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Selenium isotope geochemistry: A new approach to characterizing the environmental chemistry of selenium. Final report

Description: High levels of selenium in the environment will be a prominent water quality issue in the western United States for many years. Selenium accumulation is linked to increased rates of death and deformity in migratory birds, blind staggers in livestock, and selenosis in humans. In California, agricultural drain waters and oil refinery effluent contribute to high selenium content in the San Joaquin Valley and the San Francisco Bay. The importance of these industries to California`s economy precludes simple abatement, while the complexity of selenium cycling precludes simple remediation. The purpose of this project is to measure variations in the isotopic composition of selenium in water and soil samples caused by natural processes and to show, for the first time, the value of isotopic measurements in characterizing selenium pollution. The research seeks to identify sources of selenium pollution, determine processes in the selenium cycle, and support selenium remediation studies. The project required the successful integration of three components: (1) appropriate sampling a field setting showing Se enrichment and possibly isotopic fractionation, (2) analytical chemical methods for isolating and purifying the various species of Se in waters and sediment, and (3) mass spectroscopic instrumentation for high precision isotope abundance measurements.
Date: February 5, 1997
Creator: Volpe, A.M. & Esser, B.K.
Partner: UNT Libraries Government Documents Department

Evidence for Groundwater Contamination Vulnerability in California?s Central Valley

Description: The California Water Resources Control Board, in collaboration with the US Geological Survey and Lawrence Livermore National Laboratory, has implemented a program to assess the susceptibility of groundwater resources. Advanced techniques such as groundwater age dating using the tritium-helium method, extensive use of oxygen isotopes of the water molecule ({delta}{sup 18}O) for recharge water provenance, and analysis of common volatile organic compounds (VOCs) at ultra-low levels are applied with the goal of assessing the contamination vulnerability of deep aquifers, which are frequently used for public drinking water supply. Over 1200 public drinking water wells have been tested to date, resulting in a very large, tightly spaced collection of groundwater ages in some of the heavily exploited groundwater basins of California. Smaller scale field studies that include shallow monitoring wells are aimed at assessing the probability that nitrate will be transported to deep drinking water aquifers. When employed on a basin-scale, groundwater ages are an effective tool for identifying recharge areas, defining flowpaths, and determining the rate of transport of water and entrained contaminants. De-convolution of mixed ages, using ancillary dissolved noble gas data, gives insight into the water age distribution drawn at a well, and into the effective dilution of contaminants such as nitrate at long-screened production wells. In combination with groundwater ages, low-level VOCs are used to assess the impact of vertical transport. Special studies are focused on the fate and transport of nitrate with respect to vulnerability of aquifers in agricultural and formerly agricultural areas.
Date: December 13, 2005
Creator: Moran, J E; Leif, R; Esser, B K & Singleton, M J
Partner: UNT Libraries Government Documents Department

Radiochemical Analyses of the Filter Cake, Granular Activated Carbon, and Treated Ground Water from the DTSC Stringfellow Superfund Site Pretreatment Plant

Description: The Department of Toxic Substance Control (DTSC) requested that Lawrence Livermore National Laboratory (LLNL) evaluate the treatment process currently employed at the Department's Stringfellow Superfund Site Pretreatment Plant (PTP) site to determine if wastes originating from the site were properly managed with regards to their radioactivity. In order to evaluate the current management strategy, LLNL suggested that DTSC characterize the effluents from the waste treatment system for radionuclide content. A sampling plan was developed; samples were collected and analyzed for radioactive constituents. Following is brief summary of those results and what implications for waste characterization may be made. (1) The sampling and analysis provides strong evidence that the radionuclides present are Naturally Occurring Radioactive Material (NORM). (2) The greatest source of radioactivity in the samples was naturally occurring uranium. The sample results indicate that the uranium concentration in the filter cake is higher than the Granular Activated Carbon (GAC) samples. (11 -14 and 2-6 ppm respectively). (3) No radiologic background for geologic materials has been established for the Stringfellow site, and comprehensive testing of the process stream has not been conducted. Without site-specific testing of geologic materials and waste process streams, it is not possible to conclude if filter cake and spent GAC samples contain radioactivity concentrated above natural background levels, or if radionuclides are being concentrated by the waste treatment process. Recommendation: The regulation of Technologically Enhanced, Naturally Occurring Radioactive Materials (T-NORM) is complex. Since the results of this study do not conclusively demonstrate that natural radioactive materials have not been concentrated by the treatment process it is recommended that the DTSC consult with the Department of Health Services (DHS) Radiological Health Branch to determine if any further action is warranted. If it were deemed desirable to establish a background for the Stringfellow setting LLNL would recommend that additional ...
Date: September 16, 2005
Creator: Esser, B K; McConachie, W; Fischer, R; Sutton, M & Szechenyi, S
Partner: UNT Libraries Government Documents Department

