Jeanne B. Jaeschke Isabelle M. Cozzarelli Doug Kent Mark Engle Adam Mumford Adam Benthem Bridgette Polite Shaun M. Baesman 20200819 spreadsheet Reston, VA U.S. Geological Survey Image citation: June 2016, Kalla Fleger https://doi.org/10.5066/P961J30G Isabelle M. Cozzarelli Douglas B. Kent Martin Briggs Mark A. Engle Adam Benthem Katherine J. Skalak Adam C. Mumford Jeanne Jaeschke Aïda Farag John W. Lane, Jr Denise M. Akob 2020 publication These metadata sets present the comprehensive geochemical composition of solid and water samples from the site of a 11.4ML (million liters) wastewater spill discovered in January, 2015. Analyses of a pipeline sample (analyses of select analytes), supplied by the North Dakota Department of Health are also included. The spill was near Blacktail Creek, north of Williston, ND. The leak was from a pipeline located approximately 70m from Blacktail Creek. The creek flows 17km before entering the Little Muddy River, a tributary to the Missouri River. The study included samples collected in waters upstream and downstream from Blacktail Creek in February and June 2015, June 2016, and June 2017. These data sets include field measurements of pH, temperature, dissolved oxygen, sulfide and specific conductance; laboratory analyses of major ions, trace elements, alkalinity, ammonium, delta deuterium and delta oxygen-18 of water, strontium and radium isotopes; non-volatile dissolved organic carbon (NVDOC), low molecular weight organic acids (LMWOA), and hydrocarbons at surface-water sites. Geomorphic characteristics and watershed similarity tables are included. Sediments were collected in February and June 2015, June 2016, and June 2017 for analysis of carbon, nitrogen, radium and uranium isotopes and extractable ammonium, strontium, and barium. Duplicate water samples and field blanks were collected during each sampling campaign. Two groundwater seep sites were sampled in June 2017 for a select number of analytes. This data release includes twelve data tables provided in two zip folders both as Excel (*.xlxs) and machine readable 'comma-separated values' format (*.csv): 1) data dictionary; 2) descriptions of sampling site locations; 3) summary of field sampling procedures; 4) field measurements, NVDOC, ammonium, alkalinity, strontium isotopes, deuterium and oxygen-18 isotopes, LMWOA and hydrocarbons; 5) concentrations of major anions, cations and trace elements; 6) radiochemistry for sediment samples; 7) extractable ammonium, barium, and strontium concentrations from sediment samples; 8) measured and computed composition of water extracts and pore water concentrations; 9) carbon and nitrogen from sediments; 10) geomorphic characteristics; 11) watershed similarity analysis; and 12) Quality Assurance/Quality Control (QA/QC). This metadata publication’s citation will be added to “Geochemical Indicators of Oil and Gas Wastewater can Trace Potential Exposure Pathways Following Releases to Surface Waters”, Cozzarelli et al., USGS ScienceBase associated manuscript in review, summer of 2020. Production of oil and gas (OG) resources in the Williston Basin, North Dakota could pose human and environmental health risks, in part due to large amounts of wastewater produced, often with complex geochemistry and largely uncharacterized impacts on surface waters. Wastewater can contain elevated concentrations of major ions including salts (also referred to as brines), and trace inorganic and inorganic constituents that can enter the environment through leaks, spills, or direct disposal. Releases have resulted in water-quality effects at other sites in West Virginia (Akob, et al., 2016). The potential effects of wastewater releases on groundwater and surface water quality has been documented in the Williston Basin region in Montana and North Dakota by Cozzarelli et al. (2017), Lauer et al. (2016), Gleason et al. (2014), and Mills et al. (2011). The purpose of this data-collection effort was to document the chemical concentrations of wastewater-affected sites and determine the potential effects of this spill in Blacktail Creek and Little Muddy River. The geochemical results of samples collected in 2015-2017 could be used as a tool to assist management decisions at wastewater spill sites, thereby limiting potential environmental risks and damages. 201502 201506 201606 201706 ground condition Complete None planned -103.6590 -103.5447 48.4275 48.1467 ISO 19115 Topic Category environment USGS Thesaurus water properties geochemistry chemical analysis chromatography oxygen isotope analysis surface water quality nutrient content (water) water pH salinity water temperature oxygen content (water) radium strontium barium None major ions anions cations trace elements strontium isotopes radium isotopes NVDOC ammonium unconventional oil and gas production brine spills semi-volatile hydrocarbons USGS Metadata Identifier USGS:5ee01a8582ce7e579c7089b2 Geographic Names Information System (GNIS) Blacktail Creek Williston Basin Common geographic areas North Dakota Williams Little Muddy none Bakken None. Please see 'Distribution Info' for details. none Jeanne B Jaeschke U.S. Geological Survey, WATER Physical Scientist mailing and physical

Mail Stop 431, 12201 Sunrise Valley Dr

Reston VA 20192 US 703-648-5872 jaeschke@usgs.gov Denise M. Akob Adam C. Mumford William Orem Mark A. Engle J. Grace Klinges Douglas B. Kent Isabelle M. Cozzarelli 20160518 publication Environmental Science & Technology vol. 50, issue 11 n/a American Chemical Society (ACS) https://doi.org/10.1021/acs.est.6b00428 Standard Methods For the Examination of Water and Wastewater 201701 publication n/a Standard Methods For the Examination of Water and Wastewater https://www.standardmethods.org/action/showCitFormats?doi=10.2105%2FSMWW.2882.087 U.S. EPA. 1993 publication n/a U.S. EPA. https://www.epa.gov/esam/epa-method-3501-determination-ammonia-nitrogen-semi-automated-colorimetry ASTM 2015 publication West Conshohocken, PA ASTM http://www.astm.org/cgi-bin/resolver.cgi?D1426 Tyler B. Coplen Joe D. Wildman Julie. Chen 200205 publication Analytical Chemistry vol. 63, issue 9 n/a American Chemical Society (ACS) https://doi.org/10.1021/ac00009a014 Tyler B. Coplen 19940101 publication Pure and Applied Chemistry vol. 66, issue 2 n/a Walter de Gruyter GmbH https://doi.org/10.1351/pac199466020273 