First posted September 13, 2022 For additional information, contact: Director, Wyoming-Montana Water Science CenterU.S. Geological Survey3162 Bozeman AvenueHelena, MT 59601Contact Pubs Warehouse The Williston Basin has been a leading oil and gas producing area for more than 50 years. While oil production initially peaked within the Williston Basin in the mid-1980s, production rapidly increased in the mid-2000s, largely because of improved horizontal (directional) drilling and hydraulic fracturing methods. In 2012, energy development associated with the Bakken Formation was identified as a priority requiring collaboration toward improved timeliness of issuing permits for new wells combined with reasonable measures to maintain environmental quality. Shortly thereafter, the Bakken Federal Executive Group was created to address common challenges associated with energy development. The Bakken Federal Executive Group partner agencies identified a gap in current understanding of the cumulative environmental challenges attributed to energy development throughout the area, resulting in an effort to aggregate scientific data and identify additional research and information needs related to natural resources within areas of energy development in the Williston Basin. As part of this effort, water resources in the area (including groundwater; streams and rivers; and lakes, reservoirs, and wetlands) were characterized and described in terms of physical occurrence, flow characteristics, recharge, water quality, and water use. Similarly, waters produced during energy-development activities also were characterized even though these waters are not considered usable resources within the area. Groundwater resources were characterized by the major hydrogeologic units, or aquifers, identifying the units that supply most groundwater used for domestic, stock, agricultural, and industrial purposes. The groundwater characterization included other deeper hydrogeologic units in the Williston Basin that may be a useable source of water with treatment, have utility as a reservoir for reinjection of produced waters, or be a source of minerals and energy resources. A generalized groundwater budget and flow system identifying the sources of recharge (stream infiltration, precipitation, and movement [leakage] from other aquifers) and the general groundwater flow direction is included for each of the major hydrogeologic units. Rivers and streams within the Williston Basin with 10 or more years of continuous streamflow data were identified. For a subset of these sites, streamflow characteristics, including the monthly and annual mean flow, were generated to identify seasonal and interannual changes in streamflow and thus provide information on the drivers and reliability of streamflow at the seasonal or multiyear scale. Daily streamflow and annual extreme flows (peak and low flow) also were estimated for the subset of sites. The daily streamflow and annual extreme flow values provide information on short-term or extreme events that are relevant to infrastructure design and evaluating spills, leaks, or accidental discharges of water or petroleum products. Surface-water features (lakes, ponds, and wetlands) were classified using the Cowardin system and identified on the National Wetlands Inventory maps generated by the U.S. Fish and Wildlife Service. The spatial distribution of the surface-water features was analyzed by State, county, and specifically in comparison to the Prairie Pothole Region. The proximity of the surface-water features to energy development infrastructure (specifically oil or gas well pads) was evaluated. It was determined that, although oil or gas wells are often near a surface-water feature, most surface-water features do not have wells nearby, with the exception of wells in the Prairie Pothole Region. Water-quality data were aggregated from two data sources: (1) the Water-Quality Portal, sponsored by the U.S. Geological Survey (USGS), U.S. Environmental Protection Agency (EPA), and National Water Quality Monitoring Council; and (2) a data compilation completed as part of the USGS National Water-Quality Assessment project. The Water-Quality Portal integrates publicly available water-quality data from databases maintained by the USGS, EPA, and U.S. Department of Agriculture, including water-quality data from Tribal, State, and local databases. Water-quality data for 15 commonly measured water-quality constituents were aggregated for groundwater, rivers and streams, and lakes and reservoirs. For each aggregated dataset (groundwater, rivers and streams, and lakes and reservoirs), analyses of the water-quality data included summary statistics, maps of spatial distribution of constituent values, boxplots of constituent values by timeframe or hydrogeologic unit, spatial comparisons of site locations and constituent values to petroleum well density, and comparisons of the constituent values measured to EPA drinking-water standards/guidelines. Produced water includes all fluids brought to the surface along with the targeted hydrocarbons as part of the oil and gas exploration and extraction processes. These fluids may include formation water (waters that co-exist with rock/oil/gas), hydraulic fracturing fluids, and other combinations