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PROPOSAL NARRATIVE New Groundwater Tracer Systems for Managed Recharge Lead co-PI: A. T. Fisher, UCSC I. Introduction and Motivation A. Groundwater and Overdraft in California Groundwater supplies ~40% of annual fresh water demand in California under "normal" hydrologic conditions, and up to ~60% of demand during dry years [1]. Increasing population, continuing agricultural and municipal development, and anticipated changes to the state's hydrologic cycle in response to a changing climate (including the intensity, location, and seasonal variability of precipitation) all pose challenges for the successful management of water resources. Unfortunately, many groundwater basins in California are currently in overdraft and continued pumping is harming environmental resources and systems [2-4]. Groundwater overdraft can lead to land subsidence (and an associated loss of storage capacity), seawater intrusion, reductions in base flow to streams, and reductions in both surface and groundwater quality and the health of aquatic habitat [5-8]. California operates the most extensive and expensive water transfer system in the world, but is struggling to capture, store, and distribute fresh water across the state. Existing reservoirs and infrastructure are inadequate, and many parts of the state are "off the grid," effectively restricted to meeting growing water demand with local supplies. Enhanced groundwater replenishment and storage will be increasingly important throughout California in coming years [1], but work is needed to understand the impacts of this water management strategy on subsurface water supplies and quality. In addition, new regulations require development of tools to assess and operate recharge systems. We will address these needs with the work proposed, while accomplishing fundamental research.

B. Managed Recharge, Retention Time, and the Needs for Tracer Studies Managed aquifer recharge (MAR) mitigates groundwater overdraft by facilitating the transfer of surface water into aquifers. Additionally, it can improve water quality and provide a buffer against droughts and other variability in the hydrologic cycle. The most common method of MAR uses surface infiltration through spreading basins or ponds for aquifer replenishment, similar to soil-aquifer treatment [e.g., 9, 10]. The chemical composition of infiltrating water changes as it passes through the vadose zone into an underlying aquifer, where it mixes with ambient groundwater. Changes to water quality arise from physical and biogeochemical processes, often leading to improved groundwater quality [e.g., 9, 11, 12] Regulations prescribed by the California Department of Public Health (CDPH) require that artificially recharged water has a sustained travel time through aquifers prior to production, in order to allow sufficient dilution, attenuation, and biogeochemical processing of potential contaminants and pathogens [13]. CDPH requires the largest safety margins (12-24 month travel times) for use of modeling studies to estimate retention time to wells based on physical aquifer characteristics. More confidence is assigned to studies involving intrinsic tracers, where a nine-month travel time is required. By far the greatest confidence is assigned to studies involving introduced tracers (six-month travel time). One of the best tracers for determining groundwater travel times, sulfur hexafluoride (SF6), was developed more than a decade ago [14, 15]. SF6 has been used to date for more than ten experiments in California [e.g., 14, 15-18]. However, the California Air Resources Board (CARB) is in the process of regulating emission of SF6; its rules will limit methods of introduction of this strong green house gas to the atmosphere. Furthermore, the U.S. EPA has recently determined that SF6 and other greenhouse gases are pollutants, and future federal regulations may prevent widespread use of SF6 as a groundwater tracer. Most tracers used in surface hydrology (e.g., Br, rhodamine dye) cannot be used economically to tag large volumes associated with managed recharge, frequently >12 million liters/day (>10 ac-ft/day).

New Groundwater Tracer Systems for Managed Recharge Lead co-PI: A. T. Fisher, UCSC

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Several other tracers have been proposed as replacements for SF6, including introduced isotopes of helium, boron, or xenon. Xenon isotopes have been tested as MAR tracers by LLNL [15, 19] but conventional sampling and analytical methods are too costly for broad application. 3He has been tested in conjunction with SF6 [16], and 10B-enriched borate was tested in conjunction with Xenon isotopes [20], but these alternatives are too complex and expensive for routine use.

II. Project Goals, Methods, and Responsibilities A. Project Goals We propose to conduct highly controlled MAR tracer experiments with newly developed sampling and analytical methods that will test the accuracy of travel time calculations, and assess protocols and costs for widespread use. We will focus particularly on two developmental groundwater tracers that have not been used extensively in groundwater studies: the noble gas Xenon (Xe, introduced) and the cosmogenic isotope Sulfur-35 (35S, intrinsic). These tracers will be used simultaneously with SF6 (introduced) during MAR operations at a field site in southern Santa Cruz County, where there is an extensive network of monitoring wells with dedicated sampling pumps and other infrastructure needed to trace flow paths, travel times, and changes to water quality. Samples will be collected both manually and continuously using novel osmotic pumping systems, which operate autonomously for months at a time without electric power or moving parts. The development of the latter sampling strategy will reduce a long-standing limitation and one of the primary costs of the current method: the need for field personnel to travel to (often remote) field sites to sample wells frequently following a predetermined schedule that may not be consistent with flow rates or pathways. Samples will be analyzed for Xe content using an innovative noble gas–membrane inlet mass spectrometer (NG-MIMS), capable of identifying tracer concentrations much more rapidly and at a fraction of the cost associated with conventional mass spectrometry. Samples will also be collected for analysis of SF6, 35S, major ions and water isotopes, allowing a side-by-side comparison of multiple tracers, and an assessment of MAR impacts on water quality. Work will be completed by a diverse team of UC and LLNL researchers, post-docs, graduate students, and undergraduate students, in partnership with colleagues from a local water agency who will provide staff support and access to key facilities, equipment, and data. This study will have important implications for MAR operations in the region, where the viability of operating additional projects is being assessed; will provide data and samples for use in student theses, presentations, and peer-reviewed papers; and will have broad applicability across California.

B. Novel experimental and analytical techniques Tracer introduction by diffusion tubing: A gas mixture of Xe and SF6 will be introduced by gas diffusion through silicone tubing, which will be installed at the bottom of a MAR pond (Fig. 1) when the system is dry (between operating seasons). Introduction of gas by diffusion tubing [21, 22] has the great advantage that no tracer gas is directly lost to the atmosphere. Previous studies of bubbling SF6 through the water column showed that the dissolution efficiency may be as low as 4% [23], which is not economical for Xe. A previous experiment diffusing Xe into a pond suggested dissolution efficiency close to 100% (LLNL, unpublished data). This injection method also leads to better known rates of introduction. Both SF6 and Xe are inert, pose no health risks, and have been approved for use in potable aquifers.


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Figure 1. A. Regional map showing central coastal California, with HS-MAR (filled dot.) B. Areal photograph showing Watsonville Sloughs and HS-MAR recharge pond at lower left. C. Map of HS-MAR with locations of wells screened in shallow and deeper aquifers (open and filled circles, respectively). Tracer injection and sampling of MAR water during experiments will be completed from the NE side of the pond, inside a locked gate.

OsmoSamplers: OsmoSamplers [24] will be deployed to collect a continuous record of tracer concentrations. OsmoSamplers (Fig. 2) are polycarbonate tubes with an internal dialysis membrane that separates a flexible, supersaturated salt reservoir from a small-diameter sampling coil, which is prefilled with deionized water. The deionized water is drawn through the membrane into the salt reservoir, pulling ambient fluid samples up and into a sample coil. OsmoSamplers have been used mainly in estuaries and the deep ocean, where they have collected and stored high-quality solute and gas samples for up to five years before recovery [e.g.,25, 26, 27]. Researchers recently adapted OsmoSamplers for use in groundwater studies [Fig. 2., 12], but thus far they have never been used for groundwater tracer studies. For the present application, we will use gas-tight copper tubing, and test fast-sampling reverse-osmosis membranes, rather than conventional dialysis membranes, to increase the sample rate as needed for tracer studies (to get daily resolution). Samples will be collected manually from the same wells while the OsmoSamplers are deployed, using dedicated pumps, allowing a side-by-side comparison of results based on the different methods. NG-MIMS: A new bench top Noble Gas Membrane Inlet Mass Spectrometer (NG-MIMS), recently developed at LLNL (Record of Invention filed in March 2011), can measure real time concentrations of noble gases dissolved in groundwater and surface water [28, 29]. In the new NG-MIMS, water flows along a semi-permeable membrane, through which the gases dissolved in the sample are extracted [30]. Reactive gases (e.g., N2, O2, H2O) are removed by traps and getters and the noble gases are continuously measured in the mass spectrometer. The MIMS measures the concentrations of all noble gases (He, Ne, Ar, Kr, Xe) simultaneously every 10 seconds. Besides the arrival of the tracer Xe, this suite of noble gas concentrations will reveal important characteristics of gas partitioning and air entrapment processes during MAR [16, 31, 32]. The NG-MIMS provides fast and cost-effective noble gas analyses.