I.M. Cozzarelli K.J. Skalak D.B. Kent M.A. Engle A. Benthem A.C. Mumford K. Haase A. Farag D. Harper S.C. Nagel L.R. Iwanowicz W.H. Orem D.M. Akob J.B. Jaeschke J. Galloway M. Kohler D.L. Stoliker G.D. Jolly 201702 publication Science of The Total Environment vol. 579 n/a Elsevier BV https://doi.org/10.1016/j.scitotenv.2016.11.157 Mark A. Engle Francisco R. Reyes Matthew S. Varonka William H. Orem Lin Ma Adam J. Ianno Tiffani M. Schell Pei Xu Kenneth C. Carroll 201605 publication Chemical Geology vol. 425 n/a Elsevier BV https://doi.org/10.1016/j.chemgeo.2016.01.025 Sally A. Entrekin Kelly O. Maloney Katherine E. Kapo Annika W. Walters Michelle A. Evans-White Kenneth M. Klemow 20150923 publication PLOS ONE vol. 10, issue 9 n/a Public Library of Science (PLoS) https://doi.org/10.1371/journal.pone.0137416 S Epstein T Mayeda 195311 publication Geochimica et Cosmochimica Acta vol. 4, issue 5 n/a Elsevier BV https://doi.org/10.1016/0016-7037(53)90051-9 Robert A. Gleason Tara L. Contributions by Chesley-Preston James L. Coleman Seth S. Haines Karen E. Jenni Timothy L. Nieman Zell E. Peterman Max Post van der Burg Todd M. Preston Bruce D. Smith Brian A. Tangen Joanna N. Thamke 2014 publication n/a US Geological Survey https://doi.org/10.3133/sir20145017 International Organization for Standardization 2016 publication n/a International Organization for Standardization https://www.iso.org/standard/61076.html Ed Kaiser Jeff Rohrer 2015 publication Sunnyvale, CA Thermo Fisher Scientific https://assets.thermofisher.com/TFS-Assets/CMD/Application-Notes/an-114-ic-trace-anions-high-purity-water-an71546-en.pdf Nancy E. Lauer Jennifer S. Harkness Avner Vengosh 20160427 publication Environmental Science & Technology vol. 50, issue 10 n/a American Chemical Society (ACS) https://doi.org/10.1021/acs.est.5b06349 Christopher T. Mills Martin B. Goldhaber Craig A. Stricker JoAnn M. Holloway Jean M. Morrison Karl J. Ellefsen Donald O. Rosenberry Roland S. Thurston 201106 application/service Applied Geochemistry vol. 26 n/a Elsevier BV https://doi.org/10.1016/j.apgeochem.2011.03.040 Kinga Revesz Tyler Coplen 2008 publication n/a US Geological Survey https://doi.org/10.3133/tm10C2 Deborah L. Stoliker Deborah A. Repert Richard L. Smith Bongkeun Song Denis R. LeBlanc Timothy D. McCobb Christopher H. Conaway Sung Pil Hyun Dong-Chan Koh Hee Sun Moon Douglas B. Kent 20160311 publication Environmental Science & Technology vol. 50, issue 7 n/a American Chemical Society (ACS) https://doi.org/10.1021/acs.est.5b06155 U.S. EPA 1974 publication n/a U.S. EPA http://www.caslab.com/EPA-Method-415_1 U.S. EPA 1980 publication n/a U.S. EPA https://www.epa.gov/esam/epa-method-9031-radium-226-drinking-water-radon-emanation-technique U.S. EPA 1980 publication n/a U.S. EPA U.S. EPA 1993 publication n/a U.S. EPA https://www.epa.gov/sites/production/files/2015-06/documents/epa-350.1.pdf U.S. EPA 1993 publication Cincinnati, OH U.S. EPA https://www.epa.gov/sites/production/files/2015-08/documents/method_300-0_rev_2-1_1993.pdf U.S. EPA 1994 publication Cincinnati, OH U.S. EPA https://www.epa.gov/sites/production/files/2015-08/documents/method_200-7_rev_4-4_1994.pdf U.S. EPA 1994 publication Cincinnati, OH U.S. EPA https://www.epa.gov/esam/epa-method-2008-determination-trace-elements-waters-and-wastes-inductively-coupled-plasma-mass US Geological Survey 2015 publication n/a US Geological Survey https://doi.org/10.3133/twri09 U. S. Geological Survey 2012 publication Washington, DC U. S. Geological Survey http://pubs.water.usgs.gov/twri9A Markus Christian Weissenberger Sukhmeet Dhillon 20140930 publication n/a Society of Petroleum Engineers https://doi.org/10.2118/171650-MS Mary Jo Baedecker Robert P. Eganhouse Barbara A. Bekins Geoffrey N. Delin 201111 publication Journal of Contaminant Hydrology vol. 126, issue 3-4 n/a Elsevier BV ppg. 140-152 https://doi.org/10.1016/j.jconhyd.2011.06.006 for quality assurance please refer to table 12 Quality Assurance/Quality Control (QA/QC) No formal logical accuracy tests were conducted Data set is considered complete for the information presented, as described in the abstract. Users are advised to read the rest of the metadata record carefully for additional details. No formal positional accuracy tests were conducted No formal positional accuracy tests were conducted North Dakota Department of Environmental Quality 20170701 tabular digital data https://deq.nd.gov/Spills/ Digital and/or Hardcopy 2008 2016 publication date NDDOH OG wastewater spill size was compiled from the North Dakota Department of Health (NDDOH) OG spills database. Spills from 2008 to 2016 were tabulated from the NDDOH OG spill database and the volume of “Oil”, “Produced Water”, and “Other Chemicals” were assigned a geographic location based on the reported well’s American Petroleum Institute’s (API) database on well head location and were total volumes were calculated for each watershed (Hydrologic Unit Code, HUC12) was calculated. American Petroleum Institute 2017 tabular digital data www.API.org Digital and/or Hardcopy 2008 2016 publication date API geographic location of the reported well’s American Petroleum Institute’s (API) database on well head location U.S. Geological Survey 20200501 tabular digital data https://www.usgs.gov/core-science-systems/ngp/national-hydrography/access-national-hydrography-products Digital and/or Hardcopy 20200501 publication date NHDplus Data used to calculate each watershed (Hydrologic Unit Code, HUC12), The watershed size was determined using the largest recorded NHDPlus’s drainage size for streams within each HUC12 watershed using the ArcGIS Join function. Homer, Collin G Dewitz, Jon A Yang, Limin Jin, Suming Danielson, Patrick Xian, George Coulston, J. Herold, N.D. Wickham, J.D. Megown, K 20150501 tabular digital data Photogrammetric Engineering and Remote Sensing, v. 81, no. 5, p. 345–354 http://www.ingentaconnect.com/content/asprs/pers/2015/00000081/00000005/art00002 Digital and/or Hardcopy 2015 publication date NLCD Agricultural activity in each watershed was derived from the National Landcover Database Arthur Cooper 2011 dataset https://www.sciencebase.gov U.S. Geological Survey https://doi.org/10.5066/f7b56gn1 Digital and/or Hardcopy 2020 publication date NFHAP Fish habitat health data from National Fish Habitat