Vadose zone transport field study: Detailed test plan for simulated leak tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

AL Ward; GW Gee

2000-06-23

The US Department of Energy (DOE) Groundwater/Vadose Zone Integration Project Science and Technology initiative was created in FY 1999 to reduce the uncertainty associated with vadose zone transport processes beneath waste sites at DOE's Hanford Site near Richland, Washington. This information is needed not only to evaluate the risks from transport, but also to support the adoption of measures for minimizing impacts to the groundwater and surrounding environment. The principal uncertainties in vadose zone transport are the current distribution of source contaminants and the natural heterogeneity of the soil in which the contaminants reside. Oversimplified conceptual models resulting from thesemore » uncertainties and limited use of hydrologic characterization and monitoring technologies have hampered the understanding contaminant migration through Hanford's vadose zone. Essential prerequisites for reducing vadose transport uncertainly include the development of accurate conceptual models and the development or adoption of monitoring techniques capable of delineating the current distributions of source contaminants and characterizing natural site heterogeneity. The Vadose Zone Transport Field Study (VZTFS) was conceived as part of the initiative to address the major uncertainties confronting vadose zone fate and transport predictions at the Hanford Site and to overcome the limitations of previous characterization attempts. Pacific Northwest National Laboratory (PNNL) is managing the VZTFS for DOE. The VZTFS will conduct field investigations that will improve the understanding of field-scale transport and lead to the development or identification of efficient and cost-effective characterization methods. Ideally, these methods will capture the extent of contaminant plumes using existing infrastructure (i.e., more than 1,300 steel-cased boreholes). The objectives of the VZTFS are to conduct controlled transport experiments at well-instrumented field sites at Hanford

Hydrologic processes in deep vadose zones in interdrainage arid environments

USGS Publications Warehouse

Walvoord, Michelle Ann; Scanlon, Bridget R.; Hogan, James F.; Phillips, Fred M.; Scanlon, Bridget R.

2004-01-01

A unifying theory for the hydrology of desert vadose zones is particularly timely considering the rising population and water stresses in arid and semiarid regions. Conventional models cannot reconcile the apparent discrepancy between upward flow indicated by hydraulic gradient data and downward flow suggested by environmental tracer data in deep vadose zone profiles. A conceptual model described here explains both hydraulic and tracer data remarkably well by incorporating the hydrologic role of desert plants that encroached former juniper woodland 10 to 15 thousand years ago in the southwestern United States. Vapor transport also plays an important role in redistributing moisture through deep soils, particularly in coarse-grained sediments. Application of the conceptual model to several interdrainage arid settings reproduces measured matric potentials and chloride accumulation by simulating the transition from downward flow to upward flow just below the root zone initiated by climate and vegetation change. Model results indicate a slow hydraulic drying response in deep vadose zones that enables matric potential profiles to be used to distinguish whether precipitation episodically percolated below the root zone or was completely removed via evapotranspiration during the majority of the Holocene. Recharge declined dramatically during the Holocene in interdrainage basin floor settings of arid and semiarid basins. Current flux estimates across the water table in these environmental settings, are on the order of 0.01 to 0.1 mm yr-1 and may be recharge (downward) or discharge (upward) depending on vadose zone characteristics, such as soil texture, geothermal gradient, and water table depth. In summary, diffuse recharge through the basin floor probably contributes only minimally to the total recharge in arid and semiarid basins.

Climate variability and vadose zone controls on damping of transient recharge

USGS Publications Warehouse

Corona, Claudia R.; Gurdak, Jason J.; Dickinson, Jesse; Ferré, T.P.A.; Maurer, Edwin P.

