A critical component of the State Water Resource Control Board's Groundwater Ambient Monitoring and Assessment (GAMA) Program is to assess the major threats to groundwater resources that supply drinking water to Californians (Belitz et al., 2004). Nitrate is the most pervasive and intractable contaminant in California groundwater and is the focus of special studies under the GAMA program. This report presents results of a study of nitrate contamination in the aquifer beneath the cities of Morgan Hill and Gilroy, CA, in the Llagas Subbasin of Santa Clara County, where high nitrate levels affect several hundred private domestic wells. The main objectives of the study are: (1) to identify the main source(s) of nitrate that issue a flux to the shallow regional aquifer (2) to determine whether denitrification plays a role in the fate of nitrate in the subbasin and (3) to assess the impact that a nitrate management plan implemented by the local water agency has had on the flux of nitrate to the regional aquifer. Analyses of 56 well water samples for major anions and cations, nitrogen and oxygen isotopes of nitrate, dissolved excess nitrogen, tritium and groundwater age, and trace organic compounds, show that synthetic fertilizer is the most likely source of nitrate in highly contaminated wells, and that denitrification is not a significant process in the fate of nitrate in the subbasin except in the area of recycled water application. In addition to identifying contaminant sources, these methods offer a deeper understanding of how the severity and extent of contamination are affected by hydrogeology and groundwater management practices. In the Llagas subbasin, the nitrate problem is amplified in the shallow aquifer because it is highly vulnerable with high vertical recharge rates and rapid lateral transport, but the deeper aquifers are relatively more protected by laterally extensive aquitards. Artificial recharge delivers low-nitrate water and provides a means of long-term remediation. Examination of nitrate concentration in relation to groundwater age indicates that the nitrate management plan has not yet resulted in a decrease in the flux of nitrate to the shallow aquifer in the areas tested.

Nitrate is the number one drinking water contaminant in the United States. It is pervasive in surface and groundwater systems, and its principal anthropogenic sources have increased dramatically in the last 50 years. In California alone, one third of the public drinking-water wells has been lost since 1988 and nitrate contamination is the most common reason for abandonment. Effective nitrate management in groundwater is complicated by uncertainties related to multiple point and non-point sources, hydrogeologic complexity, geochemical reactivity, and quantification of dentrification processes. In this paper, we review an integrated experimental and simulation-based framework being developed to study the fate of nitrate in a 25 km-long groundwater subbasin south of San Jose, California, a historically agricultural area now undergoing rapid urbanization with increasing demands for groundwater. The modeling approach is driven by a need to integrate new and archival data that support the hypothesis that nitrate fate and transport at the basin scale is intricately related to hydrostratigraphic complexity, variability of flow paths and groundwater residence times, microbial activity, and multiple geochemical reaction mechanisms. This study synthesizes these disparate and multi-scale data into a three-dimensional and highly resolved reactive transport modeling framework.

A critical component of the State Water Resource Control Board's Groundwater Ambient Monitoring and Assessment (GAMA) Program is to assess the major threats to groundwater resources that supply drinking water to Californians (Belitz et al., 2004). Nitrate concentrations approaching and greater than the maximum contaminant level (MCL) are impairing the viability of many groundwater basins as drinking water sources Source attribution and nitrate fate and transport are therefore the focus of special studies under the GAMA program. This report presents results of a study of nitrate contamination in the aquifer beneath the City of Livermore, where high nitrate levels affect both public supply and private domestic wells. 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, 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 above the MCL of 45 mg NO{sub 3} L{sup -1}. In this area, artificial recharge of imported water via local arroyos induces flux of the contaminant to the regional aquifer. The low {delta}{sup 15}N value (3.1{per_thousand}) in this location implicates synthetic fertilizer. Geochemical modeling supports the hypothesis of separate sources, one including organic carbon, as from animal waste, and one not. 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.