Action Plan’s Habitat Condition Index (HCI) score, which is calculated for rivers and watersheds throughout the country, was used to calculate the average HCI score for streams in each HUC12 watershed. Sally A. Entrekin Kelly O. Maloney Katherine E. Kapo Annika W. Walters Michelle A. Evans-White Kenneth M. Klemow 20150923 publication PLOS ONE vol. 10, issue 9 n/a Public Library of Science (PLoS) ppg. e0137416 https://doi.org/10.1371/journal.pone.0137416 Digital and/or Hardcopy 2015 publication date Entrekin et al Soil permeability was identified from the US general soils map and compiled by Entrekin et al. (2015) for HUC 12 watersheds. Site locations: Approximately 15 miles north of Williston, a leak of potentially toxic wastewater was detected near the western North Dakota pipeline into Blacktail Creek and the Little Muddy River, which feeds the Missouri River. The leak was reported to state officials in January 2015. Three different matrices are presented in this data release; surface water, seeps, sediments and a pipeline sample. Samples were collected at seven sites along Blacktail Creek and the Little Muddy River during one week in February 2015, two weeks in June 2015, one week in June 2016, and one week in June 2017. Four of the sampling sites were at Blacktail Creek Reference “BCR” (WBS-09), “Spill” (WBS-08), “4.7 km” (WBS-07), and “7.2 km (1)” (WBS-05). Water samples were collected at three sites on Little Muddy River: “LMR” (WBS-04), “22.9 km (1)” (WBS-02), and “43.8 km”, (WBS-10). Duplicate sampling was done at two locations every time for sites designated “7.2 km (2)” (WBS-03) and “22.9 km (2)” (WBS-06). Field blanks were collected at every sampling event except for February 2015. In 2016, cores were collected at the spill and the 4.7 km sites. In 2017, two ground water seep sites, identified as WBS S-GW Blacktail Creek Reference (BCR), and WBS S-GW 7.2 km, were sampled. Sediment samples were collected from the upper one to three centimeters of the soil surface and creek/stream bed bottom. A sample from the pipeline wastewater was supplied by the North Dakota Department of Health in 2015. Site locations were chosen to avoid on-going active remediation, focusing on collecting water samples from the impacted areas downstream. The spill site experienced active remediation during collection years. February 2015 was the only time site 43.8 km was sampled. Site locations including sample name, sampling date, latitude and longitude, and descriptive distances in relation from the pipeline spill are identified in Table S2. 2015 Materials and Methods: Water samples collected from the Blacktail Creek and the Little Muddy River sites were frozen due to the below zero temperature measurements during the February 2015 collection event. Water samples were obtained by augering through the ice. During February and June 2015, June 2016, and June 2017 sampling, in-line filtration was performed using either a 0.20 µm Whatman® Nuclepore (Whatman Inc., Piscataway, NJ), a 0.20 Supor® (Pall, Port Washington, NY), or a 0.22 µm Millipore® Sterivex ™ polyethersulfone filter (Burlington, MA). Field measurements were made at the time each water sample was collected for temperature in degrees Celsius, pH, dissolved oxygen (DO), and specific conductance. Water samples were collected using a peristaltic pump and oxygen-impermeable Masterflex L/S® High-Performance Precision Pump Tubing, C-Flex®, (Cole-Parmer, Vernon Hills, IL), in 2015-2016. During the June 2017 field sampling event, Tygon® E-Food tubing, (Cole-Parmer, Vernon Hills, IL), was used. Analyses for major cations and trace elements, alkalinity, 87Sr/86Sr (strontium) isotopes, anions, ammonium (NH3-N), a sum of NH4+ and NH3 expressed as total ammonia nitrogen, deuterium and oxygen-18 (δ2H/ δ18O), low molecular weight organic acids (LMWOA), semi-volatile hydrocarbons, and non-volatile dissolved organic carbon (NVDOC) was performed. Sediments were characterized for carbon and nitrogen (CN), and extractable ammonium, strontium, barium, and radium isotopes for most collection events. Deeper sediment samples were collected in the incised river corridor on a low lying, subaerial sediment deposits using a portable vibracorer in a 2-inch diameter aluminum pipe collected to a depth of 0.5 m or refusal. Cores were sectioned in the lab in Reston, Virginia and samples put in Whirlpaks®. Sampling for water, sediment, and core analyses were conducted by a two-person team using USGS “clean hands/dirty hands” described in Akob et al. (2016). An unfiltered, acidified (HNO3) sample of the pipeline wastewater was analyzed for NVDOC, ammonium, 87Sr/86Sr isotopes, cations, and select anions (Cozzarelli, et al., 2017). Duplicate samples were collected at one site per sampling day, and field equipment blanks were collected once per sampling week. For in situ sampling: temperature, pH, DO, sulfide, and specific conductance; water collection for the seven field sites, purpose, method/filter, quantity, bottle/container type, action, preservation for major and trace elements, alkalinity, 87Sr/86Sr isotopes, anions, ammonium, LMWOA, semi-volatile hydrocarbons, CN, radium isotopes and NVDOC for February 2015, June 2015, June 2016, and June 2017 are listed in Table S3. In the field, water data for temperature, pH, DO, and specific conductance were recorded using a YSI (Xylem brand, Baton Rouge, LA) multiparameter sonde, calibrated daily. Sulfide was measured with a CHEMetrics sulfide test kit and P2000/P3000 spectrophotometer. Field measurements, in most cases were recorded in duplicate or triplicate, with a reported value as an average, or median of the two or three data points. Water collection reported values for field measurements, NVDOC, ammonium, alkalinity, 87Sr/86Sr isotopes, δ2H/δ18O isotopes, LMWOA and semi-volatile hydrocarbons are reported in Table S4. Laboratory analyses for anions, cations, and trace elements are listed in Table S5. Sediment and core radiochemistry analyses are listed in Table S6. Laboratory results from extractable ammonium, strontium, and barium are included in Table S7. Water extract and pore water composition is reported in Table S8. Carbon and nitrogen analyses are found in Tables S9. Geomorphic characteristics from the background, spill site and 4.7 km are presented in