2018-01-01

Increasing demand on groundwater resources motivates understanding of the controls on recharge dynamics so model predictions under current and future climate may improve. Here we address questions about the nonlinear behavior of flux variability in the vadose zone that may explain previously reported teleconnections between global-scale climate variability and fluctuations in groundwater levels. We use hundreds of HYDRUS-1D simulations in a sensitivity analysis approach to evaluate the damping depth of transient recharge over a range of periodic boundary conditions and vadose zone geometries and hydraulic parameters that are representative of aquifer systems of the conterminous United States (U.S). Although the models were parameterized based on U.S. aquifers, findings from this study are applicable elsewhere that have mean recharge rates between 3.65 and 730 mm yr–1. We find that mean infiltration flux, period of time varying infiltration, and hydraulic conductivity are statistically significant predictors of damping depth. The resulting framework explains why some periodic infiltration fluxes associated with climate variability dampen with depth in the vadose zone, resulting in steady-state recharge, while other periodic surface fluxes do not dampen with depth, resulting in transient recharge. We find that transient recharge in response to the climate variability patterns could be detected at the depths of water levels in most U.S. aquifers. Our findings indicate that the damping behavior of transient infiltration fluxes is linear across soil layers for a range of texture combinations. The implications are that relatively simple, homogeneous models of the vadose zone may provide reasonable estimates of the damping depth of climate-varying transient recharge in some complex, layered vadose zone profiles.

HEAT AND MASS TRANSFER IN THE VADOSE ZONE WITH PLANT ROOTS. (R825414)

EPA Science Inventory

Abstract

The vadose zone is the intermediate medium between the atmosphere and groundwater. The modeling of the processes taking place in the vadose zone needs different approaches to those needed for groundwater transport problems because of the marked changes in envi...

Karst system vadose zone hydrodynamics highlighted by an integrative geophysical and hydrogeological monitoring

NASA Astrophysics Data System (ADS)

Watlet, A.; Van Camp, M. J.; Francis, O.; Poulain, A.; Hallet, V.; Rochez, G.; Kaufmann, O.

2015-12-01

The vadose zone of karst systems plays an important role on the water dynamics. In particular, temporary perched aquifers can appear in the subsurface due to changes of climate conditions, diminished evapotranspiration and differences of porosity relative to deeper layers. It is therefore crucial, but challenging, to separate the hydrological signature of the vadose zone from the one of the saturated zone for understanding hydrological processes that occur in the vadose zone. Although many difficulties are usually encountered when studying karst environments due to their heterogeneities, cave systems offer an outstanding opportunity to investigate vadose zone from the inside with various techniques. We present results covering two years of hydrogeological and geophysical monitoring at the Rochefort Cave Laboratory (RCL), located in the Variscan fold-and-thrust belt (Belgium), a region that shows many karstic networks within Devonian limestone units. Hydrogeological data such as flows and levels monitoring or tracer tests performed in both vadose and saturated zones bring valuable information on the hydrological context of the studied area. Combining those results with geophysical measurements allows validating and imaging them with more integrative techniques. A microgravimetric monitoring involves a superconducting gravimeter continuously measuring at the surface of the RCL. Early in 2015, a second relative gravimeter was installed in the underlying cave system located 35 meters below the surface. This set up allows highlighting vadose gravity changes. These relative measurements are calibrated using an absolute gravimeter. 12 additional stations (7 at the surface, 5 in the cave) are monitored on a monthly basis by a spring gravimeter. To complete these gravimetric measurements, the site has been equipped with a permanent Electrical Resistivity Tomography (ERT) monitoring system comprising an uncommon array of surface, borehole and cave electrodes. Although such

SENSITIVE PARAMETER EVALUATION FOR A VADOSE ZONE FATE AND TRANSPORT MODEL

EPA Science Inventory

This report presents information pertaining to quantitative evaluation of the potential impact of selected parameters on output of vadose zone transport and fate models used to describe the behavior of hazardous chemicals in soil. The Vadose 2one Interactive Processes (VIP) model...

Tackling the Challenge of Deep Vadose Zone Remediation at the Hanford Site

NASA Astrophysics Data System (ADS)

Morse, J. G.; Wellman, D. M.; Gephart, R.

