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Per- and polyfluoroalkyl substances in waters associated with oil and gas development in the Denver Basin

Use of per- and polyfluoroalkyl substances (PFAS) in the petroleum industry could be a cause for concern due to the large volumes of produced water (PW) generated during oil and gas extraction, the reuse of these wastes in water-stressed regions, and adverse health outcomes related to PFAS exposures. However, PW PFAS characterization is nearly absent in the literature, and hydraulic fracturing (HF) chemical disclosures often omit the identities of additives as proprietary. Here we evaluate PFAS in PW samples from three petroleum wells in the Denver Basin during their first year of production. Total concentrations of targeted PFAS (Σ 40 PFAS) were < 35 ng/L in PW samples, with short-chain PFAS like perfluorobutanoic acid persisting throughout the sampled duration. Analysis of freshwater inputs for hydraulic fracturing (Σ 40 PFAS ~ 113 ng/L) and mixed fracture fluid (Σ 40 PFAS ~ 69 ng/L) indicated much of the targeted PFAS content was derived from the input water, and not from HF additives, however samples subjected to oxidation indicated the presence of PFAS precursors that would not be detected by targeted analysis. This study highlights that while PFAS content is low in the studied PWs, the potential for redistribution of PFAS in the environment may be a consideration for reuse applications.

Colorado, Nebraska, Wyoming↗

Tectonic influence on axial-transverse sediment routing in the Denver Basin

Detrital zircon U-Pb and (U-Th)/He ages from latest Cretaceous–Eocene strata of the Denver Basin provide novel insights into evolving sediment sourcing, recycling, and dispersal patterns during deposition in an intracontinental foreland basin. In total, 2464 U-Pb and 78 (U-Th)/He analyses of detrital zircons from 21 sandstone samples are presented from outcrop and drill core in the proximal and distal portions of the Denver Basin. Upper Cretaceous samples that predate uplift of the southern Front Range during the Laramide orogeny (Pierre Shale, Fox Hills Sandstone, and Laramie Formation) contain prominent Late Cretaceous (84–77 Ma), Jurassic (169–163 Ma), and Proterozoic (1.69–1.68 Ga) U-Pb ages, along with less abundant Paleozoic through Archean zircon grain ages. These grain ages are consistent with sources in the western U.S. Cordillera, including the Mesozoic Cordilleran magmatic arc and Yavapai-Mazatzal basement, with lesser contributions of Grenville and Appalachian zircon recycled from older sedimentary sequences. Mesozoic zircon (U-Th)/He ages confirm Cordilleran sources and/or recycling from the Sevier orogenic hinterland. Five of the 11 samples from syn-Laramide basin fill (latest Cretaceous–Paleocene D1 Sequence) and all five samples from the overlying Eocene D2 Sequence are dominated by 1.1–1.05 Ga zircon ages that are interpreted to reflect local derivation from the ca. 1.1 Ga Pikes Peak batholith. Corresponding late Mesoproterozoic to early Neoproterozoic zircon (U-Th)/He ages are consistent with local sourcing from the southern Front Range that underwent limited Mesozoic–Cenozoic unroofing. The other six samples from the D1 Sequence yielded detrital zircon U-Pb ages similar to pre-Laramide units, with major U-Pb age peaks at ca. 1.7 and 1.4 Ga but lacking the 1.1 Ga age peak found in the other syn-Laramide samples. One of these samples yielded abundant Mesozoic and Paleozoic (U-Th)/He ages, including prominent Early and Late Cretaceous peaks. We propose that fill of the Denver Basin represents the interplay between locally derived sediment delivered by transverse drainages that emanated from the southern Front Range and a previously unrecognized, possibly extraregional, axial-fluvial system. Transverse alluvial-fluvial fans, preserved in proximal basin fill, record progressive unroofing of southern Front Range basement during D1 and D2 Sequence deposition. Deposits of the upper and lower D1 Sequence across the basin were derived from these fans that emanated from the southern Front Range. However, the finer-grained, middle portion of the D1 Sequence that spans the Cretaceous-Paleogene boundary was deposited by both transverse (proximal basin fill) and axial (distal basin fill) fluvial systems that exhibit contrasting provenance signatures. Although both tectonic and climatic controls likely influenced the stratigraphic development of the Denver Basin, the migration of locally derived fans toward and then away from the thrust front suggests that uplift of the southern Front Range may have peaked at approximately the Cretaceous-Paleogene boundary.