Table S10. Data used for the watershed similarity analysis is reported in Table S11. Quality Assurance/Quality Control (QA/QC), including sample matrix, method detection limit, limits of quantification, and method references are recorded in Table S12. Water-quality sampling was done according to standard field procedures (U.S. Geological Survey, [http://pubs.water.usgs.gov/twri9A]). Using an aliquot of the pipeline wastewater bottle that was received from the North Dakota Department of Health, a select number of anions, major cations, ammonium, and NVDOC were measured; these results are reported in Tables S4 and S5. Major cation concentrations were measured as milligrams per liter (mg/L) in filtered field-acidified water samples using a Perkin Elmer™ Optima 4300DV inductively coupled plasma-optical emission spectrometer (ICP-OES) (Perkin Elmer, Waltham, MA) following a modified version of EPA Method 200.7 version 4.4. (U.S. Environmental Protection Agency, 1994) except for barium. Barium was determined by inductively coupled plasma-atomic emission spectrometer (ICP-AES) Thermo-Electron iCAP 6500. Approximately 80% of cation water samples were run in duplicate along with blanks, calibration standards, and external standards. The precision of repetitive measurements with the IC-OES is typically less than 5%. Internal standards were used to compensate for system drift and for analysis of complex matrices that might affect the instruments performance. Results include average, standard deviation (STDEV), and percent relative standard deviation (%RSD). Trace element concentrations were measured as micro grams per liter (μg/L) in filtered field-acidified water samples using an Agilent 7900™ Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) (Perkin Elmer, Waltham, MA). Approximately 20% of the water samples analyzed by ICP-MS were run in duplicate along with blanks and calibration standards. Internal standards were used to compensate for system drift and for analysis of complex matrices which might affect the instruments performance. The precision of repetitive measurements was typically less than 3%. The detection limits for the ICP-MS analyses range from ppt (ng/L) to ppb (μg/L), depending on the element. When elements were run on both ICP-OES and ICP-MS, the cutoff is >0.5 mg/L for ICP-OES, <0.5 mg/L for ICP-MS, based on our reported MDL/LOQ values (method detection limit) / (Limits of quantification). Alkalinity concentrations were measured as mg/L bicarbonate (HCO3-) in filtered field water samples using an automatic titrator, a TIM900™ Titration Manager, TIM900™ version 2.1 software, and an ABU901 Autoburette. This analytical system adds a titrant ~ 0.02347N sulfuric acid (H2SO4) using drops to bring a water sample to a pH of 4.2 or lower until an inflection point is reached, under conditions of constant monitoring via a pH meter and an electrode. Analyses were run in triplicate provided that the sample volumes were sufficiently large. Alkalinity data includes average, median (if run in triplicate), n (number of analyses), STDEV, and %RSD. Radiogenic strontium (87Sr/86Sr) isotopes were measured in field filtered, acidified water samples using a multiple collector-ICP-MS at the Center for Earth and Environmental Science at the University of Texas in El Paso, following chemical purification using Eichrom Sr resin (Eichrom Technologies, Lisle, IL).  The method is cited by Cozzarelli et al. (2017). Accuracy was assessed during this investigation through the repeated analysis of secondary standard EN-1 (mean=0.70917, std. error=0.000003, n=12) with every sample batch over 2016-2019 analyses dates. Agreement with the accepted value of 0.709174 was obtained. Accuracy across a wider range of values was demonstrated by the determination of standard BCR-2 (0.70498) relative to its median reported value in GeoReM of 0.70501±0.00004.  Long-term external precision of the data is 0.00002 (2s), based on repeated analysis of EN-1 (n=12) over 2016-2019 analyses dates. Major anions were measured as mg/L in filtered field water samples using suppressed ion chromatography, a Dionex™ 120 and Thermo Dionex™ ICS 1000 Ion Chromatograph (IC) (Thermo Fisher, Sunnyvale, CA) with an ED50 Electrochemical Detector and a high capacity AS14 anion-exchange column (Thermo Scientific, Waltham, MA). The AS14 column uses a carbonate/bicarbonate eluent coupled with suppressed conductivity detection for determination of inorganic anions (chloride, bromide, nitrate, phosphate, and sulfate) in diverse sample matrices and meets the performance requirements specified in US EPA Method 300.0 (A). Analyses were run in duplicate/triplicate provided that the sample volume is sufficiently large. Water samples were run in conjunction with blanks, certified reference material standards, and calibration/check standards. Anion data includes average, median (if run in triplicate), n, STDEV, and %RSD. Ammonium (NH4) concentrations were measured as NH3, as N in filtered field water samples on an AQ2 Discrete Seal Analyzer that uses a robotic sampling arm working in conjunction with a stepper motor-driven syringe. The syringe is used for aspirating, dispensing, and mixing the sample and reagent into miniaturized test tubes (reaction wells). The sample and reagents were incubated in the reaction wells for a pre-programmed time.  A single aliquot is then transferred into the stop/flow Optical Quality Glass Cuvette. Alkaline phenol and hypochlorite react with ammonia to form indophenol blue, the blue color formed is intensified by sodium nitroferricyanide dehydrate, and then measured spectrophotometrically at 650-660 nm.  