2010-12-01

The Central Plateau of the Hanford Site in Washington State contains some 800 waste disposal sites where 1.7 trillion liters of contaminated water was once discharged into the subsurface. Most of these sites received liquids from the chemical reprocessing of spent uranium fuel to recover plutonium. In addition, 67 single shell tanks have leaked or are suspected to have leaked 3.8 million liters of high alkali and aluminate rich cesium-contaminated liquids into the sediment. Today, this inventory of subsurface contamination contains an estimated 550,000 curies of radioactivity and 150 million kg (165,000 tons) of metals and hazardous chemicals. Radionuclides range from mobile 99Tc to more immobilized 137Cs, 241Am, uranium, and plutonium. A significant fraction of these contaminants likely remain within the deep vadose zone. Plumes of groundwater containing tritium, nitrate, 129I and other contaminants have migrated through the vadose zone and now extend outward from the Central Plateau to the Columbia River. During most of Hanford Site history, subsurface studies focused on groundwater monitoring and characterization to support waste management decisions. Deep vadose zone studies were not a priority because waste practices relied upon that zone to buffer contaminant releases into the underlying aquifer. Remediation of the deep vadose zone is now central to Hanford Site cleanup because these sediments can provide an ongoing source of contamination to the aquifer and therefore to the Columbia River. However, characterization and remediation of the deep vadose zone pose some unique challenges. These include sediment thickness; contaminant depth; coupled geohydrologic, geochemical, and microbial processes controlling contaminant spread; limited availability and effectiveness of traditional characterization tools and cleanup remedies; and predicting contaminant behavior and remediation performance over long time periods and across molecular to field scales. The U

Evaluation of deep vadose zone contaminant flux into groundwater: Approach and case study

NASA Astrophysics Data System (ADS)

Oostrom, M.; Truex, M. J.; Last, G. V.; Strickland, C. E.; Tartakovsky, G. D.

2016-06-01

For sites with a contaminant source located in the vadose zone, the nature and extent of groundwater contaminant plumes are a function of the contaminant flux from the vadose zone to groundwater. Especially for thick vadose zones, transport may be relatively slow making it difficult to directly measure contaminant flux. An integrated assessment approach, supported by site characterization and monitoring data, is presented to explain current vadose zone contaminant distributions and to estimate future contaminant flux to groundwater in support of remediation decisions. The U.S. Department of Energy Hanford Site (WA, USA) SX Tank Farm was used as a case study because of a large existing contaminant inventory in its deep vadose zone, the presence of a limited-extent groundwater plume, and the relatively large amount of available data for the site. A predictive quantitative analysis was applied to refine a baseline conceptual model through the completion of a series of targeted simulations. The analysis revealed that site recharge is the most important flux-controlling process for future contaminant flux. Tank leak characteristics and subsurface heterogeneities appear to have a limited effect on long-term contaminant flux into groundwater. The occurrence of the current technetium-99 groundwater plume was explained by taking into account a considerable historical water-line leak adjacent to one of the tanks. The analysis further indicates that the vast majority of technetium-99 is expected to migrate into the groundwater during the next century. The approach provides a template for use in evaluating contaminant flux to groundwater using existing site data and has elements that are relevant to other disposal sites with a thick vadose zone.

Evaluation of Deep Vadose Zone Contaminant Flux into Groundwater: Approach and Case Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oostrom, Martinus; Truex, Michael J.; Last, George V.

For sites with a contaminant source located in the vadose zone, the nature and extent of groundwater contaminant plumes are a function of the contaminant flux from the vadose zone to groundwater. Especially for thick vadose zones, transport may be relatively slow making it difficult to directly measure contaminant flux. An integrated assessment approach, supported by site characterization and monitoring data, is presented to explain current vadose zone contaminant distributions and to estimate future contaminant flux to groundwater in support of remediation decisions. The U.S. Department of Energy Hanford Site (WA, USA) SX Tank Farm was used as a casemore » study because of a large existing contaminant inventory in its deep vadose zone, the presence of a limited-extent groundwater plume, and the relatively large amount of available data for the site. A predictive quantitative analysis was applied to refine a baseline conceptual model through the completion of a series of targeted simulations. The analysis revealed that site recharge is the most important flux-controlling process for future contaminant flux. Tank leak characteristics and subsurface heterogeneities appear to have a limited effect on long-term contaminant flux into groundwater. The occurrence of the current technetium-99 groundwater plume was explained by taking into account a considerable historical water-line leak adjacent to one of the tanks. The analysis further indicates that the vast majority of technetium-99 is expected to migrate into the groundwater during the next century. The approach provides a template for use in evaluating contaminant flux to groundwater using existing site data and has elements that are relevant to other disposal sites with a thick vadose zone.« less