OsmoSamplers and the NG-MIMS are theoretically well suited to be combined, but there is a technical challenge in transferring the sample from the coil through the membrane without disturbing the high-resolution temporal signal. UC graduate students will collaborate closely with LLNL staff to find the optimal method of extraction. The combination of Xenon as an


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introduced tracer, high-resolution (continuous) sampling, and the NG-MIMS as analytical tool is truly novel and has potential for being transformational in hydrologic research.

Figure 2. Novel experimental systems to be adapted for use in the present study. A. OsmoSampling system prepared for deployment in a groundwater well. B. Example data from an OsmoSampler pilot study of chemical variability. Lines show data collected with an autonomous OsmoSampler, whereas symbols show results of analyses from samples pumped manually from the same wells. C. Cross plot of [NO3] versus [Cl] data from an OsmoSampler in a groundwater well at the MAR site to be tested in the proposed study, showing abrupt changes in major solute concentrations as a result of mixing between end-members (ambient groundwater, natural recharge, MAR water). D. LLNL NG-MIMS system arrayed on workbench.

Sulfur-35: We also propose to explore use of 35S as an intrinsic tracer for groundwater age dating. The advantages of this tracer include: 1) a half life of 87.4 days, being well-suited for determining travel times of weeks to one year, as appropriate for MAR operations and CDPH rules, 2) natural occurrence in the environment, allowing virtually continuous recharge with source water, and 3) allowing assessment of mean travel times under different recharge conditions throughout long-term MAR operations. Because 35S is naturally occurring, there is no cost associated with “tagging” the source water, nor is there the need to for regulatory approval. Results from 35S will be compared to results from simultaneous introduced tracer experiments. Large volume (5-20 liter depending on sulfate concentration) samples will be collected for 35S analysis. 35S activity will be determined using a customized batch method based on techniques developed at LLNL [33]. Processed samples will be analyzed on liquid scintillation counters (Quantulus model 1220) having ultra low background, located in a deep basement laboratory at LLNL.

C. Experimental Field Site The primary field site comprises the Harkins Slough MAR (HS-MAR) system (Figs. 1, 3), located near Santa Cruz, and operated by the Pajaro Valley Water Management Agency (PVWMA). The PVWMA is permitted to divert up to 2000 ac-ft/yr from Harkins Slough (a nearby wetland) during the winter rainy season when there is sufficient flow and relatively high water quality. Diverted water is passed through a sand filter and pumped into a recharge pond, which is a modified natural depression ~3 ha in area. Infiltration through the base of this pond creates a local water table mound, temporarily increasing storage within a perched aquifer that overlies a clay layer ~30 m below the base of the pond (Fig 3). Recharged water is recovered


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from the shallow aquifer using dedicated wells that encircle the pond. UCSC researchers have collaborated with the PVWMA and others on studies of shallow processes during MAR at this site, to assess the spatial and temporal distribution of infiltration and biogeochemistry [12, 34, 35] but no tracer tests have been run to date. Proposed work will leverage experience gained during earlier projects, accelerating the pace of discovery through the proposed tracer studies.

Figure 3: Three-dimensional cartoon showing geometry of proposed MAR tracer experiments, using the Harkins Slough facility. Two introduced tracers will be added to the infiltration pond during the early stages of MAR (Xe, SF6), whereas an intrinsic tracer (35S) will be added throughout MAR diversions from Harkins Slough. When the HS-MAR system was established, the

PVWMA installed ten monitoring wells screened in the (shallow) perched aquifer (PV11 and MW-1 to MW-9), and subsequently added a monitoring well screened in the regional (deep) Aromas aquifer (DMW-1). In 2011 the PVWMA added three additional monitoring wells screened in the deeper aquifer, but at somewhat shallower depths (medium, MMW-1 to MMW-3) (Fig. 1C). The complete set of 14 monitoring wells is instrumented with pressure loggers to record water levels, and dedicated bladder pumps to permit efficient collection of high-quality samples. Monitoring and sampling from the complete set of wells will allow direct inter-comparison of tracer behavior, in addition to evaluation of MAR fate and influence in this setting

D. Experimental and Analytical Plan We propose a three-year project including two primary field seasons and an additional year for continued sampling, data analysis, and preparation of reports, presentations, thesis chapters, and papers. When the project begins (July 2012), the MAR pond will be dry. We will collect multiple rounds of background samples from monitoring wells and nearby Harkins Slough, and activate and calibrate water level loggers installed in wells for the coming year. OsmoSamplers will be deployed in two of the shallow monitoring wells and two of the deeper wells, selected on the basis of historical chemical and water level data, in consultation with the PVWMA. The tracer injection system will be assembled and deployed in the field prior to the start of MAR operations. Gas emitter tubing will be extended from the side of the pond, while the pond is dry, and fittings established along the pond margin where gas manifold systems can be attached for injection. Fluid sampling lines also will be installed across the base of the pond, so that samples can be collected before, during, and after tracer injection. Once diversion from Harkins Slough to the pond begins (most likely in December or January), we will collect several rounds of samples (wells, pond, slough) in rapid succession, and deploy a fifth gas-tight OsmoSampler in the pond (by boat), to provide a continuous record of MAR water composition. Tracer injection will begin 5-7 days after the start of MAR operations and submersion of the tracer emitting tubing, when diversion rates are 12-15 ac-ft/day and whole-pond infiltration rates are >1 m/day (Racz et al., 2011), with injection continuing for 5–7 days. To be able to detect 1%


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of tagged water we will increase the concentration of Xenon by more than a factor of 10, relative to background, requiring introduction of ~25 L of xenon into HS MAR pond during the tracer injection period. We will similarly increase SF6 concentrations above detection level by several orders of magnitude, to assure utility of the tracer following dilution and mixing. Synoptic sampling of the pond and wells will occur on a schedule of every 2 days (for 10 days), 5 days (for 20 days), 10 days (for 60 days), then monthly until end of water year. Samples for Xe and SF6 will be collected simultaneously. OsmoSampler data will confirm whether gas loss occurs during sampling with dedicated pumps. MAR is likely to end after 3–5 months of operations, but sampling will continue to assess MAR water travel times and fate for the full operational cycle. The OsmoSampler deployed in the pond will be recovered 2-3 weeks after the end of tracer injection, and OsmoSamplers in wells will be collected after 4-6 months, based on results of analyses from samples recovered from these same wells using pumps. Samples will be extracted from OsmoSampler tubing, then analyzed using methods described previously. Samples will be collected for 35S analysis monthly from the pond when wet and every other month from 5 nearby wells. All noble gas and 35S samples will be analyzed at LLNL; SF6 samples will be analyzed at UCSB. Samples also will be collected for analysis of water isotopes, major ions (including nutrients), dissolved oxygen, and DOC. This will allow assessment of additional intrinsic tracers and evaluation of changes to water quality associated with MAR. This topic is of fundamental concern to stakeholders and regulators, and contemporaneous colocation of tracer and water quality studies will provide fundamental information on impacts of MAR on water quality. Repeating the experiment in the second project year will provide numerous benefits, in addition to demonstration of experimental replicability, potentially including: changing injection duration and/or methods, adjusting sampling frequency, and modification of materials and/or wells selected for OsmoSampler deployment. The majority of samples collected during the first project year will be analyzed by June 2013 (some sampling will continue through the summer) so that results can be assessed and adjustments made to the field equipment, sampling, and analytical plan for the second project year. In addition, there are numerous conventional production wells located around the HS-MAR system, but these wells are cycled on and off at irregular intervals, and it is not apparent which wells might best be sampled to assess the longer-term fate of MAR water. Results from the first year will be used to target production wells to be included in second tracer experiment year. Samples collected during the second project year will be analyzed during Summer-Fall 2014. The remaining part of the third project year will be used for collaboration among the groups on interpretation of tracer testing and water quality results using available conceptual, analytical, and numerical models. Students and researchers will also prepare materials for presentations, thesis chapters, and papers to be submitted to peer-reviewed journals. These will emphasize particularly the implications for experimental results for aquifer replenishment and groundwater recharge in general, including the use of new tracer, sampling, and measurement systems to test development and operation of MAR facilities.