of water and chemicals used during oil and gas well drilling, development, treatments, recompletions, and workovers. Produced water datasets were aggregated from two sources: the USGS National Produced Waters Geochemical database (ver. 2.1) and a series of projects focused specifically on sampling produced water in the Williston Basin from 2010 to 2014. The National Produced Waters Geochemical database was useful for a general understanding of produced-water chemistry. Produced waters are characterized by extreme salinity and contain elevated concentrations of other constituents (including arsenic, barium, cadmium, lead, zinc, radium-226/radium-228, and ammonia) that could negatively affect water and aquatic resources if released. Produced waters also have a generally unique chemical (isotopic) signature that may be useful in tracking water from different geologic units; for example, the oxygen/deuterium and strontium ratio values measured in brine waters from the Bakken Formation are distinct from brines collected from other geologic units in the Williston Basin.Water-use information related to energy production in the area also was aggregated and summarized. The summary of water use is not limited to oil and gas production but includes water used to produce all types of energy resources in the Williston Basin, including coal/lignite, thermoelectric power, oil and gas, hydropower, biomass and biofuels, wind, geothermal, and solar. Each State has its own methods for regulating and reporting water usage within its jurisdiction. These methods can introduce problems when examining water use from sources, such as the Missouri River or Fox Hills aquifer, that are shared across political boundaries. Without the one-to-one match for usage types and amounts used from a water source, it is difficult to develop a comprehensive water budget for the water source being evaluated. A large amount of freshwater is required to prepare a well for oil and gas well production; in some cases, 3 to 7 million gallons of water are needed per well. The EPA estimates that hydraulic fracturing in the Williston Basin uses between 70 to 140 billion gallons per year. Water also is used for myriad other purposes related to ancillary oil and gas extraction. In addition to water used for immediate energy development, the expanded human workforce migrating into the area and other support staff who have moved into the area during the development also use water.Research and information needs were identified that could be relevant in the evaluation of the effects of energy development on water resources. Information needs related to the evaluation of groundwater resources include the following: improved potentiometric-surface maps for glacial units; availability of a uniform stream network digital geographic coverage that spans the international boundary with Canada; enhanced surface-water use information with regards to the gain and loss of streamflow to shallow groundwater, which would increase understanding groundwater and surface-water interactions; and expanded geophysical assessments. Gaps in the availability of streamflow data include the lack of information on ice-jam flooding despite potential for effects to infrastructure (pipelines, roads, and facilities) and an understanding of the cumulative effects of largely undocumented stock and diversion dams. Although this study resulted in the aggregation of a large quantity of water-quality data, the availability of consistently collected, systematically processed and reported data over large parts of the Williston Basin is sparse. Few samples have been analyzed for constituents that may indicate the effect of energy development on water resources. Constituents that could be considered include boron, chloride, bromide, iodine, fluoride, manganese, lithium, radium, strontium isotopes, volatile organic compounds, and isotopes of inorganic ions (such as hydrogen and carbon). Collaboration between Tribal, Federal, State, and local entities to identify a common study design, common monitoring constituents, and consistent sampling locations would generate datasets with broad utility and would likely result in overall cost savings for monitoring over time. Similarly, there is a need for standardized sample collection, processing, laboratory analytical methods, and the collection of ancillary data for produced waters sampling. Additional characterization of the range of chemical, microbial, and isotopic compositions and quantities of “end-member” produced waters, and the collection of time-series datasets to document the changes in produced waters during and after well development also were needs identified during this study. Water-use estimates would be improved through the implementation of comprehensive studies of water use from groundwater and surface-water sources using consistent methodologies across the Williston Basin. The submission of chemical and water data related to hydraulic fracturing collected by the oil and gas industry would add to the quantity of available data. Consistent implementation of regulations and monitoring controls across political boundaries (State, county, and international) would further improve the consistency of data available for the estimates of water use.