Evaluation of deep vadose zone contaminant flux into groundwater: Approach and case study.

PubMed

Oostrom, M; Truex, M J; Last, G V; Strickland, C E; Tartakovsky, G D

2016-06-01

For sites with a contaminant source located in the vadose zone, the nature and extent of groundwater contaminant plumes are a function of the contaminant flux from the vadose zone to groundwater. Especially for thick vadose zones, transport may be relatively slow making it difficult to directly measure contaminant flux. An integrated assessment approach, supported by site characterization and monitoring data, is presented to explain current vadose zone contaminant distributions and to estimate future contaminant flux to groundwater in support of remediation decisions. The U.S. Department of Energy Hanford Site (WA, USA) SX Tank Farm was used as a case study because of a large existing contaminant inventory in its deep vadose zone, the presence of a limited-extent groundwater plume, and the relatively large amount of available data for the site. A predictive quantitative analysis was applied to refine a baseline conceptual model through the completion of a series of targeted simulations. The analysis revealed that site recharge is the most important flux-controlling process for future contaminant flux. Tank leak characteristics and subsurface heterogeneities appear to have a limited effect on long-term contaminant flux into groundwater. The occurrence of the current technetium-99 groundwater plume was explained by taking into account a considerable historical water-line leak adjacent to one of the tanks. The analysis further indicates that the vast majority of technetium-99 is expected to migrate into the groundwater during the next century. The approach provides a template for use in evaluating contaminant flux to groundwater using existing site data and has elements that are relevant to other disposal sites with a thick vadose zone. Copyright © 2016 Elsevier B.V. All rights reserved.

Soil Flushing Through a Thick Vadose Zone: Perchlorate Removal Documented at Edwards AFB, California

NASA Astrophysics Data System (ADS)

Battey, T. F.; Shepard, A. J.; Tait, R. J.

2007-12-01

There are currently few viable alternatives for perchlorate remediation in the vadose zone, particularly for the relatively thick vadose zones that are typical in the arid southwest where many perchlorate sites occur. Perchlorate in the vadose zone occurs in the form of highly soluble salts that may represent a risk to human or ecological receptors, and may also represent a threat to the underlying groundwater. A soil flushing treatability study was conducted at Edwards Air Force Base in the Mojave Desert of southern California at a site with a 129-foot thick vadose zone consisting primarily of clayey sand. This study utilized an infiltration gallery in conjunction with extraction, treatment, and re-injection of groundwater at the site, which contained perchlorate-contaminated soil and groundwater. The study objective was to evaluate the effectiveness of the infiltration gallery to 1) introduce treated groundwater back into the aquifer and 2) wash the perchlorate from the vadose zone soils to the aquifer. The infiltration gallery consisted of slotted PVC pipes within a highly permeable engineered bed of washed gravel. The initial water introduced into the gallery was amended with potassium bromide tracer. A downhole neutron probe was used to track the movement of the wetting front downward and outward from the gallery. Successive neutron measurements in vertical access tubes revealed that the introduced water reached the 125-foot bottom of the access tubes 14 weeks after the water was introduced into the gallery. The bromide tracer was detected in groundwater immediately below the gallery approximately 1 week later. The infiltration gallery was able to sustain an average flow rate of 2.3 gallons per minute. Prior to infiltration, the perchlorate concentration in groundwater below the gallery was 4,500 µg/L. Approximately 18 weeks after the start of infiltration, a perchlorate spike of 72,400 µg/L was detected below the gallery. The increase in perchlorate