E. Collaborator Responsibilities UCSC personnel will be primarily responsible for coordination with the PVWMA, establishment of sample sites, operation of well monitoring equipment (pressure gauges, OsmoSamplers), synoptic sampling completed with dedicated bladder pumps, and sample analysis for water isotopes and major ions. UCSB personnel will be primarily responsible for injection of SF6 and analysis of SF6 and 35S samples. LLNL personnel will be primarily


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responsible for Xe injection and analysis of samples using the NG-MIMS, and will facilitate the 35S analysis. UCSC and UCSB graduate students will train in residence at LLNL on these techniques. It is anticipated that UCSC personnel will complete much of the field sampling, because the field site is relatively close, but UCSB and LLNL personnel will be involved in sampling particularly at the start of each of the first two project years, when sampling is most intense, and will teach other personnel how to collect samples for the various tracers. In addition, PVWMA personnel will complete synoptic sampling and will contribute to tracer sample collection (please see letter of support and budget justification).

III. UC Laboratory Fees Research Program Goals This project will establish new collaborations between LLNL, UCSC, and UCSB faculty, researchers, and students, with each bringing unique tools and expertise to the full project. This UC-Lab collaboration will provide mutual benefit. UCSC personnel have worked for several years to understand infiltration processes associated with the HS-MAR system, have experience with OsmoSampler systems, and established a strong working relationship with the PVWMA, but has not participated in groundwater tracer experiments. The UCSB team brings expertise and leadership in use of SF6 in groundwater tracer experiments, and is developing 35S as a potential tracer in collaboration with LLNL. The LLNL team developed the NG-MIMS and has particular expertise using noble gases to trace groundwater recharge. The facilities, expertise, access and cooperation that will be provided by the PVWMA will make this MAR tracer study one of the most comprehensive and nuanced to date, greatly enhancing the applicability of results broadly across the state and elsewhere. The proposed study will enhance research excellence and innovation by addressing fundamental theoretical and practical issues of water reuse and groundwater recharge processes and management. These field studies of MAR will involve the establishment of partly controlled, natural laboratories, in which the most cryptic and least understood part of the hydrologic cycle, groundwater recharge, can be quantified. The proposed work will 1) help to assess the meaning of travel time and groundwater age during the first few months of MAR, and 2) provide a direct, quantitative comparison of introduced and intrinsic tracer response, both of which are important for resource management. This project will engage and train UC graduate students, who will spend considerable time in residence at LLNL. The project will facilitate personnel exchanges between UC campuses and bring LLNL expertise more broadly to the UC system and surrounding communities. This project will also provide outstanding opportunities for a LLNL postdoctoral researcher, and for undergraduate researchers at UCSC and UCSB. This project is at the interface of basic and applied research, and will provide samples and data that allow assessment of: vadose zone processes during MAR, using intrinsic versus introduced tracers, and patterns of groundwater "age" in association with MAR. These results are essential for sustainable management of water resources in California, contributing significantly to development of statewide "water security" in the face of rising demand, reduced water quality, and ongoing and future climate change [1]. This project provides value in sharing access to unique tools and expertise at reasonable cost. Most of the personnel costs will support students and a postdoctoral researcher. Access to wells and use of dedicated pumps, and contributions by PVWMA staff, will bring enormous benefit to this project at no cost. Project personnel are contributing considerable additional resources (equipment, supplies, field vehicles, etc.), as discussed in the budget justification.


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24. Jannasch, H. W., C. G. Wheat, J. Plant, M. Kastner, D. Stakes, Continuous chemical monitoring with osmotically pumped water samplers: OsmoSampler design and applications, Limnol. Oceanogr.: Methods 2, 102-113, 2004.

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Principal Investigator: A. T. Fisher, UCSC

BIOGRAPHICAL SKETCH and OTHER SUPPORT

NAME: Andrew T. Fisher POSITION TITLE: Professor EDUCATION/TRAINING (Begin with baccalaureate or other initial professional education, such as nursing, and include postdoctoral training.)

INSTITUTION AND LOCATION DEGREE YEAR(s) FIELDS OF STUDY University of Miami, RSMAS Ph.D. 1984-89 Marine Geology, Geophysics, Hydrogeology

Stanford University B.S. 1980-84 Geology

A. Positions and Selected Honors.

1995 - present Assistant, Associate, Full Professor, Department of Earth and Planetary Sciences, University of California, Santa Cruz

2011 Bennett Lecturer, University of Leicester 2006 Fellow, Geological Society of America 2003-04 National Science Foundation – RIDGE Distinguished Lecturer 1996-97 JOI-USSAC Distinguished Lecturer 1993-95 Associate Scientist, Department of Geological Sciences and Indiana Geol. Survey, Indiana University 1989 F.G. Walton Smith Prize (best dissertation from RSMAS in 1989) B. Selected peer-reviewed publications (in chronological order, *student/former student coauthor).

*Spinelli, G. A., Fisher, A. T., Wheat, C. G., *Tryon, M. D., Brown, K. M., Flegal, A. R., Groundwater seepage into northern San Francisco Bay: implications for dissolved metals budgets, Wat. Resour. Res., 38 (7): 10.1029/2001WR000827, 2002.

Fisher, A. T., Marine hydrogeology: future prospects for major advances, Hydrogeol. J., 13: 69-97, DOI: 10.1007/s10040-004-0400-y, 2005.

*Ruehl, C., A. T. Fisher, C. Hatch*, M. Los Huertos, G. Stemler*, and C. Shennan. Differential gauging and tracer tests resolve seepage fluxes in a strongly-losing stream. Journal of Hydrology, 300: 235-248, 2006.

*Hatch, C. E., A. T. Fisher, J. S. Revenaugh, J. Constantz, and C. Ruehl*. Quantifying surface water - ground water interactions using time series analysis of streambed thermal records: method development. Water Resources Research, 42(10): 10.1029/2005WR004787, 2006.

*Ruehl, C., A. T. Fisher, M. Los Huertos, S. Wankel, C. Kendall, C. Hatch*, and C. Shennan. Nitrate dynamics within the Pajaro River, a nutrient-rich, losing stream. Journal of North American Benthological Society, 26(2): 191-206, 2007.

*Hutnak, M., A. T. Fisher, The influence of sedimentation, local and regional hydrothermal circulation, and thermal rebound on measurements of heat flux from young seafloor, J. Geophys. Res., 112, B12101, doi:10.1029/2007JB005022, 2007.

*Hutnak, M., Fisher, A. T., Harris, R., Stein, C., Wang, K., *Spinelli, G., Schindler, H., Villinger, H., Silver, E., Large heat and fluid fluxes driven through mid-plate outcrops on 21–23 Ma seafloor, Nature Geoscience, doi: 10.1038/ngeo264, 2008.

Becker, K., and A. T. Fisher, Borehole tests at multiple depths resolve distinct hydrologic intervals in 3.5-Ma upper oceanic crust on the eastern flank of the Juan de Fuca Ridge, J. Geophys. Res., 113, doi:10.1029/2007JB005446, 2008.

Fisher, A. T., Wheat, C. G., Seamounts as conduits for massive fluid, heat, and solute fluxes on ridge flanks, Oceanography, 23 (1): 74-87, 2010.

*Hatch, C. E., A. T. Fisher, C. Ruehl*, G. Stemler*, Spatial and temporal variations in streambed hydraulic conductivity quantified with time-series thermal methods, J. Hydrol., 389, doi: 10.1016/j.jhydrol.2010.05.046, 276-288, 2010.

Davis, E. E., and Fisher, A. T., Seafloor heat flow: methods and observations, Harsh K. Gupta (ed.), Encyclopedia of Solid Earth Geophysics, DOI 10.1007/ 978-90-481-8702-7, 2010.

Fisher, A. T., C. G. Wheat, K. Becker, J. Cowen, B. Orcutt, S. Hulme, K. Inderbitzen*, A. Turner*, T. Pettigrew, E. E. Davis, H. Jannasch, K. Grigar, R. Adudell, R. Meldrum, R. Macdonald, and K. Edwards, Design, deployment, and status of borehole observatory systems used for single-hole and cross-hole experiments, IODP Expedition 327, eastern flank of the Juan de Fuca Ridge, In A.T. Fisher, T. Tsuji, and K. Petronotis, Proc. IODP, Expedition 327, College Station, TX (Integrated Ocean Drilling Program), doi:10.2204/iodp.proc.327.107.2011.