A minimum of 80% of the field water samples were run in duplicate. Blanks, calibration standards and certified reference material standards were run in each batch. Reference AQ2 Method EPA-103A. Results were expressed mg/L ammonia-nitrogen, NH3-N. Hydrogen-isotope ratio (δ2H) and oxygen-isotope ratio (δ18O) analyses were measured as ‰ (per mil) in filtered, unfiltered, and unfiltered-preserved field water samples. A hydrogen equilibration technique (Coplen, et al., 1991; Révész and Coplen, 2008) was used. For oxygen isotope analysis, the CO2 equilibration technique of Epstein and Mayeda (1953), which has been automated (Révész and Coplen, 2008), was used. Reporting of δ2H and δ18O results were reported in per mil relative to VSMOW (Vienna Standard Mean Ocean Water) and were normalized (Coplen, 1994) on scales such that the oxygen and hydrogen isotopic values of SLAP (Standard Light Antarctic Precipitation) were -55.5 per mil and -428 per mil, respectively. The 2-sigma uncertainties of the isotopic results were 0.2 per mil for oxygen, and 2 per mil for hydrogen, unless otherwise indicated. These uncertainties indicate that if the same sample were resubmitted for isotopic analysis, the newly measured value would be within the uncertainty bounds 95% of the time. All water samples were run three or more times. The two isotope reference materials (standards) with their isotope span cover the isotope values of unknown samples were loaded onto every analysis run. The acceptance criteria for the QC water samples were the same as the field water samples. For each batch of water samples, a graph was made of δ2H plotted against δ18O. If outliers were noted, then they were reanalyzed for either one or both of δ2H and δ18O. Low molecular weight organic acid concentrations for lactate, acetate, propionate, formate, butyrate, pyruvate, and benzoate were measured as mg/L in unfiltered field water samples using a Dionex™ ICS2100 Ion Chromatograph with an IonPac AS11-HC anion exchange column, a potassium hydroxide gradient pump, and an IonPac AG11-HC on-guard column (Thermo Scientific, Waltham, MA). These columns were designed for the separation of monovalent carboxylic acids: lactate, acetate, propionate, formate, butyrate, and pyruvate. The microporous resins on the on-guard cartridge ensure optimum long-term performance of the guard. The high capacity of this column increases retention times to 48 minutes and contributes to a higher resolution. The Dionex™ IonPac AG11-HC guard column is packed with a microporous resin which has a lower capacity. This method is modified from the Dionex™ Fisher Scientific Determination of Trace Anions in High-Purity Waters Using Direct Injection and Two-Step Isocratic Ion Chromatography, Application Note 114 method (Kaiser, et al., n.d.) (Thermo Fisher Scientific, Sunnyvale, CA). Water samples were injected through a 50-micron loop and were run in triplicate if there were enough sample volumes. Low molecular weight organic acid concentrations for lactate, acetate, propionate, butyrate, and benzoate were measured as mg/L in unfiltered field water samples that contained elevated concentrations of sodium, chloride, or sulfate were analyzed using an Agilent 1220 Infinity liquid chromatograph with a Dionex™ Acclaim OA column and matching guard column. This column was designed for organic acid separation from a wide range of aqueous matrices. Formate and pyruvate co-elude with this method. Waters samples were filtered through a 0.22µm Sterivex™ filter and acidified with reagent grade hydrochloric acid (HCl) prior to injection. A 25 µL sample was injected, with a sample loop capacity up to 100 µL for dilute samples. Reported values include median, STDEV, and %RSD. Blanks, calibration standards, certified reference material standards, and external standards were run with each batch of water samples. The method was modified from Weissenberger et al. (2014). Non-volatile dissolved organic carbon concentrations were measured as mg/L of Carbon (C) in filtered field-HCl acidified water samples using a Shimadzu TOC-VCSN analyzer Total Organic Carbon Analyzer (Shimadzu Corporation, Columbia, MD) and ASI-V autosampler. The instrument employs a combination high temperature combustion/non-dispersive infrared detector (NDIR) technique. The acidified water samples were sparged with Ultra Zero air to remove the inorganic carbon. Water samples were then injected into a combustion tube containing a platinum catalyst and heated, oxidizing all carbon compounds in the sample to CO2 gas. The CO2 generated by oxidation was detected using a non-dispersive infrared detector (NDIR). Water samples were run in duplicate or triplicate if sample volumes were sufficiently large. Water samples were run in conjunction with blanks, certified reference material standards, and calibration/check standards. NVDOC data includes average, median (if run in triplicate), n, STDEV, and %RSD. This method is modified from EPA Method 415.1, 1.11. Semi-volatile hydrocarbons concentrations were measured as μg/L in unfiltered water samples preserved with mercuric chloride, analyzed by headspace solid phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC/MS) using an Agilent 7890A+ gas chromatograph coupled to an Agilent 5977A quadrupole mass spectrometer using a modification of Baedecker et al (2011) and ISO Method 17943 (2016). Hydrocarbons were sorbed onto a SPME fiber as the sample was heated and vortexed, and the fiber then desorbed in the GC inlet. The compounds of interest were condensed on the head of the column by cooling the GC oven to -50 degree C and separated on an Agilent HP-5MS column as the oven was ramped to 285 degree C. Eluting peaks were detected using the mass spectrometer in Selected Ion Monitoring mode. Compounds were identified based on comparison of retention times and major ions to authentic standards. Quantification was based on an external standard curve composed of authentic standards. Variations in extraction efficiency were controlled for with deuterated internal standards corresponding to compounds of interest. Approximately 20% of water samples were run in duplicate, and certified reference materials and blanks were run every five water samples to quantify accuracy. Changes in extraction and/or chromatographic efficiency were controlled using deuterated internal standard compounds. Detection limits were in the high PPT (ng/L) to low PPB (μg/L) range, depending on the target compound.  