mW/m 2 ) in the ancient (1.8–1.6 Ga) basement terranes of the region. Collectively, the geochemical and geological data suggest that (1) the N 2 + He + Ar gas association is sourced from a crustal reservoir, (2) the gas association migrates preferentially along structures in the Precambrian basement, and (3) the sourcing process relates to heating of the crust. Prospecting for noble-gas accumulations may target areas with elevated Cenozoic heat flow, ancient crust, and deep crustal structures that focus gas migration. High-purity CO 2 gas may also migrate through regional basement structures, however, there is not always a clear spatial association. Rather, CO 2 accumulations are more clearly associated with zones of high heat flow (>63 mW/m 2 ) that sit above hot upper mantle and are proximal to Cenozoic volcanic rocksnear the plateau margins. These observations are consistent with previous interpretations of a magmatic gas source, which were based on geochemical measurements.

Colorado Plateau↗

USGS2017

Evidence for degassing of fresh magma during the 2004-2008 eruption of Mount St. Helens: Subtle signals from the hydrothermal system

Results from chemical and isotopic analyses of water and gas collected between 2002 and 2016 from sites on and around Mount St. Helens are used to assess magmatic degassing related to the 2004-2008 eruption. During 2005 the chemistry of hot springs in The Breach of Mount St. Helens showed no obvious response to the eruption, and over the next few years, changes were subtle, giving only slight indications of perturbations in the system. By 2010 however, water chemistry, temperatures, and isotope compositions (δD and δ 18 O) clearly indicated some inputs of volatiles and heat associated with the eruption, but the changes were such that they could be attributed to a pre-existing, gas depleted magma. An increase of ~ 1.5‰ in the δ 13 C values of dissolved carbon in the springs was noted in 2006 and continued through 2009, a change that was mirrored by a similar shift in δ 13 C-CO 2 in bubble gas emissions. These changes require input of a new source of carbon to the hydrothermal system and provide clear evidence of CO 2 from an undegassed body of magma. Rising trends in 3 He/ 4 He ratios in gas also accompanied the increases in δ 13 C. Since 2011 maximum R C /R A values are ≥ 6.4 and are distinctly higher than 5 samples collected between 1986 and 2002, and provide additional evidence for some involvement of new magma as early as 2006, and possibly earlier, given the unknown time needed for CO 2 and He to traverse the system and arrive at the springs.

Washington↗

USGS2016

Mineral thermometry and fluid inclusion studies of the Pea Ridge iron oxide-apatite–rare earth element deposit, Mesoproterozoic St. Francois Mountains Terrane, southeast Missouri, USA

Mineral thermometry and fluid inclusion studies were conducted on variably altered and mineralized samples from the Mesoproterozoic Pea Ridge iron oxide-apatite (IOA)-rare earth element (REE) deposit in order to constrain P-T conditions, fluid chemistry, and the source of salt and volatiles during early magnetite and later REE mineralization. Scanning electron microscopy (SEM)-cathodoluminescence and SEM-backscatter electron images show that quartz and rutile precipitated before, during, and after magnetite and REE mineral growth. Ti-in-quartz and Zr-in-rutile equilibration temperatures range from ≤350° to 750°C in the amphibole, magnetite, hematite, and silicified zones where T increased during magnetite and quartz growth and dropped precipitously after fracturing and brecciation. Late drusy quartz cements within a REE-rich breccia pipe record the lowest T (≤315°–400°C). Liquid-, vapor-rich, and hypersaline (±hematite, calcite) fluid inclusions are common and liquid CO 2 is present locally. Salinities define three populations: saline (10–27 wt % NaCl equiv), hypersaline (34–>60 wt % NaCl equiv), and dilute (0–10 wt % NaCl equiv ). The wide range of eutectic melting temperatures (−67° to −19°C) suggests that saline inclusions trapped variable proportions of a CaCl-MgCl-FeCl-bearing fluid end member and an NaCl-KCl fluid end member. Homogenization temperatures and pressures of these saline inclusions suggest they were trapped when fluids unmixed into brine and vapor at T <350°C, P <15 MPa, and a depth of ~1.5 km. Hypersaline inclusions were trapped at low T and P (~200°C and ~1 MPa) along the V + L + H curve when the system vented to the paleosurface. Data for dilute inclusions in late drusy quartz from the REE-rich breccia pipe are indicative of a boiling epithermal environment. The Na/Cl, Na/K, and Cl/Br ratios of fluid inclusion extracts provide evidence for mixtures of magmatic hydrothermal fluids and evaporated seawater. Extracts from magnetite, hematite, and pyrite plot in the magmatic-hydrothermal field, indicating that Fe was derived from a magmatic source. Their enrichments in Mg and Ca are consistent with a mafic magmatic source. The positive correlation between Na/Mg and Na/Ca ratios may be due to halite saturation or albitization of igneous rocks. Extracts from barite in the REE-rich breccia pipes are enriched in Na and Br and plot near the seawater evaporation trend. He is highly enriched relative to Ne and Ar in fluid inclusion extracts, which precludes air as a source of He. Although the He is mostly of crustal origin, pyrite with a 3 He/ 4 He (R/R A ) of 0.1 contains up to 12% mantle He. Many extracts have low 20 Ne/ 22 Ne ratios due to nucleogenic production of 22 Ne in high F/O minerals such as fluorapatite or F biotite. The arrays of data for 3 He/ 4 He (R/R A ) and 22 Ne/ 20 Ne suggest that volatiles were derived from two sources, a moderate F mafic magma containing mantle He and a high F silicic magma with crustal He. Together with other evidence cited in this report, these data (1) support a magmatic hydrothermal origin for the Mesoproterozoic magnetite-apatite deposit with ore fluids derived from a concealed mafic to intermediate-composition intrusion, (2) suggest that the REE minerals in breccia pipes were either derived from apatite or precipitated in response to decompression and cooling during breccia pipe formation, (3) provide evidence for the influx of basinal brine, magmatic fluids from granitic intrusions, and meteoric water after breccia pipe formation, and (4) show that Pea Ridge was relatively unaffected by the late Paleozoic Mississippi Valley-type (MVT) Pb-Zn system in overlying Cambrian sedimentary rocks.

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