*Schmidt, C. M., A. T. Fisher, A. J. Racz*, B. Lockwood and M. Los Huertos, Linking denitrification and infiltration rates during managed groundwater recharge, Env. Science & Tech., dx.doi.org/10.1021/es2023626, 2011.

*Racz, A. J., Fisher, A. T., *Schmidt, C. M., Lockwood, B. S., Los Huertos, M., Spatial and temporal infiltration dynamics during managed aquifer recharge, Ground Water, doi: 10.1111/j.1745-6584.2011.00875.x, 2011.

*Schmidt, C. M., A. T. Fisher, A. Racz*, C. G. Wheat, M. Los Huertos, B. Lockwood, Rapid nutrient load reduction during infiltration of managed aquifer recharge in an agricultural groundwater basin, Hydrol. Processes, in press, 2012.

*Russo, T. A., Fisher, A. T., Roche, J. W, Improving riparian wetland conditions based on infiltration and drainage behavior during and after controlled flooding, J. Hydrology, in press, 2012.

C. Research Support.

Name of Individual: Andrew T. Fisher ACTIVE Project Number (Principal Investigator): 210032 Source: Balance Hydrologics Title of Project (or Subproject): Influence of Managed Aquifer Recharge of Recycled Water on the Carmel River Lagoon Role: Subcontractor for infiltration testing, modeling The major goals of this project are to determine the potential for development of a constructed wetland and groundwater infiltration system for improving habitat for threatened fish OVERLAP: None.

Dates Project: 8/11-12/12 Annual Direct Costs: $22,455

Percent Effort: 4%

Project Number (Principal Investigator): OCE-1131210 (Fisher) Source: U.S. National Science Foundation Title of Project (or Subproject): Discovery, sampling, and quantification of flows from cool, massive ridge-flank hydrothermal springs on Dorado Outcrop, eastern Pacific Ocean Role: co-Principle Investigator The major goals of this project are to locate, sample, and measure flows of fluid, heat, and solutes from seafloor hydrothermal springs OVERLAP: None.

Dates of Project: 10/11-9/13 Annual Direct Costs: $54,597

Percent Effort: 8%

Project Number (Principal Investigator): OCE-1031808 (Fisher) Source: U.S. National Science Foundation Title of Project (or Subproject): Completion of single- and cross-hole hydrogeologic experiments on the eastern flank of the Juan de Fuca Ridge using a borehole network The major goals of this project are to conduct large-scale hydrogeologic, geochemical, and microbiological experiments in long-term borehole observatories OVERLAP: None.


Percent Effort: 4%

Project Number (Principal Investigator): ANT-0838947 (Fisher) Source: U.S. National Science Foundation (three awards) Title of Project (or Subproject): Integrative Study of Marine Ice Sheet Stability and Subglacial Life Habitats in West Antarctica-Robotic Access to Grounding -zones for Exploration and Science Role: co-Principle Investigator The major goals of this project are to develop and deploy tool to determine heat flow into base of Antarctic Ice Sheet, assess ice budgets and dynamics, sample subglacial fluids and microbiology OVERLAP: None.


Percent Effort: 6%

Principal Investigator: A. T. Fisher, UCSC Project Number (Principal Investigator): 149703 (Fisher) Source: University of Southern California (from U.S. NSF) Title of Project: Center for Deep Energy Biosphere Investigations Role: co-Principle Investigator The major goals of this project are to support a NSF Science and Technology Center, conduct hydrogeologic research on seafloor hydrothermal systems and the associated biosphere OVERLAP: None.


Percent Effort: 6%

Project Number (Principal Investigator): T327A07, B07 (Fisher) Source: Consortium for Ocean Leadership (two awards) Title of Project: Characterization of multi-scale permeability using borehole and regional hydrothermal models Role: Principle Investigator The major goals of this project are to assess the nature of hydrogeologic properties and processes in the upper oceanic crust. OVERLAP: None.


Percent Effort: 8%

Project Number (Principal Investigator): 2007CA195G (Fisher) Source: National Institutes for Water Resources Title of Project: Improving aquifer storage recovery operation to reduce nutrient load and benefit water supply Role: Principle Investigator The major goals of this project are to quantify infiltration processes and their influence on water supply and quality during managed recharge. OVERLAP: Assessed shallow infiltration conditions and processes at same site proposed for tracer studies in present proposal


Percent Effort: 4%

Andrew T. Fisher COMPLETE Project Number (Principal Investigator): KA0000056 (Fisher) Source: UC-CITRIS Program Title of Project: Developing a real-time sensor network for monitoring managed recharge Role: co-Principle Investigator The major goals of this project were to develop tools that could be used for real-time monitoring of MAR, focusing on thermal measurements. OVERLAP: None


Percent Effort: 0%

Project Number (Principal Investigator): OCE-1031808 (Fisher) Source: U.S. National Science Foundation Title of Project (or Subproject): Large-scale, long-term, multi-directional, cross-hole experiments in the upper oceanic crust using a borehole observatory network The major goals of this project were to establish a set of long-term borehole observatories, including associated experimental systems, for study of crustal hydrogeology, geochemistry, and microbiology. OVERLAP: None.


Percent Effort: 8%

Principal Investigator: Andrew Fisher-UCSC

BIOGRAPHICAL SKETCH and OTHER SUPPORT Limit to 3 pages per person

NAME Jordan F Clark

POSITION TITLE Professor

EDUCATION/TRAINING (Begin with baccalaureate or other initial professional education, such as nursing, and include postdoctoral training.)

INSTITUTION AND LOCATION DEGREE (if applicable)

YEAR(s) FIELD OF STUDY

Yale College B.S. 1988 Geology & Geophysics Columbia University (Lamont-Doherty Earth Obs) M.S. 1991 Earth Science Columbia University (Lamont-Doherty Earth Obs) Ph.D. 1995 Earth Science

A. Positions and Honors.

Assistant, Associate, & Full Professor, Dept. of Geological Sciences and Program of Environmental Studies, University of California, Santa Barbara 1996-present UC Water Resources Center Coordinating Board, 2003-2007 IAEA planning committee on Isotopes in Managed Aquifer Recharge, 2005 Post-doctoral Fellowship, Isotope Hydrology Group, Lawrence Livermore National Laboratory, 1995-1996 DOE Global Change Distinguished Postdoctoral Fellowship, 1995 Lawrence Livermore National Laboratory Graduate Fellowship, 1994 Heezen Award for Graduate Research in Geology, Columbia University, 1994

B. Selected peer-reviewed publications most relevant to proposed project (out of 66 total publications).

1) Clark, J. F. and K. K. Turekian (1990) Time scale of hydrothermal water - rock reactions in Yellowstone National Park based on radium isotopes and radon. Journal of Volcanology and Geothermal Research, 40, 169-180.

2) Stute, M., P. Schlosser, J. F. Clark, and W. S. Broecker (1992) Paleotemperatures in the southwestern United States derived from noble gas measurements in groundwater. Science, 256, 1000-1003.

3) Clark, J. F., R. Wanninkhof, P. Schlosser, H. J. Simpson (1994) Gas exchange in the tidal Hudson River using a dual tracer technique. Tellus, 46B, 274-285.

4) Stute, M., J. F. Clark, P. Schlosser, W. S. Broecker, and G. Bonani (1995) A high altitude continental paleotemperature record derived from noble gases dissolved in groundwater from the San Juan Basin, New Mexico. Quaternary Research, 43, 209-220.

5) Stute, M., M. Forster, H. Frischkorn, A. Serejo, J. F. Clark, P. Schlosser, W. S. Broecker, and G. Bonani (1995) 5° C cooling of tropical Brazil during the last glacial maximum. Science, 269, 379-383.

6) Clark, J. F., P. Schlosser, M. Stute, and H. J. Simpson (1996) SF6-3He tracer release experiment: A new method of determining longitudinal dispersion coefficients in large rivers. Environmental Science and Technology, 30, 1527-1532.

7) Clark, J. F., M. Stute, P. Schlosser, S. Drenkard, and G. Bonani (1997) An isotope study of the Floridan aquifer in Southeastern Georgia: Implications for groundwater flow and paleoclimate. Water Resources Research, 33, 281-289.

8) Aeschbach-Hertig, W., P. Schlosser, M. Stute, H. J. Simpson, A. Ludin, and J. F. Clark (1998) A 3H/3He study of groundwater flow in a fractured bedrock aquifer, Ground Water, 36, 661-670.