GAMA-LLNL Alpine Basin Special Study: Scope of Work

Description: For this task LLNL will examine the vulnerability of drinking water supplies in foothills and higher elevation areas to climate change impacts on recharge. Recharge locations and vulnerability will be determined through examination of groundwater ages and noble gas recharge temperatures in high elevation basins. LLNL will determine whether short residence times are common in one or more subalpine basin. LLNL will measure groundwater ages, recharge temperatures, hydrogen and oxygen isotopes, major anions and carbon isotope compositions on up to 60 samples from monitoring wells and production wells in these basins. In addition, a small number of carbon isotope analyses will be performed on surface water samples. The deliverable for this task will be a technical report that provides the measured data and an interpretation of the data from one or more subalpine basins. Data interpretation will: (1) Consider climate change impacts to recharge and its impact on water quality; (2) Determine primary recharge locations and their vulnerability to climate change; and (3) Delineate the most vulnerable areas and describe the likely impacts to recharge.
Date: December 12, 2011
Creator: Singleton, M J; Visser, A; Esser, B K & Moran, J E
Partner: UNT Libraries Government Documents Department

Intrinsic and Extrinsic Chemical and Isotopic Tracers for Characterization Of Groundwater Systems

Description: In many regions, three dimensional characterization of the groundwater regime is limited by coarse well spacing or borehole lithologic logs of low quality. However, regulatory requirements for drinking water or site remediation may require collection of extensive chemical and water quality data from existing wells. Similarly, for wells installed in the distant past, lithologic logs may not be available, but the wells can be sampled for chemical and isotopic constituents. In these situations, a thorough analysis of trends in chemical and isotopic constituents can be a key component in characterizing the regional groundwater system. On a basin or subbasin scale, especially in areas of intensive groundwater management where artificial recharge is important, introduction of an extrinsic tracer can provide a robust picture of groundwater flow. Dissolved gases are particularly good tracers since a large volume of water can be tagged, there are no real or perceived health risks associated with the tracer, and a very large dynamic range allows detection of a small amount of tagged water in well discharge. Recent applications of the application of extrinsic tracers, used in concert with intrinsic chemical and isotopic tracers, demonstrate the power of chemical analyses in interpreting regional subsurface flow regimes.
Date: September 13, 2007
Creator: Moran, J E; Singleton, M J; Carle, S F & Esser, B K
Partner: UNT Libraries Government Documents Department

Hydrologic resources management program. FY 1995 progress report

Description: This report presents the results of FY 1995 technical studies conducted by the Lawrence Livermore National Laboratory (LLNL) as part of the Hydrology and Radionuclide Migration Program (HRMP), a multi-agency program sponsored by the U.S. Department of Energy, Nevada Operations Office (DOE/NV), to address the environmental consequences of nuclear weapons testing at the Nevada Test Site (NTS). A priority is to better characterize the complex near-field environment in order to assess and predict the movement of radionuclides in groundwater. Other participating organizations include the Los Alamos National Laboratory (LANL), the U.S. Geological Survey (USGS) and the Desert Research Institute (DRI) of the University of Nevada. A radiologic source term in excess of 10{sup 8} curies of tritium, fission products, activation products and actinides is residual from more than three decades of underground nuclear weapons testing at the Nevada Test Site (NTS). Burial depths to insure containment of these explosions necessitated firing approximately one third of the more than 800 underground nuclear tests within one cavity radius or below the static water table. Work at LLNL has focused on studies of radionuclide transport under saturated, partially saturated or unsaturated conditions as well as investigations of the stable, radiogenic and cosmogenic isotope systematics of NTS groundwaters. LLNL has prioritized these studies because of the significance for potential radionuclide migration at the Nevada Test Site. LLNL utilizes expertise in nuclear weapons testing, radiochemical diagnostics, nuclear test phenomenology, mass spectrometry, aqueous geochemistry and field and laboratory studies of radionuclide migration to bring a unique measurement and interpretative capability to this research.
Date: March 1, 1996
Creator: Smith, D.K.; Esser, B.K. & Kenneally, J.M.
Partner: UNT Libraries Government Documents Department