Core samples of the Topopah Spring Member of the Paintbrush Tuff from drill hole UE25A#1 were analyzed for Sr and Nd isotopes and selected minor and trace elements to constrain the origin of a zcolitized zone associated with the lower vitrophyre. The Sm-Nd radiogenic isotope system was unperturbed by the alteration, but the Rb-Sr system was severely disturbed in the altered zone. The thick, densely welded high-silica rhyolite is remarkably uniform in composition with only a slight decrease in initial 87Sr/86Sr ratios with depth (0.7129–0.7125). Quartz latite in the upper part of the Topopah Spring has significantly lower initial Sr isotope ratios (0.7095–0.7114). Locally in the altered zone, Sr and Ca were gained in substantial amounts, and K, Rb, and Y were removed. Ti, Zr, Nb, Ba, La, Ce, Sm, and Nd were relatively immobile during the alteration. Sr added to the altered zone had an isotopic composition of 0.7119 ± 0.0002 and was probably derived from dissolution of glass in the bulk Topopah Spring (high silica rhyolite + quartz latite) and transported downward by infiltration.

Samples of Bakken Formation core from the Fleckton 1-20 well in Ward County, North Dakota, were analyzed using the Strontium Residual Salt Analysis (SrRSA) method to assess pore-water communication among the upper, middle, and lower sections of the unit by analyzing 87Sr/86Sr in pore-water salts leached from the core. Major and trace element analyses were also conducted on bulk-rock samples and leachates (Elemental Residual Salt Analysis or ERSA). The middle part of the Bakken Formation, a calcareous and dolomitic siltstone to fine sandstone, is encased between two black shales—the upper and lower sections of the formation. These units are informal and herein named the upper, middle, and lower Bakken members. Strontium isotope measurements and concentration of some solutes in leachates indicate that pore water in the black shale of the upper Bakken member has remained isolated from pore water in the middle Bakken member except for within a few feet immediately near the contact where elemental profiles indicate diffusive mixing. The SrRSA 87Sr/86Sr values from the middle Bakken member are consistent with produced water collected from 28 wells in Montana and North Dakota. In contrast to the similarity in 87Sr/86Sr values, ratios of concentrations such as K/Rb, Ca/Sr, Ca/Mg, and Na/Cl are slightly different between the pore-water leachates and produced water values. The differences in K/Rb and Ca/Sr are probably due to selective adsorption of Rb leading to larger K/Rb ratios and minor dissolution of carbonate minerals leading to larger Ca/Sr ratios in the leachates.

Brine (also referred to as ‘produced water’) samples were collected from 28 wells producing oil from the Late Devonian-Early Mississippian Bakken and Three Forks Formations in the Williston Basin of eastern Montana and western North Dakota. The samples were analyzed for major ions, trace metals, stable isotopes, and strontium isotopes. The brines in these formations are highly saline with total dissolved solids averaging 308 g/L, almost ten times the salinity of modern seawater. Relative to modern seawater, the brines are enriched approximately 10 to 20 times in [Na], [K], [Cl], and [Br]. Greater enrichments of 100 to 400 times in [Li], [B], [Sr] and [Rb], and 2,000 to 10,000 times in [Cs] and [Ba] are probably due to water-rock interaction (WRI). WRI is further indicated by 87Sr/86Sr values typically between 0.710 and 0.711—considerably larger than marine values of 0.7081 to 0.7083 during this depositional interval. Bakken Formation sediments were deposited in a stratified water column with salinity increasing with depth. The deeper water may have been saturated in calcium carbonate and possibly gypsum, but there is no evidence that halite saturation had been attained. Therefore, brines may have been introduced into the Bakken Formation from the underlying Devonian Prairie Formation or from the overlying Charles Formation before these brines were diluted or replaced by meteoric water. Alternatively, salinity of the native pore water was increased by membrane filtration driven by overpressuring within the Bakken Formation.