9) Clark, J. F, M. L. Davisson, G. B. Hudson, and P. A. Macfarlane (1998) Noble gases, stable isotopes, and radiocarbon as tracers of flow in the Dakota aquifer, Colorado and Kansas. Journal of Hydrology, 211, 151-167.

10) Clark, J. F. and G. B. Hudson (2001) Quantifying the flux of hydrothermal fluids into Mono Lake by use of helium isotopes. Limnology and Oceanography, 46, 189-196.

11) Gamlin, J. D., J. F. Clark, G. Woodside, and R. Herndon (2001) Large-scale tracing of ground water with sulfur hexafluoride. Journal of Environmental Engineering, ASCE, 127, 171-174.

12) Rademacher, L. K., J. F. Clark, G. B. Hudson, D. C. Erman, and N. A. Erman (2001) Chemical evolution of shallow groundwater as recorded by springs, Sagehen basin, Nevada County California. Chemical Geology, 179, 37-51.

13) Rademacher, L. K., J. F. Clark, and G. B. Hudson (2002) Temporal changes in stable isotope composition of spring waters: Implications for recent changes in climate and atmospheric circulation, Geology, 20, 139-142.

14) Rademacher, L. K., J. F. Clark, and J. R. Boles (2003) Groundwater residence times and flow paths in fractured rock determined using environmental tracers in the Mission Tunnel; Santa Barbara County, California, USA. Environmental Geology, 43, 557-567.

15) Clark, J. F., G. B. Hudson, M. L. Davisson, G. Woodside, and R. Herndon (2004) Geochemical imaging of flow near an artificial recharge facility, Orange County, CA. Ground Water, 42, 167-174.


16) Rademacher, L. K., J. F. Clark, D. W. Clow, G. B. Hudson (2005) Old groundwater influence on stream hydrochemistry and catchment response in a small Sierra Nevada catchment: Sagehen Creek, California. Water Resources Research, 41, W02004, doi:10.1029/2003WR002805.

17) Clark, J. F., G. B. Hudson, and D. Avisar (2005) Gas transport below artificial recharge ponds: Insights from dissolved noble gases and a dual gas (SF6 and 3He) tracer experiment. Environmental Science and Technology, 39, 3939-3945.

18) Avisar, D. and J. F. Clark (2005) Evaluating travel times beneath an artificial recharge pond using sulfur hexafluoride. Environmental and Engineering Geoscience, 11, 309-317.

19) Clark, J. F. (2006) Managing aquifer recharge: How can isotope hydrology help? Water & Environment News, Newsletter of the Isotope Hydrology Section, International Atomic Energy Agency, 21, 10.

20) Clark, J. F. and G. B. Hudson (2006) Excess air: A new tracer for artificially recharged surface water. In: Recharge Systems for Protecting and Enhancing Groundwater Resources, IHP-VI, Series on Groundwater No. 13, UNESCO, p. 342-347. Available at www.iah.org/recharge/downloads/Recharge_systems.pdf

21) McDermott, J. A., D. Avisar, T. Johnson, and J. F. Clark (2008) Groundwater travel times near spreading ponds: Inferences from geochemical and physical approaches. Journal of Hydrologic Engineering, ASCE, 13, 1021-1028.

22) Schladow, S. G. and J. F. Clark (2008) Use of Tracers to Quantify Subsurface Flow Through a Mining Pit. Ecological Applications, 18 Supplement, A55-A71.

23) Clark, J. F., L. Washburn, and K. Schwager (2010) Variability of gas composition and flux intensity in natural marine hydrocarbon seeps. Geo-Marine Letters, 30, 379-388, doi:10.1007/s00367-009-0167-1.

24) Morrissey, S. K., J. F. Clark, M Bennett, E. Richardson, and M. Stute (2010) Groundwater reorganization in the Floridan aquifer following Holocene sea-level rise. Nature Geoscience, 3, 683-687, doi:10.1038/NGEO956.

25) Kline, K. R., D. M. Mackay, L. Rastegarzadeh, Y. M. Nelson, J. F. Clark (2011) In-Situ Rates of Ethanol Biodegradation in a Sulfate-Reducing Aquifer Determined using Single Well Push-Pull Tests. Ground Water Monitoring and Remediation, 31, 103-110 doi:10.1111/j1745-6592.2011.01347.x.

26) Fisher, A. T., J. Cowen, C. G. Wheat, and J. F. Clark (2011), Preparation and injection of fluid tracers during IODP Expedition 327, eastern flank of Juan de Fuca Ridge in Proc. IODP 327, edited by A. T. Fisher, T. Tsuji and K. Petronotis. doi:10.2204/iodp.proc.327.108.2011, Integrated Ocean Drilling Program Management International, Inc., Tokyo.


Include all current and pending support. Also list grants completed within the last three years. For current and pending support specify if there is any overlap with this application. NAME OF INDIVIDUAL ACTIVE Source: NSF Title of Project: Collaborative Research: Completion of single- and cross-hole hydrogeologic experiments on the eastern flank of the Juan de Fuca Ridge using a borehole network Role: Co-PI/UCSB lead PI The major goals of this project are to evaluate the hydrology of the upper seafloor crust. My role is to help run borehole tracer experiments. OVERLAP: None

Dates of Approved: 10/1/10-9/30/13 Annual Direct Costs: $43k/yr

Percent Effort 15%

NAME OF INDIVIDUAL ACTIVE Source WateReuse Foundation Title of Project Development of New Tracers for Determining Travel Time Near MAR Operation Role: Lead PI The major goals of this project are to evaluate boron-10 and sulfur-35 as new tracers of near-field flow at MAR facilities using spreading ponds OVERLAP: This project’s goal shares some of the same goals of the proposed project though it differs in that it is focused mostly on the development of two new methodology using 10B and 35S.

Dates of Approved 11/01/10-8/01/13 Annual Direct Costs: $48k/yr

Percent Effort 15%


NAME OF INDIVIDUAL COMPLETED Source California Energy Commission (sub contract from Desert Research Institute) Title of Project: Investigation of Methods of Potential Value for Monitoring Groundwater Recharge in the Mountains of California Role: Lead PI at UCSB The major goals of this project were to evaluate various methods to assess groundwater recharge in Sagehen Basin OVERLAP: None

Dates of Approved: 4/1/99-12/13/11 Annual Direct Costs: $35k

Percent Effort 15%

NAME OF INDIVIDUAL COMPLETE Source: Water Replenishment District of Southern California Title of Project: 2010 Rio Hondo-Groundwater Tracer Study Role: Lead PI The major goal of this project was to determine if the low screen intervals in two productions wells were isolated, would travel times increase. We showed they did. OVERLAP: None

Dates of Approved: 1/1/10-12/31/11 (after 1yr weather delay) Annual Direct Costs: $25k

Percent Effort: 10%

NAME OF INDIVIDUAL COMPLETE Source: American Petroleum Institute Title of Project: Evaluation of Push-Push Tests for Site Characterization at Vandenberg AFB Role: Lead PI The major goal of this project was to quantify the biodegradation rate of ethanol at Site 60, Vandenberg AFB OVERLAP: None


Percent Effort 10%

NAME OF INDIVIDUAL COMPLETE Source: NSF Title of Project Collaborative research: Large-scale, long-term, multi-directional, cross-hole experiments in the upper oceanic crust using a borehole observatory network Role: Co-PI/UCSB lead PI The major goals of this project were to finish construction of the necessary analytical tools to complete the borehole experiments after the IODP cruise to the Juan de Fuca Ridge flank OVERLAP: None


Percent Effort 5%

Principal Investigator: Fisher


NAME Ate Visser

POSITION TITLE Postdoc




University of Amsterdam, Amsterdam, The Netherlands

MSc 1997-2004 Physical Geography

Utrecht University, Utrecht, The Netherlands PhD (cum laude)

2004-2009 Groundwater Hydrology

Lawrence Livermore National Laboratory 2010-present Noble Gas Isotope Hydrology


Associate Editor for Hydrogeology Journal 1st prize for best geosciences publication 2009, awarded by the Netherlands Geological Survey. Record of Invention filed for the development of the Noble Gas Membrane Inlet Mass Spectrometer (NG-MIMS), March 2011.

B. Selected peer-reviewed publications (in chronological order). Visser, A., Kroes, J., Van Vliet, M T.H., Blenkinsop, S., Fowler, H.J., Broers, H.P. (2012) Climate change

impacts on the leaching of a heavy metal contamination in a small lowland catchment. Journal of Contaminant Hydrology 127: 47-64, doi:10.1016/j.jconhyd.2011.04.007.