Uncertainties associated with the definition of a hydrologic source term for the Nevada Test Site

Description: The U.S. Department of Energy, Nevada Operations Office (DOE/NV) Environmental Restoration Division is seeking to evaluate groundwater contamination resulting from 30 years of underground nuclear testing at the Nevada Test Site (NTS). This evaluation requires knowledge about what radioactive materials are in the groundwater and how they are transported through the underground environment. This information coupled with models of groundwater flow (flow paths and flow rates) will enable predictions of the arrival of each radionuclide at a selected receptor site. Risk assessment models will then be used to calculate the expected environmental and human doses. The accuracy of our predictions depends on the validity of our hydrologic and risk assessment models and on the quality of the data for radionuclide concentrations in ground water at each underground nuclear test site. This paper summarizes what we currently know about radioactive material in NTS groundwater and suggests how we can best use our limited knowledge to proceed with initial modeling efforts. The amount of a radionuclide available for transport in groundwater at the site of an underground nuclear test is called the hydrologic source term. The radiologic source term is the total amount of residual radionuclides remaining after an underground nuclear test. The hydrologic source term is smaller than the radiologic source term because some or most of the radionuclide residual cannot be transported by groundwater. The radiologic source term has been determined for each of the underground nuclear tests fired at the NTS; however, the hydrologic source term has been estimated from measurements at only a few sites.
Date: May 1, 1995
Creator: Smith, D.K.; Esser, B.K. & Thompson, J.L.
Partner: UNT Libraries Government Documents Department

California GAMA Special Study: An isotopic and dissolved gas investigation of nitrate source and transport to a public supply well in California's Central Valley

Description: This study investigates nitrate contamination of a deep municipal drinking water production well in Ripon, CA to demonstrate the utility of natural groundwater tracers in constraining the sources and transport of nitrate to deep aquifers in the Central Valley. The goal of the study was to investigate the origin (source) of elevated nitrate and the potential for the deep aquifer to attenuate anthropogenic nitrate. The site is ideal for such an investigation. The production well is screened from 165-325 feet below ground surface and a number of nearby shallow and deep monitoring wells were available for sampling. Furthermore, potential sources of nitrate contamination to the well had been identified, including a fertilizer supply plant located approximately 1000 feet to the east and local almond groves. A variety of natural isotopic and dissolved gas tracers including {sup 3}H-{sup 3}He groundwater age and the isotopic composition of nitrate are applied to identify nitrate sources and to characterize nitrate transport. An advanced method for sampling production wells is employed to help identify contaminant contributions from specific screen intervals. Nitrate transport: Groundwater nitrate at this field site is not being actively denitrified. Groundwater parameters indicate oxic conditions, the dissolved gas data shows no evidence for excess nitrogen as the result of denitrification, and nitrate-N and -O isotope compositions do not display patterns typical of denitrification. Contaminant nitrate source: The ambient nitrate concentration in shallow groundwater at the Ripon site ({approx}12 mg/L as nitrate) is typical of shallow groundwaters affected by recharge from agricultural and urban areas. Nitrate concentrations in Ripon City Well 12 (50-58 mg/L as nitrate) are significantly higher than these ambient concentrations, indicating an additional source of anthropogenic nitrate is affecting groundwater in the capture zone of this municipal drinking water well. This study provides two new pieces of evidence that the ...
Date: April 14, 2010
Creator: Singleton, M J; Moran, J E; Esser, B K; Roberts, S K & Hillegonds, D J
Partner: UNT Libraries Government Documents Department

Saturated Zone Denitrification at California Dairies

Description: Denitrification can effectively mitigate the problem of high nitrate concentrations in groundwater under dairy operations by reducing nitrate to N{sub 2} gas, at sites where biogeochemical conditions are favorable. We present results from field studies at central California dairies that document the occurrence of saturated-zone denitrification in shallow groundwater using biomolecular indicators, stable isotope compositions of nitrate, and measurements of dissolved excess N{sub 2} gas. Excess N{sub 2} concentrations provide a measure of the extent to which nitrate in groundwater has been partially or completely denitrified. Abundant excess N{sub 2} and young {sup 3}H/{sup 3}He apparent groundwater ages indicate high denitrification rates near manure lagoons where multiple lines of evidence indicate seepage of lagoon water into the groundwater system. Natural tracers of lagoon water include high chloride and dissolved organic carbon concentrations, distinctive trace organic compounds, and high groundwater {delta}{sup 18}O values (relative to other recharge sources). Proximal to the lagoons, NH{sub 4}{sup +} may be present in groundwater, but is strongly adsorbed on to sediment particles. Bubble formation in the lagoons causes the exsolution of other gases (N{sub 2}, Ar, Ne, He, etc.), which partition into the gas phase and strip the lagoon water of its dissolved gas load, providing a unique tracer of lagoon seepage in groundwater.
Date: February 27, 2006
Creator: Singleton, M J; Esser, B K; Moran, J E; McNab, W W & Beller, H R
Partner: UNT Libraries Government Documents Department