Colorado↗

Geologic framework for the national assessment of carbon dioxide storage resources: Denver Basin, Colorado, Wyoming, and Nebraska

This is a report about the geologic characteristics of five storage assessment units (SAUs) within the Denver Basin of Colorado, Wyoming, and Nebraska. These SAUs are Cretaceous in age and include (1) the Plainview and Lytle Formations, (2) the Muddy Sandstone, (3) the Greenhorn Limestone, (4) the Niobrara Formation and Codell Sandstone, and (5) the Terry and Hygiene Sandstone Members. The described characteristics, as specified in the methodology, affect the potential carbon dioxide storage resource in the SAUs. The specific geologic and petrophysical properties of interest include depth to the top of the storage formation, average thickness, net-porous thickness, porosity, permeability, groundwater quality, and the area of structural reservoir traps. Descriptions of the SAU boundaries and the overlying sealing units are also included. Assessment results are not contained in this report; however, the geologic information included here will be used to calculate a statistical Monte Carlo-based distribution of potential storage volume in the SAUs.

Colorado, Nebraska, Wyoming↗

Geologic sources and concentrations of selenium in the West-Central Denver Basin, including the Toll Gate Creek watershed, Aurora, Colorado, 2003-2007

Toll Gate Creek, in the west-central part of the Denver Basin, is a perennial stream in which concentrations of dissolved selenium have consistently exceeded the Colorado aquatic-life standard of 4.6 micrograms per liter. Recent studies of selenium in Toll Gate Creek identified the Denver lignite zone of the non-marine Cretaceous to Tertiary-aged (Paleocene) Denver Formation underlying the watershed as the geologic source of dissolved selenium to shallow ground-water and surface water. Previous work led to this study by the U.S. Geological Survey, in cooperation with the City of Aurora Utilities Department, which investigated geologic sources of selenium and selenium concentrations in the watershed. This report documents the occurrence of selenium-bearing rocks and groundwater within the Cretaceous- to Tertiary-aged Denver Formation in the west-central part of the Denver Basin, including the Toll Gate Creek watershed. The report presents background information on geochemical processes controlling selenium concentrations in the aquatic environment and possible geologic sources of selenium; the hydrogeologic setting of the watershed; selenium results from groundwater-sampling programs; and chemical analyses of solids samples as evidence that weathering of the Denver Formation is a geologic source of selenium to groundwater and surface water in the west-central part of the Denver Basin, including Toll Gate Creek. Analyses of water samples collected from 61 water-table wells in 2003 and from 19 water-table wells in 2007 indicate dissolved selenium concentrations in groundwater in the west-central Denver Basin frequently exceeded the Colorado aquatic-life standard and in some locations exceeded the primary drinking-water standard of 50 micrograms per liter. The greatest selenium concentrations were associated with oxidized groundwater samples from wells completed in bedrock materials. Selenium analysis of geologic core samples indicates that total selenium concentrations were greatest in samples containing indications of reducing conditions and organic matter (dark gray to black claystones and lignite horizons). The Toll Gate Creek watershed is situated in a unique hydrogeologic setting in the west-central part of the Denver Basin such that weathering of Cretaceous- to Tertiary-aged, non-marine, selenium-bearing rocks releases selenium to groundwater and surface water under present-day semi-arid environmental conditions. The Denver Formation contains several known and suspected geologic sources of selenium including: (1) lignite deposits; (2) tonstein partings; (3) organic-rich bentonite claystones; (4) salts formed as secondary weathering products; and possibly (5) the Cretaceous-Tertiary boundary. Organically complexed selenium and/or selenium-bearing pyrite in the enclosing claystones are likely the primary mineral sources of selenium in the Denver Formation, and correlations between concentration of dissolved selenium and dissolved organic carbon in groundwater indicate weathering and dissolution of organically complexed selenium from organic-rich claystone is a primary process mobilizing selenium. Secondary salts accumulated along fractures and bedding planes in the weathered zone are another potential geologic source of selenium, although their composition was not specifically addressed by the solids analyses. Results from this and previous work indicate that shallow groundwater and streams similarly positioned over Denver Formation claystone units at other locations in the Denver Basin also may contain concentrations of dissolved selenium greater than the Colorado aquatic-life standard or the drinking- water standard.