228Ra and 226Ra in sediments and select cores were measured by counting daughter isotopes by gamma-ray spectroscopy. Samples for radium analyses were sealed for 30 days for ingrowth of radium daughter isotopes. To expedite counting, samples for 226Ra were counted using its 186 keV peak. Because 226Ra analyses using its 186 keV peak may have interference from a 235U peak, the 186 peak was used primarily to screen samples prior to counting by 226Ra daughter isotopes. Results from both 226Ra analyses and 228Ra analyses are included with 226Ra analyses by daughter isotopes in Table S6. Uranium and radium activity are provided in becquerels (disintegrations per second) per kilogram sediment dry weight. Concentrations can be calculated from the formula Ci = (Ait1/2i)/{(Na)(ln2)}, where i refers to the specific radionuclide, Ci to the concentration (moles/kg sediment), Ai the activity, t1/2,i the half-life (seconds), Na Avogadro’s number (dimensionless), and ln2 is the natural logarithm of 2. Samples taken in 2017 were analyzed by ALS Environmental (Fort Collins, CO); 226Ra was measured by radon emanation as described by EPA Method 903.1, and 228Ra was measured using gas flow proportional counting as described by EPA Method 904. CN quantitative analyses for carbon and nitrogen sediment samples were measured using a Thermo Fisher Scientific™ Flash 2000 Elemental Analyzer (Thermo Fisher Scientific Inc., Waltham, MA). The operation of the elemental analyzer was based on the complete and instantaneous oxidation of the sample by “flash combustion” whereby all organic and inorganic substances are converted into combustion products. The ground dried sediments, which were contained in a tin capsule, were introduced into the instrument automatically by a MAS200R autosampler tray. From the tray they then dropped into the oxidation/reduction reactor column. Flash combustion causes oxidation of 85-95% of the sample. Complete oxidation of reduced carbon and sulfur is achieved when the mixture of gases passes over the catalyst layer of chromic oxide. A thermal conductivity detector measures the individual components of the gas mixture as they elute from the column. The signal produced from the thermal conductivity detector is passed to an A/D converter, and the peaks are integrated by the EAGER Xperience data system. A chromatogram and an analysis report (containing raw data and calculated values) are used to calculate the percent composition of carbon and nitrogen. Sediment-bound ammonium was analyzed using extractions with potassium chloride (KCl) (Stoliker, et al., 2016). Ten grams of wet sediments were reacted with 13.3 grams of 2.0 mole/L potassium chloride. Samples were then tumbled end over end for approximately two hours, placed in a centrifuge and spun down. The samples were filtered through a 0.20 μm in-line filter then measured on an AQ2 Discrete Seal Analyzer. A modified EPA Method 305.1 version 2 was used. Following this method, alkaline phenol and hypochlorite react with ammonia to form indophenol blue; the blue color formed is intensified by sodium nitroferricyanide dihydrate. The sample is then measured spectrophotometrically at 650-600 nm. Ammonium plus ammonia was reported. Short-term sediment-bound chemical forms of Ba and Sr were determined by ICP-OES (Thermo iCAP 6500, Thermo Fisher Scientific Inc, Waltham, MA) following method cited in Cozzarelli et al (2017). All instrument values were either exported or entered into an Excel spreadsheet and all calculations were made using Excel function keys. 2017 Processing steps for Table S11: Table S-11 is a watershed scale analysis to determine locations with characteristics similar to where the spill occurred on the Blacktail River. We utilized multiple, publicly available databases to score each watershed based on 6 characteristics: 1) OG wastewater spill size, 2) distance of spills to the nearest stream, 3) Current fish habitat health, 4) groundwater permeability, 5) agricultural activity in the basin, and 6) watershed size. A total of the 809 HUC 12 watersheds in the Bakken region of North Dakota were investigated and 298 had known spills as well as a fish habitat assessment. The databases used to quantify these characteristics were compiled using the following procedures: 1) OG wastewater spill size was compiled from the North Dakota Department of Health (NDDOH) OG spills database. Spills from 2008 to 2016 were tabulated from the NDDOH OG spill database and the volume of “Oil”, “Produced Water”, and “Other Chemicals” were assigned a geographic location based on the reported well’s American Petroleum Institute’s (API) database on well head location and were total volumes were calculated for each watershed (Hydrologic Unit Code, HUC12) was calculated. 2) The likely distance of each spill to a stream was computed using ArcGIS Pro’s Near function using the API well head location database to the nearest intersection with the National Hydrological Database (NHDPlus) stream location. 3) Fish habitat health data from National Fish Habitat Action Plan’s Habitat Condition Index (HCI) score, which is calculated for rivers and watersheds throughout the country, was used to calculate the average HCI score for streams in each HUC12 watershed. 4) Soil permeability was identified from the US general soils map and compiled by Entrekin et al. (2015) for HUC 12 watersheds. 5) Agricultural activity in each watershed was derived from the National Landcover Database (NLCD) and HUC12 watershed averages for each landcover class was compiled by Entrekin et. al 2015. For the purpose of identifying agriculture activity in the watershed our analysis used the percentage of cover of both “Cropland” and “Pasture” for our rankings. 6) The watershed size was determined using the largest recorded NHDPlus’s drainage size for streams within each HUC12 watershed using the ArcGIS Join function. Sites without spills or fish surveys were excluded from the analysis leaving 298 HUC12 watersheds. Each of the 6 metrics were ranked by quartile and watersheds with similar characteristics were identified using ArcGIS’s Similarity function. NDDOH API NHDplus NFHAP Entrekin et al 202006 Adam J Benthem U.S. Geological Survey, NORTHEAST REGION Hydrologist mailing address