Visser, A., I. Dubus, H.P. Broers, S. Brouyère, M. Korcz, Ph. Orban, P. Goderniaux, J. Batlle-Aguilar, N. Surdyk, N. Amraoui, H. Job, J.L. Pinault and M.F.P. Bierkens. 2009. Comparison of methods for the detection and extrapolation of trends in groundwater quality. Journal of Environmental Monitoring, 11, 2030 - 2043, doi:10.1039/B905926C.

Visser, A., H.P. Broers, R. Heerdink and M.F.P. Bierkens. 2009. Trends in pollutant concentrations in relation to time of recharge and reactive transport at the groundwater body scale. Journal of Hydrology 369(3-4): 427-439, doi:10.1016/j.jhydrol.2009.02.008.

Visser, A., J.D. Schaap, H.P. Broers and M.F.P. Bierkens. 2009. Degassing of 3H/3He, CFCs and SF6 by denitrification: measurements and two-phase transport simulations. Journal of Contaminant Hydrology 103(3-4): 206-218, doi:10.1016/j.jconhyd.2008.10.013.

Visser, A., R. Heerdink, H.P. Broers and M.F.P. Bierkens. 2009. Travel time distributions derived from particle tracking in ground water models containing weak sinks. Ground Water 47(2): 237-245, doi: 10.1111/j.1745-6584.2008.00542.x.

Visser, A., H.P. Broers and M.F.P. Bierkens. 2007. Dating degassed groundwater with 3H/3He. Water Resources Research 43 (10): WR10434, doi:10.1029/2006WR005847

Visser, A., H.P. Broers, B. Van der Grift and M.F.P. Bierkens. 2007. Demonstrating Trend Reversal of Groundwater Quality in Relation to Time of Recharge determined by 3H/3He. Environmental Pollution 148 (3): 797-807, doi:10.1016/j.envpol.2007.01.027.

Visser, A., R. Stuurman and M.F.P. Bierkens. 2006. Real-time forecasting of water table depth and soil moisture profiles. Advances in Water Resources 29 (5): 692-706, doi:10.1016/j.advwatres.2005.07.011.

Principal Investigator: Fisher C. Research Support.

Include all current and pending support. Also list grants completed within the last three years. For current and pending support specify if there is any overlap with this application. Ate Visser COMPLETE Project Number (Principal Investigator) Prof. Dr. Hans Peter Broers Source: Department of Economic Affairs, Agriculture and Innovation, The Netherlands Title of Project AquaTempo: groundwater dating for drinking water production Role: Co-PI The major goal of this project was to improve the water quality prognosis of a drinking water production well field by applying a combination of environmental groundwater age tracers (85Kr, 3H/3He, 39Ar). OVERLAP: None

Dates of Approved Project: August 2009 – December 2011 Annual Direct Costs $150,000

Percent Effort 50%


BIOGRAPHICAL SKETCH and OTHER SUPPORT

NAME Bradley Keith Esser

POSITION TITLE Group Leader, Environmental Radiochemistry Chemical Sciences Division, Lawrence Livermore National Laboratory




University of Arizona (Tucson, AZ) B.S. (with highest distinction)

1979 Ecology & Evolutionary Biology

University of Arizona (Tucson, AZ) B.S. (with high distinction)

1983 Geosciences

Yale University (New Haven, CT) M.Phil. 1985 Geology & Geophysics Yale University (New Haven, CT) Ph.D. 1991 Geology & Geophysics Lawrence Livermore National Laboratory (Livermore, CA)

Post-Doctoral Fellowship

1990-1993

Isotope Geochemistry


Honors Hitchon Award, International Association of Geochemistry (2007) Dissertations Symposium on Chemical Oceanography (1991) Philip M. Orville Prize, Yale University (1991) Bateman Prize, Yale University (1983) Phi Beta Kappa (1979)

Positions Lawrence Livermore National Laboratory, Chemical Sciences Division

Scientific Capability and Group Leader –Environmental Radiochemistry (2001-present) Lead –Environmental Monitoring Radioanalytical Laboratory (2002-present) LLNL Lead–California Groundwater Ambient Monitoring & Assessment program (2007-present) Staff Scientist (1993-2001)

Postdoctoral Research Assistant (1990–1993); Sid Niemeyer, advisor. Yale University, Department of Geology and Geophysics

Doctoral Research Assistant (1985-1990), K. K. Turekian, advisor B. Selected peer-reviewed publications (in chronological order). Esser B. K. and Turekian K. K. (1988) Accretion rate of extraterrestrial particles determined from osmium

isotope systematics of Pacific pelagic clay and manganese nodules. Geochimica et Cosmochimica Acta 52, 1383–1388.

Esser B. K. and Turekian K. K. (1993) The osmium isotopic composition of the continental crust. Geochimica et Cosmochimica Acta 57, 3093–3104.

Esser B. K. and Turekian K. K. (1993) Anthropogenic osmium in coastal deposits. Environmental Science & Technology 27(13), 2719–2723.

Esser B. K., Volpe A., Kenneally J. M., and Smith D. K. (1994) Preconcentration and purification of rare earth elements in natural waters using silica-immobilized 8-hydroxyquinoline and a supported organophosphorus extractant. Analytical Chemistry 66(10), 1736-1742..

Esser B. K. and Volpe A. M. (2002) At-sea high-resolution chemical mapping: extreme barium depletion in


North Pacific surface water. Marine Chemistry 79(2), 67-79.

Esser B. K. and Volpe A. M. (2002) At-sea high-resolution trace-metal mapping: San Diego Bay and its plume in the coastal ocean. Environmental Science & Technology 36(13), 2826-2832.

Love A. H., Esser B. K., and Hunt J. R. (2003) Reconstructing contaminant deposition in a San Francisco Bay marina, California. Journal of Environmental Engineering 129(7):659-666.

Koester C. J., Simonich S. L., and Esser B. K. (2003) Environmental Analysis. Analytical Chemistry 75:2813-2829.

Carle S. F., Esser B. K., and Moran J. E. (2006) High-resolution simulation of basin scale nitrate transport considering aquifer system heterogeneity. Geosphere 2 (4, Special Issue: Modeling Flow and Transport in Physically and Chemically Heterogeneous Media), 195-209.

Moore K., Ekwurzel B. E., Esser B. K., Hudson G. B., and Moran J. E. (2006) Sources of groundwater nitrate revealed using residence time and isotope methods. Applied Geochemistry 21(6), 1016-1029.

Singleton, M. J., Esser, B. K., Moran, J. E., Hudson, G. B., McNab, W. W., and Harter, T. (2007). Saturated zone denitrification: Potential for natural attenuation of nitrate contamination in shallow groundwater under dairy operations. Environmental Science & Technology 41, 759-765.

McNab, W. W., Singleton, M. J., Moran, J. E., and Esser, B. K. (2007). Assessing the impact of animal waste lagoon seepage on the geochemistry of an underlying shallow aquifer. Environmental Science & Technology 41, 753-758.

Esser B. K., Singleton M., and Moran J. (2009) Identifying groundwater nitrate sources and sinks. Southwest Hydrology (Nitrates in Groundwater Special Issue) 8(4, July/August), 32.

Johnson B. E., Esser B. K., Whyte D. C., Ganguli P. M., Austin C. M., and Hunt J. R. (2009) Mercury accumulation and attenuation at a rapidly forming delta with a point source of mining. Science of the Total Environment 407, 5056-5070.

McNab Jr W. W., Singleton M. J., Moran J. E., and Esser B. K. (2009) Ion exchange and trace element surface complexation reactions associated with applied recharge of low-TDS water in the San Joaquin Valley, California. Applied Geochemistry 24(1), 129-137.

Landon M., Green C., Belitz K., Singleton M., and Esser B. (2011) Relations of hydrogeologic factors, groundwater reduction-oxidation conditions, and temporal and spatial distributions of nitrate, Central-Eastside San Joaquin Valley, California, USA. Hydrogeology Journal 19(6), 1203-1224.

Null K. A., Dimova N. T., Knee K. L., Esser B. K., Swarzenski P. W., Singleton M. J., and Paytan A. (2011) Submarine groundwater discharge in San Francisco Bay: Implications to nutrient budgets and potential ecosystem changes. Estuaries and Coasts, submitted.