Colorado↗

Quality of groundwater in the Denver Basin aquifer system, Colorado, 2003-5

Groundwater resources from alluvial and bedrock aquifers of the Denver Basin are critical for municipal, domestic, and agricultural uses in Colorado along the eastern front of the Rocky Mountains. Rapid and widespread urban development, primarily along the western boundary of the Denver Basin, has approximately doubled the population since about 1970, and much of the population depends on groundwater for water supply. As part of the National Water-Quality Assessment Program, the U.S. Geological Survey conducted groundwater-quality studies during 2003&ndash;5 in the Denver Basin aquifer system to characterize water quality of shallow groundwater at the water table and of the bedrock aquifers, which are important drinking-water resources. For the Denver Basin, water-quality constituents of concern for human health or because they might otherwise limit use of water include total dissolved solids, fluoride, sulfate, nitrate, iron, manganese, selenium, radon, uranium, arsenic, pesticides, and volatile organic compounds. For the water-table studies, two monitoring-well networks were installed and sampled beneath agricultural (31 wells) and urban (29 wells) land uses at or just below the water table in either alluvial material or near-surface bedrock. For the bedrock-aquifer studies, domestic- and municipal-supply wells completed in the bedrock aquifers were sampled. The bedrock aquifers, stratigraphically from youngest (shallowest) to oldest (deepest), are the Dawson, Denver, Arapahoe, and Laramie-Fox Hills aquifers. The extensive dataset collected from wells completed in the bedrock aquifers (79 samples) provides the opportunity to evaluate factors and processes affecting water quality and to establish a baseline that can be used to characterize future changes in groundwater quality. Groundwater samples were analyzed for inorganic, organic, isotopic, and age-dating constituents and tracers. This report discusses spatial and statistical distributions of chemical constituents and evaluates natural and human-related processes that affect water quality. Findings are synthesized to assess the vulnerability of the Denver Basin aquifer system to groundwater contamination. The chemistry of groundwater samples collected from the water-table wells was generally different from that of samples collected from the bedrock-aquifer wells. Samples from the water-table wells tended to have higher concentrations of total dissolved solids and most major ions. Concentrations of several constituents with potential human-health concerns, including nitrate, selenium, uranium, and arsenic, decreased with depth and were highest in samples from the water-table wells. Exceedances of drinking-water standards and water-quality benchmarks were more frequently associated with shallow groundwater samples; concentrations of total dissolved solids and sulfate exceeded water-quality benchmarks for about half or more of samples from the water-table wells. The sediments and rocks of the Denver Basin are natural sources of the trace elements selenium, uranium, and arsenic, which affect their concentrations in groundwater. Detections of organic contaminants, which are typically indicative of human sources of contamination to groundwater, were more frequent in samples from the water-table wells. Pesticide compounds and volatile organic compounds were detected in 33 and 62 percent, respectively, of water-table well samples. Detected organic contaminant concentrations were much less than the associated drinking-water standards. Samples collected from the bedrock aquifers had lower concentrations of total dissolved solids than did samples collected from the water-table wells, although within the bedrock-aquifer samples, concentrations increased from the Dawson to Denver to Arapahoe to Laramie-Fox Hills aquifers. Concentrations of total dissolved solids and many constituents varied spatially and with depth in the bedrock aquifers, likely as a result of ion-exchange and oxidation-reduction reactions, which are important processes affecting water quality. Major-ion chemistry generally evolved from a calcium-bicarbonate to calcium-sulfate composition, with some sodium-bicarbonate and sodium-sulfate facies in the deeper bedrock aquifers, likely resulting from longer residence times and more extensive water-rock interaction. Oxidation-reduction conditions generally evolved from oxic at the water table to anoxic with increasing depth in the bedrock aquifers. Most samples from the bedrock aquifers were anoxic. Exceedances of drinking-water standards and water-quality benchmarks for the bedrock aquifers occurred in 1 percent or less of samples for nitrate, selenium, or arsenic; there were no exceedances for uranium. Exceedances for total dissolved solids, sulfate, manganese, and iron were generally between about 10 and 20 percent for the bedrock-aquifer samples. Radon concentrations, which were only measured in samples collected from two of the bedrock aquifers, exceeded the lower proposed drinking-water standard for more than 90 percent of samples but exceeded the higher alternative standard for less than 5 percent of samples. Pesticide compounds and volatile organic compounds were detected in 3 and 22 percent, respectively, of bedrock-aquifer samples, all at concentrations that were that were much less than drinking-water standards. Water-quality data were synthesized to evaluate factors that affect spatial and depth variability in water quality and to assess aquifer vulnerability to contaminants from geologic materials and those of human origin. The quality of shallow groundwater in the alluvial aquifer and shallow bedrock aquifer system has been adversely affected by development of agricultural and urban areas. Land use has altered the pattern and composition of recharge. Increased recharge from irrigation water has mobilized dissolved constituents and increased concentrations in the shallow groundwater. Concentrations of most constituents associated with poor or degraded water quality in shallow groundwater decreased with depth; many of these constituents are not geochemically conservative and are affected by geochemical reactions such as oxidation-reduction reactions. Groundwater age tracers provide additional insight into aquifer vulnerability and help determine if young groundwater of potentially poor quality has migrated to deeper parts of the bedrock aquifers used for drinking-water supply. Age-tracer results were used to group samples into categories of young, mixed, and old groundwater. Groundwater ages transitioned from mostly young in the water-table wells to mostly mixed in the shallowest bedrock aquifer, the Dawson aquifer, to mostly old in the deeper bedrock aquifers. Although the bedrock aquifers are mostly old groundwater of good water quality, several lines of evidence indicate that young, contaminant-bearing recharge has reached shallow to moderate depths in some areas of the bedrock aquifers. The Dawson aquifer is the most vulnerable of the bedrock aquifers to contamination, but results indicate that the older (deeper) bedrock aquifers are also vulnerable to groundwater contamination and that mixing with young recharge has occurred in some areas. Heavy pumping has caused water-level declines in the bedrock aquifers in some parts of the Denver Basin, which has the potential to enhance the transport of contaminants from overlying units. Results of this study are consistent with the existing conceptual understanding of aquifer processes and groundwater issues in the Denver Basin and add new insight into the vulnerability of the bedrock aquifers to groundwater contamination.