In response to concerns expressed by the California Legislature and the citizenry of the State of California, the State Water Resources Control Board (SWRCB), implemented a program to assess groundwater quality, and provide a predictive capability for identifying areas that are vulnerable to contamination. The program was initiated in response to concern over public supply well closures due to contamination by chemicals such as MTBE from gasoline, and solvents from industrial operations. As a result of this increased awareness regarding groundwater quality, the Supplemental Report of the 1999 Budget Act mandated the SWRCB to develop a comprehensive ambient groundwater-monitoring plan, and led to the initiation of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The primary objective of the GAMA Program is to assess the water quality and to predict the relative susceptibility to contamination of groundwater resources throughout the state of California. Under the GAMA program, scientists from Lawrence Livermore National Laboratory (LLNL) collaborate with the SWRCB, the U.S. Geological Survey (USGS), the California Department of Health Services (DHS), and the California Department of Water Resources (DWR) to implement this groundwater assessment program. In 2003, LLNL carried out this vulnerability study in the groundwater basin that underlies Bakersfield, in the southern San Joaquin Valley. The goal of the study is to provide a probabilistic assessment of the relative vulnerability of groundwater used for the public water supply to contamination from surface sources. This assessment of relative contamination vulnerability is made based on the results of two types of analyses that are not routinely carried out at public water supply wells: ultra low-level measurement of volatile organic compounds (VOCs), and groundwater age dating (using the tritium-helium-3 method). In addition, stable oxygen isotope measurements help determine the recharge water source location. Interpreted together, and in the context of existing water quality and hydrogeologic data, these observable parameters help define the flow field of a groundwater basin, and indicate the degree of vertical communication between near-surface sources (or potential sources) of contamination, and deeper groundwater pumped at high capacity production wells.

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.

Isotopic tracers, such as stable isotopes of the water molecule and tritium, have been used in investigations of groundwater flow and transport and recharge water source for several decades. While these data can place hard constraints on groundwater flow rates, the degree of vertical flow between aquifers and across aquitards, and recharge source area(s), they are rarely used, even for validation, in conceptual or numerical models of groundwater flow. The Groundwater Ambient Monitoring and Assessment Program, sponsored by the California State Water Resources Control Board, and carried out in collaboration with the U.S. Geological Survey, has provided the means to gather an unprecedented number of tritium-helium groundwater ages in the basins of California. As the examples below illustrate, a collection of groundwater ages in a basin allows delineation of recharge areas (youngest ages), bulk flow rates and flowpaths, as well as a means of assessing susceptibility to anthropogenic contaminants.