As part of a feasibility study under the Nuclear Legacy Liabilities Program, the geochemistry of the crystalline bedrock at the Chalk River Laboratories site has been investigated to examine the suitability of the bedrock to host a potential deep geologic repository, termed a Geologic Waste Management Facility, for the long-term management of intermediate-level radioactive wastes for Canadian Nuclear Laboratories, formerly Atomic Energy of Canada Limited. Characterization of the groundwater and fracture-filling minerals are important considerations in assessing how the geochemical environment would affect the performance and safety of such a facility. Regional groundwater chemistry at the site has evolved over time by groundwater mixing and by rock-water interactions. Collaborative studies with the University of Waterloo and the United States Geological Survey have provided data for whole-rock, fracture minerals, and groundwater isotope systematics. The sampled groundwaters appear in general to be geologically recent in age (i.e., similar to 10 000 years) and tend to be more dilute than Canadian Shield groundwaters at similar depths from other locations. Models of groundwater evolution at the site are suggestive of mixing relationships that include significant contributions from geologically recent meteoric and postglacial melt waters.

Brine samples were collected from 30 conventional oil wells producing mostly from the Charles Formation of the Madison Group in the East and Northwest Poplar oil fields on the Fort Peck Indian Reservation, Montana. Dissolved concentrations of major ions, trace metals, Sr isotopes, and stable isotopes (oxygen and hydrogen) were analyzed to compare with a brine contaminant that affected groundwater northeast of the town of Poplar. Two groups of brine compositions, designated group I and group II, are identified on the basis of chemistry and Sr-87/Sr-86 ratios. The solute chemistry and Sr isotopic composition of group I brines are consistent with long-term residency in Mississippian carbonate rocks, and brines similar to these contaminated the groundwater. Group II brines probably resided in clastic rocks younger than the Mississippian limestones before moving into the Poplar dome to replenish the long-term fluid extraction from the Charles Formation. Collapse of strata at the crest of the Poplar dome resulting from dissolution of Charles salt in the early Paleogene probably developed pathways for the ingress of group II brines from overlying clastic aquifers into the Charles reservoir. Such changes in brine chemistry associated with long-term oil production may be a widespread phenomenon in the Williston Basin.

Integrated isotopic and hydrochemical studies of groundwater at Äspö, Sweden, support mixing models involving deep saline water, low‐solute infiltration, and Baltic Sea water. Carbon, oxygen, and strontium isotope analyses of calcite fracture fillings indicate that paleohydrologic conditions were different than those of today in terms of the isotopic composition of water flowing through fractures. Sr isotopes of whole‐rock and mineral (plagioclase, microcline, biotite, and epidote) samples are used to assess the effects of water‐rock interaction. Biotite is a major reactant in the early stages of water‐rock interaction. Strontium isotope systematics of groundwater from deep in the Hard Rock Laboratory, and underground research facility, and from low conductivity zones revealed a first order mixing line defined by a high‐chloride saline component with 66 mg/L Sr and an ancient sea water component with approximately 4.5 mg/L. Dilution with low salinity recharge has produced groundwater with variable Sr contents and 87Sr/86Sr values between 0.7186 and 0.7160. Differences between Äspö and Laxemar groundwater are shown by trends in Sr concentrations plotted against 87Sr/86Sr. The Äspö trend shows increasing 87Sr/86Sr values with increasing concentrations of Sr, whereas the Laxemar groundwater trend shows little variability in 87Sr/86Sr with increasing Sr concentrations. These trends are controlled by the differences in 87Sr/86Sr composition of the saline end members in the two areas.