Sources of groundwater nitrate revealed using residence time and isotope methods

Description: Nitrate concentrations approaching and greater than the maximum contaminant level (MCL) are impairing the viability of many groundwater basins as drinking water sources. Nitrate isotope data are effective in determining contaminant sources, especially when combined with other isotopic tracers such as stable isotopes of water and tritium-helium ages to give insight into the routes and timing of nitrate inputs to the flow system. This combination of techniques is demonstrated in Livermore, CA, where it is determined that low nitrate reclaimed wastewater predominates in the northwest, while two flowpaths with distinct nitrate sources originate in the southeast. Along the eastern flowpath, {delta}{sup 15}N values greater than 10{per_thousand} indicate that animal waste is the primary source. Diminishing concentrations over time suggest that contamination results from historical land use practices. The other flowpath begins in an area where rapid recharge, primarily of low-nitrate imported water (identified by stable isotopes of water and a tritium-helium residence time of less than 1 year), mobilizes a significant local nitrate source, bringing groundwater concentrations up to 53 mg NO{sub 3} L{sup -1}. In this area, artificial recharge of imported water via local arroyos increases the flux of nitrate to the regional aquifer. The low {delta}{sup 15}N value (3.1{per_thousand}) in this location implicates synthetic fertilizer. In addition to these anthropogenic sources, natural nitrate background levels between 15 and 20 mg NO{sub 3} L{sup -1} are found in deep wells with residence times greater than 50 years.
Date: October 7, 2004
Creator: Moore, K B; Ekwurzel, B; Esser, B K; Hudson, G B & Moran, J E
Partner: UNT Libraries Government Documents Department

Dissolved gas and isotopic tracers of denitrification

Description: We present results from field studies in California (USA) where tritium-helium age dating is used in conjunction with major gases (N{sub 2}, O{sub 2}, CH{sub 4}, CO{sub 2}), noble gases (He, Ne, Ar, Kr, Xe), and stable isotopes ({sup 15}N/{sup 14}N, {sup 18}O/{sup 16}O) in order to document nitrate loading and denitrification associated with confined animal agricultural operations and septic systems. Preliminary results show that in-field extraction of the full suite of dissolved gases will be possible using a new Gas Extraction System under development to augment the current Noble Gas Mass Spectrometry and Membrane Inlet Mass Spectrometry techniques. Ascribing observed groundwater nitrate levels to specific current and past land use practices is often complicated by uncertainty in groundwater age and the degree and locus of dentrification. Groundwater age dating at dairy field sites using the {sup 3}H-{sup 3}He method indicates that the highest nitrate concentrations (150-260 mg/L-NO3) occur in waters with apparent ages of <5 yrs, whereas older waters contain excess N{sub 2} from saturated zone denitrification [1]. At a residential septic system site in Livermore, CA, waters with young apparent ages (<1 yr) proximal to leach line drainage have lower nitrate concentrations and elevated nitrate {delta}{sup 15}N and {delta}{sup 18}O values consistent with denitrification, but little evidence for excess N{sub 2}, indicating that denitrification is occurring in the unsaturated zone. Degassing of groundwater can complicate efforts to calculate travel times [2] and to quantify denitrification. Degassed groundwater underlying dairy operations is formed by two distinct mechanisms: (1) recharge of manure lagoon water affected by biogenic gas ebullition [3] and (2) saturated zone denitrification producing N{sub 2} gas above solubility in groundwater. Gas loss due to both mechanisms is evident in the concentrations of noble gases and major gases in dairy groundwater samples.
Date: February 28, 2008
Creator: Singleton, M J; Moran, J E; Esser, B K; McNab, W W; Carle, S F & Cey, B D
Partner: UNT Libraries Government Documents Department