Colorado↗

Demonstration optimization analyses of pumping from selected Arapahoe aquifer municipal wells in the west-central Denver Basin, Colorado, 2010–2109

Declining water levels caused by withdrawals of water from wells in the west-central part of the Denver Basin bedrock-aquifer system have raised concerns with respect to the ability of the aquifer system to sustain production. The Arapahoe aquifer in particular is heavily used in this area. Two optimization analyses were conducted to demonstrate approaches that could be used to evaluate possible future pumping scenarios intended to prolong the productivity of the aquifer and to delay excessive loss of saturated thickness. These analyses were designed as demonstrations only, and were not intended as a comprehensive optimization study. Optimization analyses were based on a groundwater-flow model of the Denver Basin developed as part of a recently published U.S. Geological Survey groundwater-availability study. For each analysis an optimization problem was set up to maximize total withdrawal rate, subject to withdrawal-rate and hydraulic-head constraints, for 119 selected municipal water-supply wells located in 96 model cells. The optimization analyses were based on 50- and 100-year simulations of groundwater withdrawals. The optimized total withdrawal rate for all selected wells for a 50-year simulation time was about 58.8 cubic feet per second. For an analysis in which the simulation time and head-constraint time were extended to 100 years, the optimized total withdrawal rate for all selected wells was about 53.0 cubic feet per second, demonstrating that a reduction in withdrawal rate of about 10 percent may extend the time before the hydraulic-head constraints are violated by 50 years, provided that pumping rates are optimally distributed. Analysis of simulation results showed that initially, the pumping produces water primarily by release of water from storage in the Arapahoe aquifer. However, because confining layers between the Denver and Arapahoe aquifers are thin, in less than 5 years, most of the water removed by managed-flows pumping likely would be supplied by depleting overlying hydrogeologic units, substantially increasing the rate of decline of hydraulic heads in parts of the overlying Denver aquifer.