This paper presents results of hydrochemical and isotopic analyses of groundwater (fracture water) and porewater, and physical property and water content measurements of bedrock core at the Chalk River Laboratories (CRL) site in Ontario. Density and water contents were determined and water-loss porosity values were calculated for core samples. Average and standard deviations of density and water-loss porosity of 50 core samples from four boreholes are 2.73 +/- 12 g/cc and 1.32 +/- 1.24 percent. Respective median values are 2.68 and 0.83 indicating a positive skewness in the distributions. Groundwater samples from four deep boreholes were analyzed for strontium (Sr-87/Sr-86) and uranium (U-234/U-238) isotope ratios. Oxygen and hydrogen isotope analyses and selected solute concentrations determined by CRL are included for comparison. Groundwater from borehole CRG-1 in a zone between approximately +60 and -240 m elevation is relatively depleted in delta O-18 and delta H-2 perhaps reflecting a slug of water recharged during colder climatic conditions. Porewater was extracted from core samples by centrifugation and analyzed for major dissolved ions and for strontium and uranium isotopes. On average, the extracted water contains 15 times larger concentration of solutes than the groundwater. U-234/U-238 and correlation of Sr-87/Sr-86 with Rb/Sr values indicate that the porewater may be substantially older than the groundwater. Results of this study show that the Precambrian gneisses at Chalk River are similar in physical properties and hydrochemical aspects to crystalline rocks being considered for the construction of nuclear waste repositories in other regions. Published by Elsevier Ltd.

The Williston Basin, which includes parts of Montana, North Dakota, and South Dakota in the United States and the provinces of Manitoba and Saskatchewan in Canada, has been a leading domestic oil and gas producing region for more than one-half a century. Currently, there are renewed efforts to develop oil and gas resources from deep geologic formations, spurred by advances in recovery technologies and economic incentives associated with the price of oil. Domestic oil and gas production has many economic benefits and provides a means for the United States to fulfill a part of domestic energy demands; however, environmental hazards can be associated with this type of energy production in the Williston Basin, particularly to aquatic resources (surface water and shallow groundwater) by extremely saline water, or brine, which is produced with oil and gas. The primary source of concern is the migration of brine from buried reserve pits that were used to store produced water during recovery operations; however, there also are considerable risks of brine release from pipeline failures, poor infrastructure construction, and flow-back water from hydraulic fracturing associated with modern oilfield operations. During 2008, a multidisciplinary (biology, geology, water) team of U.S. Geological Survey researchers was assembled to investigate potential energy production effects in the Williston Basin. Researchers from the U.S. Geological Survey participated in field tours and met with representatives from county, State, tribal, and Federal agencies to identify information needs and focus research objectives. Common questions from agency personnel, especially those from the U.S. Fish and Wildlife Service, were "are the brine plumes (plumes of brine-contaminated groundwater) from abandoned oil wells affecting wetlands on Waterfowl Production Areas and National Wildlife Refuges?" and "are newer wells related to Bakken and Three Forks development different than the older, abandoned wells (in terms of potential for affecting aquatic resources)?" Of special concern were the wetland habitats of the ecologically important Prairie Pothole Region, which overlays a part of the Williston Basin and is recognized for the production of a majority of North America's migratory waterfowl. On the basis of the concerns raised by on-the-ground land managers, as well as findings from previous research, a comprehensive study was developed with the following goals: summarize existing information pertaining to oil and gas production and aquatic resources in the Williston Basin; assess brine plume migration from new and previously studied sites in the Prairie Pothole Region; perform a regional, spatial evaluation of oil and gas production activities and aquatic resources; assess the potential for brine contamination to wetlands and streams; and hold a decision analysis workshop with key stakeholders to discuss issues pertaining to oil and gas production and environmental effects and to identify information gaps and research needs. This report represents an initial, multidisciplinary evaluation of measured and potential environmental effects associated with oil and gas production in the Williston Basin and Prairie Pothole Region. Throughout this report there are reviews of current knowledge, and discussions relating to data gaps and research needs. On the basis of the information presented, future research needs include: regional geophysical and water-quality assessments to establish baselines for current conditions and estimate the extent of previous brine contamination, investigations into the direct effects of brine to biotic communities, and evaluations to identify the most effective techniques to mitigate brine contamination.