Bradley K Esser ACTIVE Project Number (Principal Investigator) : Bradley K Esser Source: California State Water Resources Control Board Title of Project: GAMA-8 - GAMA Basin Priority Program: Age-Dating California Groundwater Role: Principal Investigator The major goals of this project are to assess vulnerability in California groundwaters used for the public drinking water supply by determining their tritium-helium mean apparent age. OVERLAP: None. Provides support to analytical facility.

Dates of Approved Project: March 2008 to June 2013 Annual Costs: $959K

Percent Effort: 5%


Project Number (Principal Investigator): Bradley K Esser Source: California State Water Resources Control Board Title of Project: GAMA-12 - GAMA Special Studies Role: Principal Investigator The major goals of this project are to 1) investigate climate change impacts on high altitude basins ; 2) compile and map groundwater H3-He3 age in the State of California, and 3) provide specialized analyses for GAMA domestic wells. OVERLAP: None

Dates of Approved Project: March 1, 2011 to March 31, 2013 Annual Costs: $462

Percent Effort: 20%

Project Number (Principal Investigator): Bradley K Esser Source: California State Water Resources Control Board Title of Project: GAMA-11 - GAMA Special Studies Role: Principal Investigator The major goals of this project are to 1) develop a noble-gas membrane-inlet mass spectrometer (NG-MIMS) and demonstrate its use for measuring introduced noble gases as recharge tracers; 2) investigate the water quality of tritium-dead groundwater; and 3) provide specialized analyses for GAMA domestic wells. OVERLAP: None. Provided funding for development of an NG-MIMS (noble-gas membrane-inlet mass spectrometer).

Dates of Approved Project: December 31, 2009 to March 31, 2012 Annual Costs: $350K

Percent Effort: 20%

Project Number (Principal Investigator): Bradley K Esser Source: California State Water Resources Control Board Title of Project: GAMA-10 - GAMA Special Studies Role: Principal Investigator The major goals of this project are to 1) investigate surface water – groundwater interactions in Central Coast basins and evaluate the impact of these interactions on nitrate concentrations; 2) develop new wastewater indicator methods for groundwater, 3) develop S-35 as a short-lived tracer of groundwater recharge, and 3) provide specialized analyses for GAMA domestic wells. OVERLAP: None. Provided initial development of an analytical capability to measure S-35 at low levels.

Dates of Approved Project: March 1, 2009 to March 31, 2011 Annual Costs: $460K

Percent Effort: 20%

Project Number (Principal Investigator): Bradley K. Esser Source: LLNL G&A Title of Project: Environmental Monitoring Radioanalytical Laboratory Role: Lead The major goals of this project are to provide monitoring for radioactivity in environmental samples and to develop new radioanalytical techniques for special studies. OVERLAP: None. Supports analytical facility used to make low-level measurements of S-35 in water.

Dates of Approved Project: Ongoing Annual Direct Costs: $990K

Percent Effort: 30%

COMPLETE Project Number (Principal Investigator): Michael Singleton Source: LLNL Strategic Mission Support Title of Project: Probing Climate Change Impacts On California Water Resources Using Multiple Isotopic Tracers Role: Co-PI The major goals of this project are characterize the contribution of groundwater to stream flow in alpine basins in the Sierra Nevada. OVERLAP: None

Dates of Approved Project: May 2008 to September 2009 Annual Direct Costs: $200K

Percent Effort: 5%

Project Number (Principal Investigator): Darren Hillegonds Source: LLNL Laboratory Directed Research & Development Title of Project: Natural Perchlorate in Groundwater: Source, Formation Mechanisms, and Fate. Role: Co-PI The major goals of this project are to demonstrate that groundwater-derived perchlorate is imprinted with 36Cl/Cl indicative of source. OVERLAP: None

Dates of Approved Project: October 2008 to September 2011 Annual Direct Costs: $240K

Percent Effort: 5%



NAME Michael Singleton

POSITION TITLE Staff Chemist




Southern Methodist University BS 1997 Geology Washington University PhD 2002 Geochemistry


Lawrence Livermore National Laboratory, Livermore, CA Staff Scientist, 2006-Present Post-doctoral researcher, 2005-2006

Lawrence Berkeley National Laboratory, Berkeley, CA Post-doctoral fellow, 2002-2005 Washington University, St. Louis, MO Research Assistant, 1999-2002

B. Selected peer-reviewed publications (in chronological order). Volpe AM, Singleton MJ. Stable isotopic characterization of ammonium metavanadate (NH4VO3). Forensic science

international. [doi: 10.1016/j.forsciint.2011.01.005]. 2011;209(1-3):96-101. Zhao P., Zavarin M., Leif R. N., Powell B. A., Singleton M. J., Lindvall R. E., and Kersting A. B. (2011) Mobilization

of actinides by dissolved organic compounds at the Nevada Test Site. Applied Geochemistry, (DOI:10.1016/j.apgeochem.2010.12.004)

Singleton, M. J., and J. E. Moran (2010), Dissolved noble gas and isotopic tracers reveal vulnerability of groundwater in a small, high-elevation catchment to predicted climate changes, Water Resour. Res., 46, W00F06, doi:10.1029/2009WR008718.

Esser B. K., Singleton M. J., Moran J. E. (2009) Identifying groundwater nitrate sources and sinks. Southwest Hydrology, July/August, p. 32-33.

McNab Jr W. W., Singleton M. J., Moran J. E., and Esser B. K. (2009) Ion exchange and trace element surface complexation reactions associated with applied recharge of low-TDS water in the San Joaquin Valley, California. Applied Geochemistry 24(1), 129-137.

Singleton M. J., Esser B. K., Moran J. E., Hudson G. B., McNab W. W., and Harter T. (2007) Saturated zone denitrification: Potential for natural attenuation of nitrate contamination in shallow groundwater under dairy operations. Environ. Sci. Technol. 41(3), 759-765.

McNab W. W., Singleton M. J., Moran J. E., and Esser B. K. (2007) Assessing the impact of animal waste lagoon seepage on the geochemistry of an underlying shallow aquifer. Environ. Sci. Technol. 41(3), 753-758.

Singleton, M.J., K. Maher, D.J. DePaolo, M.E. Conrad, and P.E. Dresel. (2006) Dissolution rates and vadose zone drainage from strontium isotope measurements of groundwater in the Pasco Basin, WA unconfined aquifer. Journal of Hydrology, vol. 326, 39-58.

Singleton, M.J., K.N. Woods, M.E. Conrad, D.J. DePaolo and P.E. Dresel. (2005) Tracking sources of unsaturated zone and groundwater nitrate contamination using nitrogen and oxygen stable isotopes at the Hanford Site,


Washington. Environmental Science and Technology, vol. 39(10), 3563 – 3570. Gee, G. W., S.W. Tyler, W.H. Albright, and M.J. Singleton. (2005) Chloride Mass Balance Cautions in Predicting

Increased Recharge Rates. Vadose Zone Journal, Vol. 4, 72-78. Singleton, M.J., E.L. Sonnenthal, M.E. Conrad, D.J. DePaolo, and G.W. Gee. (2004). Multiphase reactive transport

modeling of stable isotope fractionation in unsaturated zone pore water and vapor: Application to seasonal infiltration events at the Hanford Site, WA. Vadose Zone Journal, Vol. 3, 775-785.

Singleton, M.J. and R.E. Criss. (2004) Symmetry of hydrothermal flows in the Comstock Lode mining district, Nevada: evidence for longitudnal convective rolls in geologic systems. Journal of Geophysical Research, v. 109, B03205, doi:10.1029/2003JB002660.

Singleton, M.J. and R.E. Criss. (2002) Effects of Normal Faulting on Fluid Flow in an Ore-Producing Hydrothermal System, Comstock Lode, Nevada. Journal of Volcanology and Geothermal Research, v. 115, 437-450.