Colorado↗

Groundwater availability of the Denver Basin aquifer system, Colorado

The Denver Basin aquifer system is a critical water resource for growing municipal, industrial, and domestic uses along the semiarid Front Range urban corridor of Colorado. The confined bedrock aquifer system is located along the eastern edge of the Rocky Mountain Front Range where the mountains meet the Great Plains physiographic province. Continued population growth and the resulting need for additional water supplies in the Denver Basin and throughout the western United States emphasize the need to continually monitor and reassess the availability of groundwater resources. In 2004, the U.S. Geological Survey initiated large-scale regional studies to provide updated groundwater-availability assessments of important principal aquifers across the United States, including the Denver Basin. This study of the Denver Basin aquifer system evaluates the hydrologic effects of continued pumping and documents an updated groundwater flow model useful for appraisal of hydrologic conditions.

Colorado↗

Alluvial and bedrock aquifers of the Denver Basin — Eastern Colorado's dual ground-water resource

Large volumes of ground water are contained in alluvial and bedrock aquifers in the semiarid Denver basin of eastern Colorado. The bedrock aquifer, for example, contains 1.2 times as much water as Lake Erie of the Great Lakes, yet it supplies only about 9 percent of the ground water used in the basin. Although this seems to indicate underutilization of this valuable water supply, this is not necessarily the case, for many factors other than the volume of water in the aquifer affect the use of the aquifer. Such factors as climatic conditions, precipitation runoff, geology and water-yielding character of the aquifers, water-level conditions, volume of recharge and discharge, legal and economic constraints, and water-quality conditions can ultimately affect the decision to use ground water. Knowledge of the function and interaction of the various parts of this hydrologic system is important to the proper management and use of the ground-water resources of the region. The semiarid climatic conditions on the Colorado plains produce flash floods of short duration and large peak-flow rates. However, snowmelt runoff from the Rocky Mountains produces the largest volumes of water and is typically of longer duration with smaller peak-flow rates. The alluvial aquifer is recharged easily from both types of runoff and readily stores and transmits the water because it consists of relatively thin deposits of gravel, sand, and clay located in the valleys of principal streams. The bedrock aquifer is recharged less easily because of its greater thickness (as much as 3,000 feet) and prevalent layers of shale which retard the downward movement of water in the formations. Although the bedrock aquifer contains more than 50 times as much water in storage as the alluvial aquifer, it does not store and transmit water as readily as the alluvial aquifer. For example, about 91 percent of the water pumped from wells is obtained from the alluvial aquifer, yet water-level declines generally have not exceeded 40 feet. By contrast, only 9 percent of the water pumped from wells is obtained from the bedrock aquifer, yet water-level declines in this aquifer have exceeded 500 feet in some areas. Depth to water in the alluvial aquifer generally is less than 40 feet, while depth to water in the bedrock aquifer may exceed 1,000 feet in some areas. Cost of pumping water to the surface and cost of maintaining existing supplies in areas of rapidly declining water levels in the bedrock aquifer affect water use. Water use is also affected by the generally poorer quality water found in the alluvial aquifer and, to a lesser extent, by the greater susceptibility of the alluvial aquifer to pollution from surface sources. Because of these factors, the alluvial aquifer is used primarily as a source of irrigation supply, which is the largest water use in the area. The bedrock aquifer is used primarily as a source of domestic or municipal supply, which is the smaller of the two principal uses, even though the bedrock aquifer contains 50 times more stored ground water than the alluvial aquifer.

Colorado↗

Median-permeability contour maps of the J sandstone, Dakota Group, in the Denver Basin, Colorado, Nebraska, and Wyoming

The Lower Cretaceous J sandstone of the Dakota Group (MacKenzie, 1965) is present in the Denver basin in eastern Colorado, southeastern Wyoming, and southwestern Nebraska. This informally named unit deposited during a regression of the Cretaceous epi continental sea and is composed primarily of sandstone and shale of deItaic and near-shore marine origin. The J sandstone can be divided into an upper transgressive sand, a middle marginal-marine and deltaic facies, and a lower prodelta sequence (Clark, 1978). The depth from the surface to the top of the J sandstone increases from about 4,000 ft on the gently-dipping eastern flank of the bass n to more than 8,000 ft near the steeply-dipping flank at the western boundary. Permeability values compiled in this J sandstone study were determined from cores from 134 widely scattered boreholes. Median permeabilities, rather than average permeabilities, were used in order to minimize the effect of anomalous samples. Thirty-five oil companies and independent operators supplied core data. Core Laboratories of Denver, Colorado analyzed the core, which was submitted over a period of 25 years.

Colorado, Nebraska, Wyoming↗