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Pembroke NH 03275-3718 US 603-226-7853 603-226-7894 abenthem@usgs.gov Table-S2-Site-Locations.csv Comma Separated Value (CSV) file containing data. This table describes the exact site latitude and longitude taken by GPS for each sample site and sample date. Producer Defined Site Field sample site name Producer Defined BCR Background Conditions Reference site from Blacktail Creek Producer defined Spill Site sample site just downstream from the spill area Producer defined 4.7 km (downstream of spill) surface water collection site 4.7 km downstream from the spill site Producer defined 7.2 km (1) surface water collection site 7.2 km downstream of the spill site, field replicate number one Producer defined 7.2 km (2) surface water collection site 7.2 km downstream of the spill site, field replicate number two Producer defined LMR surface water site, Little Muddy River reference site Producer defined 22.9 km (1) surface water site at USGS stream gauge (site ID 06331000) 22.9 km from spill site field replicate one Producer defined 22.9 km (2) surface water site at USGS stream gauge (site ID 06331000) 22.9 km from spill site field replicate two Producer defined 43.8 km surface water site 43.8 km downstream from the spill site Producer defined Field blank field blanks are prepared in the actual same containers as the field samples are collected in using analyte-free water Producer defined 7.2 km GW seep groundwater seep about 7.2 km downstream from the spill site Producer defined BCR GW seep groundwater seep located near the background reference site Producer defined Sample Name sample identification number Producer Defined identification number used for samples from a specific site Sampling Date A representation of time in which the smallest unit of measure is a day. The value is expressed in MMDDYYYY Producer Defined OPSE one per sampling event Producer defined 02112015 06292017 latitude (X) latitude of field sample site Producer Defined ND no data collected for the latitude, Producer defined 48.152362 48.416279 decimal degrees longitude (Y) longitude of field sample site Producer Defined ND no data collected for the longitude Producer defined -103.646640 -103.570510 decimal degrees Distance from Spill Site description of the field sample site relative to the spill site or bland description Producer Defined distance in kilometers upstream or downstream from the spill site. Most samples are surface water but groundwater seeps are noted, pipeline samples are described, and field blanks are defined Table-S3-Field-Sampling-Characteristics.csv Comma Separated Value (CSV) file containing data. This table describes the field sampling procedures for the different sampling dates, sample matrix, collection volumes, containers, and preservation. Producer Defined Data Characteristic description of the characteristic to be measured or field measurement Producer Defined Temperature sample temperature in degrees Celsius (°C) in the field Producer defined pH pH reported in standard units taken in the field Producer defined Dissolved Oxygen Dissolved oxygen in milligram per liter (mg/L) taken in the field Producer defined Specific Conductance Specific Conductivity in microsiemen per centimeter (µS/cm) taken in the field Producer defined Cations sample collected for the analysis of Cations at the laboratory Producer defined Alkalinity Alkalinity HCO3- read at the lab reported as milligram per liter as bicarbonate (mg/L as HCO3-) Producer defined Strontium Isotopes sample collected for strontium 87Sr/86Sr isotopes to be measured at the laboratory Producer defined Anions sample collected for anions to be measured at the laboratory Producer defined Ammonium sample collected for ammonium to be measured at the laboratory Producer defined Deuterium & Oxygen-18 Isotopes sample collected for Deuterium (delta2H) and oxygen-18 isotopes Producer defined LMWOA sample collected for low molecular weight organic acid Producer defined Hydrocarbons sample collected for hydrocarbons Producer defined NVDOC sample collected non-volatile dissolved organic carbon Producer defined CN sample collected Carbon Nitrogen Producer defined Radium & Uranium Isotopes sample for measuring Radium & Uranium Isotopes at the laboratory Producer defined Sulfide Dissolved sulfide measured in the field Producer defined Sampling Date A representation of time in which the smallest unit of measure is a month. The value is expressed in MM YYYY Producer Defined 022015 062017 Matrix sample matrix Producer Defined water water sample Producer defined sediment sediment sample Producer defined floodplain core A core pressed into the sediment that was then sampled into five centimeter increments with zero indicting the top of the core at the sediment surface. Producer defined Method/Filter either the instrument used to make the field measurement, the filter used to take a water sample, or the method used to take a sediment sample Producer Defined YSI sonde YSI EXO multiparameter sonde (Xylem brand, Baton Rouge, LA) Producer defined 0.20 µm Whatman® Nuclepore filter size and brand used to filter the water sample Producer defined grab sample individual sample collected without compositing or adding other samples to it Producer defined 0.20 Supor® size and brand of the filter used to collect the water sample Producer defined scoop Several centimeters of the surface sediment were collected using clean sterile scoop Producer defined 0.22 µm Sterivex filter size and brand of the filter used to collect the water sample Producer defined vibracorer sediment core then sampled into 5cm increments Producer defined Unfiltered; CHEMetrics Kit with Photometer Unfiltered water sample taken and measured at the laboratory Producer defined Quantity number of bottles and volume of the sample taken Producer Defined NA not applicable Producer defined number of samples taken (volume in mL of sample taken) Bottle/Container type sample container material or type Producer Defined NA not applicable Producer defined Whirlpak® Standard plastic sample bag Producer defined HDPE High Density Polyethylene plastic bottle Producer defined clear VOA glass Volatile Organic Analysis glass bottle, clear glass Producer defined clear clear glass bottle Producer defined amber VOA glass Volatile Organic Analysis glass bottle, amber glass Producer defined Action sample bottle preparation before the sample was taken Producer Defined NA not applicable Producer defined pre-rinse Bottles were pre-rinsed with sample that was discarded before the bottle was filled. Producer defined pre-rinse, no head space bottle was pre-rinsed with sample before taking sample, sample bottle was filled to the top Producer defined no pre-rinse sample bottle was not pre-rinsed Producer defined clean scoop clean sterile scoop Producer defined pre-rinse, fill