Multi-scale hydrogeological and hydrogeophysical approach to monitor vadose zone hydrodynamics of a karst system

NASA Astrophysics Data System (ADS)

Watlet, Arnaud; Poulain, Amaël; Van Camp, Michel; Francis, Olivier; Triantafyllou, Antoine; Rochez, Gaëtan; Hallet, Vincent; Kaufmann, Olivier

2016-04-01

The vadose zone of karst systems plays an important role on the water dynamics. In particular, temporary perched aquifers can appear in the subsurface due to changes of weather conditions, reduced evapotranspiration and the vertical gradients of porosity and permeability. Although many difficulties are usually encountered when studying karst environments due to their heterogeneities, cave systems offer an outstanding opportunity to investigate vadose zone from the inside. We present a multi-scale study covering two years of hydrogeological and geophysical monitoring of the Lomme Karst System (LKS) located in the Variscan fold-and-thrust belt (Belgium), a region (~ 3000 ha) that shows many karstic networks within Devonian limestone units. Hydrogeological data cover the whole LKS and involve e.g. flows and levels monitoring or tracer tests performed in both vadose and saturated zones. Such data bring valuable information on the hydrological context of the studied area at the catchment scale. Combining those results with geophysical measurements allows validating and imaging them at a smaller scale, with more integrative techniques. Hydrogeophysical measurements are focused on only one cave system of the LKS, at the Rochefort site (~ 40 ha), taking benefit of the Rochefort Cave Laboratory (RCL) infrastructures. In this study, a microgravimetric monitoring and an Electrical Resistivity Tomography (ERT) monitoring are involved. The microgravimetric monitoring consists in a superconducting gravimeter continuously measuring gravity changes at the surface of the RCL and an additional relative gravimeter installed in the underlying cave located 35 meters below the surface. While gravimeters are sensible to changes that occur in both the vadose zone and the saturated zone of the whole cave system, combining their recorded signals allows enhancing vadose zone's gravity changes. Finally, the surface ERT monitoring provide valuable information at the (sub)-meter scale on the

Impact of switching crop type on water and solute fluxes in deep vadose zone

NASA Astrophysics Data System (ADS)

Turkeltaub, T.; Kurtzman, D.; Russak, E. E.; Dahan, O.

2015-12-01

Switching crop type and consequently changing irrigation and fertilization regimes lead to alterations in deep percolation and solute concentrations of pore water. Herein, observations from the deep vadose zone and model simulations demonstrate the changes in water, chloride, and nitrate fluxes under a commercial greenhouse following the change from tomato to lettuce cropping. The site, located above a phreatic aquifer, was monitored for 5 years. A vadose-zone monitoring system was implemented under the greenhouse and provided continuous data on both temporal variations in water content and chemical composition of the pore water at multiple depths in the deep vadose zone (up to 20 m). Following crop switching, a significant reduction in chloride concentration and dramatic increase in nitrate were observed across the unsaturated zone. The changes in chemical composition of the vadose-zone pore water appeared as sequential breakthroughs across the unsaturated zone, initiating at land surface and propagating down toward the water table. Today, 3 years after switching the crops, penetration of the impact exceeds 10 m depth. Variations in the isotopic composition of nitrate (18O and 15N) in water samples obtained from the entire vadose zone clearly support a fast leaching process and mobilization of solutes across the unsaturated zone following the change in crop type. Water flow and chloride transport models were calibrated to observations acquired during an enhanced infiltration experiment. Forward simulation runs were performed with the calibrated models, constrained to tomato and lettuce cultivation regimes as surface boundary conditions. Predicted chloride and nitrate concentrations were in agreement with the observed concentrations. The simulated water drainage and nitrogen leaching implied that the observed changes are an outcome of recommended agricultural management practices.

Tank 241-AX-104 upper vadose zone cone penetrometer demonstration sampling and analysis plan

DOE Office of Scientific and Technical Information (OSTI.GOV)

FIELD, J.G.