This chapter contains sections titled: Introduction Description of Deposits Experimental Methods Results Discussion Conclusions

As part of the Geologic Waste Management Facility feasibility study, Atomic Energy of Canada Ltd. (AECL) is evaluating the suitability of the Chalk River Laboratories (CRL) site in Ontario, situated in crystalline rock of the southwestern Grenville Province, for the possible development of an underground repository for low-and intermediate-level nuclear waste. This paper presents petrographic and trace element analyses, U-Pb zircon dating results, and Rb-Sr, U-Pb and U-series isotopic analyses of gneissic drill core samples from the deep CRG-series characterization boreholes at the CRL site. The main rock types intersected in the boreholes include hornblende-biotite (+/- pyroxene) gneisses of granitic to granodioritic composition, leucocratic granitic gneisses with sparse mafic minerals, and garnet-bearing gneisses with variable amounts of biotite and/or hornblende. The trace element data for whole-rock samples plot in the fields of within-plate, syn-collision, and volcanic arc-type granites in discrimination diagrams used for the tectonic interpretation of granitic rocks.Zircons separated from biotite gneiss and metagranite samples yielded SHRIMP-RG U-Pb ages of 1472 +/- 14 (2 sigma) and 1045 +/- 6 Ma, respectively, in very good agreement with widespread Early Mesoproterozoic plutonic ages and Ottawan orogeny ages in the Central Gneiss Belt. The Rb-Sr, U-Pb, and Pb-Pb whole-rock errorchron apparent ages of most of the CRL gneiss samples are consistent with zircon U-Pb age and do not indicate substantial large-scale preferential element mobility during superimposed metamorphic and water/rock interaction processes. This may confirm the integrity of the rock mass, which is a positive attribute for a potential nuclear waste repository. Most U-234/U-238 activity ratios (AR) in whole rock samples are within errors of the secular equilibrium value of one, indicating that the rocks have not experienced any appreciable U loss or gain within the past 1 Ma. However, U-234/U-238 AR in fracture mineral samples collected down to borehole lengths of about 740 m deviate from the secular equilibrium value and U-234/U-238 model ages calculated for fracture mineral samples showing excess U-234 range from 593 to 1415 ka, thus providing evidence of fracture flow in the associated bedrock during the past 1.5 Ma. Rare earth element patterns are variable in fracture-filling calcites and Fe oxides/hydroxides but are similar to those observed in associated whole-rock samples. The observed Ce anomalies are very small (Ce-N/Ce-N(psi) approximate to 1), do not vary with depth, and, therefore, do not contain evidence that the studied fracture minerals precipitated from oxidizing waters at the conceptual depth of a repository. Published by Elsevier Ltd.

Groundwater, surface water, and soil in the Goose Lake oil field in northeastern Montana have been affected by Cl -rich oil-field brines during long-term petroleum production. Ongoing multidisciplinary geochemical and geophysical studies have identified the degree and local extent of interaction between brine and groundwater. Fourteen samples representing groundwater, surface water, and brine were collected for Sr isotope analyses to evaluate the usefulness of Sr-87/Sr-86 in detecting small amounts of brine. Differences in Sr concentrations and Sr-87/Sr-86 are optimal at this site for the experiment. Strontium concentrations range from 0.13 to 36.9 mg/L, and corresponding Sr-87/Sr-86 values range from 0.71097 to 0.70828. The local brine has 168 mg/L Sr and a Sr-87/Sr-86 value of 0.70802. Mixing relationships are evident in the data set and illustrate the sensitivity of Sr in detecting small amounts of brine in groundwater. The location of data points on a Sr isotope-concentration plot is readily explained by an evaporation-mixing model. The model is supported by the variation in concentrations of most of the other solutes. Published by Elsevier Ltd.