This report contains highlights of FY 2001 and 2002 technical studies conducted by the Analytical and Nuclear Chemistry Division (ANCD) at Lawrence Livermore National Laboratory (LLNL) in support of the Hydrologic Resources Management Program (HRMP) and the Underground Test Area (UGTA) Project. These programs are administered by the U.S. Department of Energy, National Nuclear Security Administration, Nevada Site Office (NNSA/NSO) through the Defense Programs and Environmental Restoration Divisions, respectively. HRMP-sponsored work emphasizes the Defense Programs goal of responsible management of natural resources at the NTS, while UGTA-funded work focuses on defining the extent of radionuclide contamination in NTS groundwater resulting from underground nuclear testing. The report is organized on a topical basis, and contains eight chapters that reflect the range of technical work performed by LLNL-ANCD in support of HRMP and UGTA. Chapter 1 describes recent hot well sampling efforts at the NTS, and presents the results of chemical and isotopic analyses of groundwater samples from six near-field wells. These include the Cambric (UE-5n), Bilby (U-3cn PS No. 2), Bourbon (UE-7nS), Nash (UE-2ce), Tybo/Benham (ER-20-5 No. 3), and Almendro (U-19v PS No. 1ds) sites. The data generated by the hot well program is vital to the development and validation of contaminant transport models at the NTS. Chapter 2 discusses the results of xenon isotope measurements of groundwater samples from the six near-field wells described in Chapter 1. This work demonstrates that fission xenon is present in the water at levels that are readily measurable and highlights the significant differences in xenon concentrations and isotopic abundances at different sites. These differences provide insight into the early cooling history of nuclear test cavities, and may assist in predicting the distribution of the source term in the near-field environment. Chapter 3 is an investigation of the distribution and abundance of actinides in a nuclear test cavity and chimney. This work demonstrates that early-time processes can widely disperse actinides at low concentrations outside the melt glass, implying that melt glass dissolution may not be the sole mechanism for the release of actinides to groundwater. The study also provides evidence for the isotopic fractionation of plutonium under the extreme conditions accompanying nuclear explosions. In Chapter 4, X-ray absorption spectroscopy measurements were used to determine the redox state of Fe and U in nuclear melt glass samples from the NTS. Both elements were found to occur in mixed valence states (Fe{sup 2+}/Fe{sup 3+} and U{sup 5+}/U{sup 6+}) in all samples. Comparison of the Fe and U redox states with published redox studies of synthetic glasses suggests that plutonium is predominantly in the Pu{sup 4+} oxidation state in the melt glasses. In Chapter 5, alpha autoradiography is used in a NTS field study to investigate the spatial distribution and transport of actinides in soils, and to help identify the size distribution and morphology of the actinide particles. It was found that {alpha}-emitting radionuclides have moved to at least 39 cm depth in the soil profile, far deeper than expected. The methodology that was developed could easily be applied to other field locations where actinides are dispersed in the soil zone. Chapter 6 summarizes the development of a method for measuring environmental levels of {sup 241}Am on the multi-collector inductively coupled plasma mass spectrometer. The method detection limit of 0.017 pCi/L is about two times lower than the best analyses possible by alpha spectrometry. Chapter 7 describes a chlorine-36 study of vertical groundwater transport processes in Frenchman Flat. Mass balance calculations developed from a {sup 36}Cl mixing model at well ER-5-3 No. 2 are used to estimate vertical transport fluxes and average vertical flow velocities through the thick volcanic section underlying the basin. The study also documents the variations in {sup 36}Cl/Cl ratios within the three principal hydrostratigraphic units in Frenchman Flat. Chapter 8 discusses an ongoing stable isotope investigation of precipitation and recharge processes in central Nevada. Precipitation, spring water, and shallow infiltration samples have been collected at four locations on a biannual basis since 1999. The results show that winter precipitation accounts for>90% of the recharge at these sites. Lysimeter data suggest that most of the evaporation occurring during recharge is due to water vapor loss through the soil zone during periods of slow infiltration. In addition to the topical investigations described above, LLNL-ANCD contributed to several other major collaborative technical products during FY 2001 and 2002.

The fate and transport of iodine in the environment is of interest because of the large production and release of {sup 129}I from anthropogenic sources. {sup 129}I has a long half-life (1.57 x 10{sup 7} years) and exhibits complex geochemical behavior. The main source of {sup 129}I in the environment is from nuclear fuel reprocessing facilities; about 2,600 kg from facilities in England and France. During 1944-1972, the Hanford Site in Washington state released about 260 kg {sup 129}I. Iodine has a unique and complex chemistry in the environment, and its fate and transport in aqueous environments is dictated by its chemical speciation. In reducing environments, aqueous iodine usually occurs as the highly mobile iodide anion (I{sup -}). Under more oxidizing conditions, iodine may be present as the more reactive iodate anion (IO{sub 3}{sup -}), which could lead to retarded transport through interaction with clays and organic matter. Co-existing iodine species (I{sup -}, IO{sub 3}{sup -}, I{sub 2}, and organoiodine compounds), in different proportions, has been reported in various terrestrial environments. However, there are conflicting reports regarding the environmental behavior of the different types of inorganic iodine and few publications on organic iodine compounds. This work examines the sorption and transport behavior of both inorganic and organic iodine species in geological samples from several complexes of the U.S. Department of Energy, where transport of radionuclides, including {sup 129}I, may occur. Experiments on soils and sediments from the Savannah River Site in South Carolina, Oak Ridge Site in Tennessee, Hanford Site in Washington, Livermore Site 300 in California, and a surface soil from Santa Fe in New Mexico near Los Alamos were carried out. Samples from Savannah River Site and Livermore Site 300 are available from different depths. In addition, a surface soil of Wisconsin with a high amount of organic matter is utilized. This wide variety of sample types provides opportunities to examine the influence of organic matter, clay mineralogy, soil pH, and texture on the environmental behavior of iodine. The effects of initial concentration and competitive sorption on iodine transport are also investigated.