Include all current and pending support. Also list grants completed within the last three years. For current and pending support specify if there is any overlap with this application. Michael Singleton ACTIVE Project Number (Principal Investigator): Bradley K Esser Source: California State Water Resources Control Board Title of Project: GAMA-12 - GAMA Special Studies Role: Task Lead The major goals of this project are to 1) investigate climate change impacts on high altitude basins ; 2) compile and map groundwater H3-He3 age in the State of California, and 3) provide specialized analyses for GAMA domestic wells. OVERLAP: None

Dates of Approved Project: March 1, 2011 to March 31, 2013 Annual Costs: $462

Percent Effort: 30%

Michael Singleton ACTIVE Project Number (Principal Investigator): Michael Singleton Source: Department of Homeland Security Title of Project (or Subproject) Compound Specific isotope signatures of CTAs in real-world sample matrices Role: PI The major goals of this project are to develop the use of compound-specific stable isotope analyses for chemical threat agents. OVERLAP: None

Dates of Approved/Proposed Project: Sept. 2011-Sept. 2012 Annual Direct Costs: $216K

Percent Effort 40%

Michael Singleton ACTIVE


Project Number (Principal Investigator): Bradley K Esser Source: California State Water Resources Control Board Title of Project: GAMA-11 - GAMA Special Studies Role: Task Lead The major goals of this project are to 1) develop a noble-gas membrane-inlet mass spectrometer (NG-MIMS) and demonstrate its use for measuring introduced noble gases as recharge tracers; 2) investigate the water quality of tritium-dead groundwater; and 3) provide specialized analyses for GAMA domestic wells. OVERLAP: None. Provided funding for development of an NG-MIMS (noble-gas membrane-inlet mass spectrometer).

Dates of Approved Project: December 31, 2009 to March 31, 2012 Annual Costs: $350K

Percent Effort 30%

Michael Singleton COMPLETE Project Number (Principal Investigator): Michael Singleton Source: Department of Homeland Security Title of Project (or Subproject) Stable Isotope Characterization of TICs/TIMs: Sulfur Isotope Composition of TETS and Precursors Role: PI The major goals of this project are to develop stable isotope signatures for tetramine. OVERLAP: NA

Dates of Approved/Proposed Project: Sept. 2011-Sept. 2012 Annual Direct Costs: $173K

Percent Effort 40%

Michael Singleton COMPLETE Project Number (Principal Investigator): Bradley K Esser Source: California State Water Resources Control Board Title of Project: GAMA-9 - GAMA Special Studies Role: Task Lead The major goals of this project are to 1) assess natural attenuation of contaminants in deep aquifer systems; 2) combine groundwater ages and introduced tracer results to determine contaminant transport rate to drinking water wells, and 3) provide specialized analyses for GAMA domestic wells. OVERLAP: None

Dates of Approved Project: March 2008 to February 2009 Annual Costs: $550K

Percent Effort: 20%

Michael Singleton COMPLETE Project Number (Principal Investigator): Michael Singleton Source: LLNL Strategic Mission Support Title of Project: Probing Climate Change Impacts On California Water Resources Using Multiple Isotopic Tracers Role: PI The major goals of this project are characterize the contribution of groundwater to stream flow in alpine basins in the Sierra Nevada. OVERLAP: None

Dates of Approved Project: May 2008 to September 2009 Annual Direct Costs: $200K

Percent Effort: 40%

Professor Andrew Fisher January 12, 2012 Earth and Planetary Sciences Department

University of California – Santa Cruz

1156 High Street, E&MS Bldg., Rm. A232

Santa Cruz, CA 95064

Subject: Intent to collaborate as a National Laboratory partner on the UC Laboratory Fees Research Program proposal entitled “New Tracers for Managed Aquifer Recharge”

Dear Professor Fisher,

I am very happy to endorse the partnership between Lawrence Livermore National Laboratory (LLNL) and your institution as described in the above joint proposal to the UC Laboratory Fees

Research Program.

We welcome this opportunity to embark upon a joint research/training program with your UC campus. We see this program as an opportunity to establish a critical foundation for training the

next generation of US technical leaders - scientists and engineers adept at understanding key

national security challenges. Ensuring this pipeline of well-trained, bright, motivated advanced degree holders in the sciences and engineering is essential to our national security. As part of the

UC Laboratory Fees Research Program, our institutions could help to make certain that such a

pipeline is a sustainable reality.

LLNL personnel will guide and supervise the introduction of xenon tracer into the managed aquifer recharge facility, and will have primary responsibility for the measurement of introduced

xenon and naturally occurring 35

S tracer in surface and groundwater samples from the facility.

These analyses will be performed at LLNL on the Noble Gas Membrane Inlet Mass Spectrometer (NG-MIMS), recently developed at LLNL, and on two ultra-low level Liquid Scintillation

Counters (LSC). LLNL personnel will also have responsibility for training UCSC graduate

students to analyze water samples on the LLNL NG-MIMs, and will facilitate the analysis of 35

S samples by Stephanie Diaz, a UCSB Ph.D. student whose UCSB advisor, Prof. Jordan Clark, is a

co-PI on the project. Stephanie has recently been awarded a Lawrence Scholarship from LLNL to

work with Dr. Esser (an LLNL co-PI) on developing 35

S as a recharge tracer.

We look forward to the opportunity to work with you in the UC Fee Program. Please feel free to contact me if you have any questions.

Best regards,

Henry F. Shaw

Deputy Associate Director for Science & Technology

Physical & Life Sciences Directorate

afisher

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P. I.: A. T. Fisher, UCSC

PAJARO VALLEY WATER MANAGEMENT AGENCY 36 BRENNAN STREET • WATSONVILLE, CA 95076

TEL: (831) 722-9292 FAX: (831) 722-3139 email: [email protected] • http://www.pvwma.dst.ca.us

January 11, 2012 Re: Support and collaboration on the proposed UC-Lab research project, "New Groundwater Tracer Systems for Managed Recharge" Andrew T. Fisher, Professor University of California, Santa Cruz Earth and Planetary Sciences Department 1156 High Street Santa Cruz, CA 95064 Dear Andy, The Pajaro Valley Water Management Agency (PVWMA) would like to support and collaborate with you and your colleagues and students on the project, "New Groundwater Tracer Systems for Managed Recharge," as described in the proposal being prepared for submission to the UC Laboratory Fees Research Program. I understand that, if it is approved, the project will run from July 2012 through June 2015. The PVWMA has a strong interest in seeing the proposed work completed, both for the broad scientific and technical benefit and because the project will assist the Agency in achieving practical goals. Results of this work would have a direct positive impact on water resource management in our region, both for activities as part of managing the Harkins Slough Managed Aquifer Recharge (MAR) project, and for potential MAR projects that could be developed elsewhere around the basin. In addition, the PVWMA is in the midst of updating our Basin Management Plan. MAR projects of similar size are being considered as a potential source of supplemental water supply. The timing for implementation of these projects, if selected, is within the 5-7 year range. Results from this study could directly influence the design of future projects. This work will also have a positive influence on many other groundwater basins in California that are experiencing overdraft and increasing demand, where new tracer tools and studies are needed to assess how best to manage limited resources. The Agency and UCSC have partnered successfully on research projects in the past, and this has been to our mutual benefit. On a more personal note, I welcome the opportunity to collaborate with you and your colleagues at UCSB and LLNL, your students, and others on this tracer study. In demonstration of our support, the PVWMA is pleased to provide services, advice, data, and technical and scientific collaboration, particularly in providing access to the Harkins Slough percolation pond, groundwater wells, dedicated pumps, a pump controller and measurement cell used for assessing stability of sample chemistry, and other infrastructure throughout the Agency's service area. We will provide you with access to the secured facilities associated with the Harkins Slough project, which will help to keep your equipment secure on site. In addition, we will provide access to data associated with operation of the Harkins Slough Managed Aquifer Recharge System, and will coordinate with you and your project colleagues with regard to these operations, so that we can collect critical samples and data. I would also

afisher

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P.I.: A. T. Fisher, UCSC

appreciate having the opportunity to collaborate on analysis of tracer results, and on preparation of numerical models of fluid and tracer transport associated with the MAR system. As you know, the Agency has an ongoing program of groundwater monitoring and sampling throughout the basin, including the area around Harkins Slough. We will coordinate this work with you and your colleagues so as to achieve mutual goals. Through dedication of staff time to assist with this work, and through collection and analysis of water samples, we calculate that the Agency will expend on the order of $65,000/year during the period of your study in support of the proposed project, for a total of about $195,000 of "in kind" support. All water samples will be collected and handled following appropriate protocols, and analyses will be completed in an EPA-certified laboratory (currently, the PVWMA uses Monterey Bay Analytical for this work). In addition, the infrastructure and equipment being made available for this project comprises an investment of several million dollars. We appreciate the opportunity to participate in this project and will be happy to address any questions. Please contact the agency at (831) 722-9292 with and questions or comments. Sincerely,

Brian Lockwood Staff Hydrologist PVWMA

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