Brine contamination of groundwater in the East Poplar oil field was first documented in the mid-1980s by the U.S. Geological Survey by using hydrochemistry, with an emphasis on chloride (Cl) and total dissolved solids concentrations. Supply wells for the City of Poplar are located downgradient from the oil field, are completed in the same shallow aquifers that are documented as contaminated, and therefore are potentially at risk of being contaminated. In cooperation with the Office of Environmental Protection of the Fort Peck Tribes, groundwater samples were collected in 2009 and 2010 from supply wells, monitor wells, and the Poplar River for analyses of major and trace elements, including strontium (Sr) concentrations and isotopic compositions. The ratio of strontium-87 to strontium-86 (87Sr/86Sr) is used extensively as a natural tracer in groundwater to detect mixing among waters from different sources and to study the effects of water/rock interaction. On a plot of the reciprocal strontium concentration against the 87Sr/86Sr ratio, mixtures of two end members will produce a linear array. Using this plotting method, data for samples from most of the wells, including the City of Poplar wells, define an array with reciprocal strontium values ranging from 0.08 to 4.15 and 87Sr/86Sr ratios ranging from 0.70811 to 0.70828. This array is composed of a brine end member with an average 87Sr/86Sr of 0.70822, strontium concentrations in excess of 12.5 milligrams per liter (mg/L), and chloride concentrations exceeding 8,000 mg/L mixing with uncontaminated water similar to that in USGS06-08 with 18.0 mg/L chloride, 0.24 mg/L strontium, and a 87Sr/86Sr ratio of 0.70811. The position of samples from the City of Poplar public-water supply wells within this array indicates that brine contamination has reached all three wells. Outliers from this array are EPU-4G (groundwater from the Cretaceous Judith River Formation), brine samples from disposal wells (Huber 5-D and EPU 1-D), USGS92-11 (a well with water that was considerably contaminated in 1992 and becoming less saline with time), and PNR-27 (only slightly below the defined trend with an 87Sr/86Sr ratio of 0.70793). Water samples from the City of Poplar wells are also enriched in anions and cations that are abundant in oil-field brine.

Ground water moving through permeable Paleozoic carbonate rocks represents the most likely pathway for migration of radioactive contaminants from nuclear weapons testing at the Nevada Test Site, Nye County, Nevada. The strontium isotopic composition (87Sr/86Sr) of ground water offers a useful means of testing hydrochemical models of regional flow involving advection and reaction. However, reaction models require knowledge of 87Sr/86Sr data for carbonate rock in the Nevada Test Site vicinity, which is scarce. To fill this data gap, samples of core or cuttings were selected from 22 boreholes at depth intervals from which water samples had been obtained previously around the Nevada Test Site at Yucca Flat, Frenchman Flat, Rainier Mesa, and Mercury Valley. Dilute acid leachates of these samples were analyzed for a suite of major- and trace-element concentrations (MgO, CaO, SiO2, Al2O3, MnO, Rb, Sr, Th, and U) as well as for 87Sr/86Sr. Also presented are unpublished analyses of 114 Paleozoic carbonate samples from outcrops, road cuts, or underground sites in the Funeral Mountains, Bare Mountain, Striped Hills, Specter Range, Spring Mountains, and ranges east of the Nevada Test Site measured in the early 1990's. These data originally were collected to evaluate the potential for economic mineral deposition at the potential high-level radioactive waste repository site at Yucca Mountain and adjacent areas (Peterman and others, 1994). Samples were analyzed for a suite of trace elements (Rb, Sr, Zr, Ba, La, and Ce) in bulk-rock powders, and 87Sr/86Sr in partial digestions of carbonate rock using dilute acid or total digestions of silicate-rich rocks. Pre-Tertiary core samples from two boreholes in the central or western part of the Nevada Test Site also were analyzed. Data are presented in tables and summarized in graphs; however, no attempt is made to interpret results with respect to ground-water flow paths in this report. Present-day 87Sr/86Sr values are compared to values for Paleozoic seawater present at the time of deposition. Many of the samples have 87Sr/86Sr compositions that remain relatively unmodified from expected seawater values. However, rocks underlying the northern Nevada Test Site as well as rocks exposed at Bare Mountain commonly have elevated 87Sr/86Sr values derived from post-depositional addition of radiogenic Sr most likely from fluids circulating through rubidium-rich Paleozoic strata or Precambrian basement rocks.