to shoulder sample bottle was pre-rinsed, the bottle was only filled to the bottle shoulder Producer defined pre-rinse, fill 2/3rds sample bottle was pre-rinsed with sample and the bottle was filled 2/3 of the way Producer defined pre-rinse with sample, minimum head space bottle was pre-rinsed with sample, and bottle almost filled to the top Producer defined Preservation sample preservation method Producer Defined NA not applicable Producer defined acidify w/double distilled Optima nitric acid, store & ship on wet ice acidified with nitric acid and chilled with wet ice Producer defined store & ship on wet ice Kept cold with ice Producer defined store & ship on dry ice sample frozen with dry ice and kept frozen Producer defined mercuric chloride, store & ship on wet ice VOL/CONC mercuric chloride added, sample kept cold on wet ice Producer defined acidify w/trace grade hydrochloric acid, store & ship on wet ice acidified with hydrochloric acid and kept cold using wet ice Producer defined acidify with double distilled Optima nitric acid ~pH 2, store and ship on wet ice acidified nitric acid (end pH 2) and chilled on wet ice Producer defined Table-S10-Geomorphology.csv Comma Separated Value (CSV) file containing data. Table-S10-Geomorphology: Geomorphic characteristics of Blacktail Creek background (BCR) and 4.2 km sites Producer Defined Site name of the sample site, see table S2 for GPS location and site description Producer Defined BCR Background Conditions Reference site from Blacktail Creek Producer defined 4.7 km surface water collection site 4.7 km downstream from the spill site Producer defined Sampling Date A representation of time in which the smallest unit of measure is a day. The value is expressed in MM/DD/YYYY Producer Defined 06/27/2017 06/27/2017 MM/DD/YYYY Data Characteristic A defined water area Producer Defined Pool An area of the stream that has greater depths and slower currents than riffles and runs. Producer defined Riffle An area of shallow water created by deposition of coarse sediment Producer defined Run An area where the water is flowing rapidly, generally located downstream of riffles. Runs are deeper than riffles. Producer defined Average River Width (m) average width of the river Producer Defined 1.5 3.0 meter Average Sediment Depth (cm) average depth of the sediment Producer Defined 10 35 centimeter Geomorphic feature storage rate (m3/km) storage rate of the described feature Producer Defined 150 1050 meter cubed per kilometer Length of Feature (m) The length of the described water feature Producer Defined 23 266 meter Percentage of measured river length The length of a stream is the distance measured along the stream channel from the source to a given point or to the outlet, a distance that may be measured on a map or from aerial photographs. On large-scale maps, it is measured along the geometrical axis, or the line of maximum depth. Producer Defined 7 78 percent Estimated Sediment storage in geomorphic unit (m3/km) estimated sediment storage in geomorphic unit in cubic meters per kilometer Producer Defined 23 700 meter cubed per kilometer This data release includes twelve data tables given both as Excel (*.xlxs) and machine readable 'comma-separated values' format (*.csv): Table-S1-Data-Dictionary: Data dictionary for data generated in the Blacktail Creek OG wastewater spill study. This table contains the detailed entity and attribute information for tables S4 - S9 and S11- S12. The entity and attribute section for descriptive tables S2, S3, and S10 are included in this metadata file. Table-S2-Site-Locations: Descriptions of sampling site locations for the Blacktail Creek OG wastewater spill study. Table-S3-Field-Sampling-Characteristics: Summary of field sampling procedures for the Blacktail Creek OG wastewater spill study. Table-S4-Field-Measurements-and-Geochemistry-of-Water-samples: Field measurements and organic acids and hydrocarbon concentrations in water samples from the Blacktail Creek OG wastewater spill study. Table-S5-Cation-Anions-Trace: Concentrations of major cations, anions, and trace elements in samples from the Blacktail Creek OG wastewater spill study. Table-S6-Radium-Analysis: Radiochemistry for sediment samples collected for the Blacktail Creek OG wastewater spill study. In stream sediment and bank seep sediments (GW seep) were analyzed. Table-S7-Extractable-NH4-Sr-Ba: KCl-extractable ammonium and HCl-extractable strontium and barium concentrations in sediments from the Blacktail Creek OG wastewater spill study. Table-S8-Seeps-extraction: Measured and computed composition of water extracts and pore water concentrations computed from replicate (Rep.) water extract compositions. Table-S9-CN-Analysis: Total C and N in sediments from the Blacktail Creek OG wastewater spill study. Table-S10-Geomorphology: Geomorphic characteristics of Blacktail Creek background (BCR) and 4.2 km sites. Table-S11-Blacktail-similarity: Data used for the watershed similarity analysis. Table-S12-QAQC: Quality Assurance /Quality Control parameters for analyses used in the Blacktail Creek OG wastewater spill study Table-S1-Data-Dictionary included with this data release contains the entity and attribute information for the heading in the first row for tables S4-S9, and S11- S12. GS ScienceBase U.S. Geological Survey mailing and physical

Denver Federal Center, Building 810, Mail Stop 302

Denver CO 80225 United States 1-888-275-8747 sciencebase@usgs.gov Unless otherwise stated, all data, metadata and related materials are considered to satisfy the quality standards relative to the purpose for which the data were collected. Although these data and associated metadata have been reviewed for accuracy and completeness and approved for release by the U.S. Geological Survey (USGS), no warranty expressed or implied is made regarding the display or utility of the data on any other system or for general or scientific purposes, nor shall the act of distribution constitute any such warranty. XLSX, CSV none https://doi.org/10.5066/P961J30G None 20200827 Jeanne B Jaeschke U.S. Geological Survey, WATER Physical Scientist mailing and physical

Mail Stop 431, 12201 Sunrise Valley Dr

Reston VA 20192 US 703-648-5872 703-648-5274 jaeschke@usgs.gov Content Standard for Digital Geospatial Metadata FGDC-STD-001-1998