Groundwater samples in the Yucca Mountain area were collected for chemical and isotopic analyses and measurements of water temperature, pH, specific conductivity, and alkalinity were obtained at the well or spring at the time of sampling. For this project, groundwater samples were analyzed for major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). The U.S. Geological Survey (USGS) performed all the fieldwork on this project including measurement of water chemistry field parameters and sample collection. The major ions dissolved in the groundwater, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) were analyzed by the USGS. All preparation and processing of samples for DOC carbon isotopic analyses and geochemical modeling were performed by the Desert Research Institute (DRI). Analysis of the DOC carbon dioxide gas produced at DRI to obtain carbon-13 and carbon-14 values was conducted at the University of Arizona Accelerator Facility (a NSHE Yucca Mountain project QA qualified contract facility). The major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of DIC were used in geochemical modeling (NETPATH) to determine groundwater sources, flow paths, mixing, and ages. The carbon isotopes of DOC were used to calculate groundwater ages that are independent of DIC model corrected carbon-14 ages. The DIC model corrected carbon-14 calculated ages were used to evaluate groundwater travel times for mixtures of water including water beneath Yucca Mountain. When possible, groundwater travel times were calculated for groundwater flow from beneath Yucca Mountain to down gradient sample sites. DOC carbon-14 groundwater ages were also calculated for groundwaters in the Yucca Mountain area. When possible, groundwater travel times were estimated for groundwater flow from beneath Yucca Mountain to down gradient groundwater sample sites using the DOC calculated groundwater ages. The DIC calculated groundwater ages were compared with DOC calculated groundwater ages and both of these ages were compared to travel times developed in ground-water flow and transport models. If nuclear waste is stored in Yucca Mountain, the saturated zone is the final barrier against the release of radionuclides to the environment. The most recent rendition of the TSPA takes little credit for the presence of the saturated zone and is a testament to the inadequate understanding of this important barrier. If radionuclides reach the saturated zone beneath Yucca Mountain, then there is a travel time before they would leave the Yucca Mountain area and flow down gradient to the Amargosa Valley area. Knowing how long it takes groundwater in the saturated zone to flow from beneath Yucca Mountain to down gradient areas is critical information for potential radionuclide transport. Radionuclide transport in groundwater may be the quickest pathway for radionuclides in the proposed Yucca Mountain repository to reach land surface by way of groundwater pumped in Amargosa Valley. An alternative approach to ground-water flow and transport models to determine the travel time of radionuclides from beneath Yucca Mountain to down gradient areas in the saturated zone is by carbon-14 dating of both inorganic and organic carbon dissolved in the groundwater. A standard method of determining ground-water ages is to measure the carbon-13 and carbon-14 of DIC in the groundwater and then correct the measured carbon-14 along a flow path for geochemical reactions that involve carbon containing phases. These geochemical reactions are constrained by carbon-13 and isotopic fractionations. Without correcting for geochemical reactions, the ground-water ages calculated from only the differences in carbon-14 measured along a flow path (assuming the decrease in carbon-14 is due strictly to radioactive decay) could be tens of thousands of years too old. The computer program NETPATH, developed by the USGS, is the best geochemical program for correcting carbon-14 activities for geochemical reactions. The DIC carbon-14 corrected ages can be further constrained by measuring the carbon isotopes of DOC. Because the only source of organic carbon in aquifers is almost always greater than 40,000 years old, any organic carbon that may be added to the groundwater would contain no carbon-14. Thus, ground-water ages determined by carbon isotopes of DOC should be maximum ages that can be used to constrain DIC corrected ages.

Water samples (referred to as puddle water samples) were collected from the surfaces of a conveyor belt and plastic sheeting in the unventilated portion of the Enhanced Characterization of the Repository Block (ECRB) Cross Drift in 2003 and 2005 at Yucca Mountain, Nevada. The chemistry of these puddle water samples is very different than that of pore water samples from borehole cores in the same region of the Cross Drift or than seepage water samples collected from the Exploratory Studies Facility tunnel in 2005. The origin of the puddle water is condensation on surfaces of introduced materials and its chemistry is dominated by components of the introduced materials. Large CO2 concentrations may be indicative of localized chemical conditions induced by biologic activity.