1999-02-02

This sampling and analysis plan (SAP) is the primary document describing field and laboratory activities and requirements for the tank 241-AX-104 upper vadose zone cone penetrometer (CP) demonstration. It is written in accordance with Hanford Tank Initiative Tank 241-AX-104 Upper Vadose Zone Demonstration Data Quality Objective (Banning 1999). This technology demonstration, to be conducted at tank 241-AX-104, is being performed by the Hanford Tanks Initiative (HTI) Project as a part of Tank Waste Remediation System (TWRS) Retrieval Program (EM-30) and the Office of Science and Technology (EM-50) Tanks Focus Area. Sample results obtained as part of this demonstration will providemore » additional information for subsequent revisions to the Retrieval Performance Evaluation (RPE) report (Jacobs 1998). The RPE Report is the result of an evaluation of a single tank farm (AX Tank Farm) used as the basis for demonstrating a methodology for developing the data and analyses necessary to support making tank waste retrieval decisions within the context of tank farm closure requirements. The RPE includes a study of vadose zone contaminant transport mechanisms, including analysis of projected tank leak characteristics, hydrogeologic characteristics of tank farm soils, and the observed distribution of contaminants in the vadose zone in the tank farms. With limited characterization information available, large uncertainties exist as to the nature and extent of contaminants that may exist in the upper vadose zone in the AX Tank Farm. Traditionally, data has been collected from soils in the vadose zone through the installation of boreholes and wells. Soil samples are collected as the bore hole is advanced and samples are screened on site and/or sent to a laboratory for analysis. Some in-situ geophysical methods of contaminant analysis can be used to evaluate radionuclide levels in the soils adjacent to an existing borehole. However, geophysical methods require compensation for

Development of the INEEL Site Wide Vadose Zone Roadmap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yonk, Alan Keith

2001-09-01

The INEEL Vadose Zone Roadmap was developed to identify inadquacies in current knowledge, to assist in contaminant management capabilities relative to the INEEL vadose zone, and to ensure that ongoing and planned Science and Technology developments will meet the risk management challenges facing the INEEL in coming years. The primary objective of the Roadmap is to determine the S&T needs that will facilitate monitoring, characterization, prediction, and assessment activities necessary to support INEEL risk management decisions and to ensure that long-term stewardship of contaminated sites at the INEEL is achieved. The mission of the Roadmap is to insure that themore » long-term S&T strategy is aligned with site programs, that it takes advantage of progress made to date, and that it can assist in meeting the milestones and budgets of operations.« less

Sensitivity of Vadose Zone Water Fluxes to Climate Shifts in Arid Settings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pfletschinger, H.; Prömmel, K.; Schüth, C.

2014-01-01

Vadose zone water fluxes in arid settings are investigated regarding their sensitivity to hydraulic soil parameters and meteorological data. The study is based on the inverse modeling of highly defined soil column experiments and subsequent scenario modeling comparing different climate projections for a defined arid region. In arid regions, groundwater resources are prone to depletion due to excessive water use and little recharge potential. Especially in sand dune areas, groundwater recharge is highly dependent on vadose zone properties and corresponding water fluxes. Nevertheless, vadose zone water fluxes under arid conditions are hard to determine owing to, among other reasons, deepmore » vadose zones with generally low fluxes and only sporadic high infiltration events. In this study, we present an inverse model of infiltration experiments accounting for variable saturated nonisothermal water fluxes to estimate effective hydraulic and thermal parameters of dune sands. A subsequent scenario modeling links the results of the inverse model with projections of a global climate model until 2100. The scenario modeling clearly showed the high dependency of groundwater recharge on precipitation amounts and intensities, whereas temperature increases are only of minor importance for deep infiltration. However, simulated precipitation rates are still affected by high uncertainties in the response to the hydrological input data of the climate model. Thus, higher certainty in the prediction of precipitation pattern is a major future goal for climate modeling to constrain future groundwater management strategies in arid regions.« less

TWRS vadose zone contamination issue expert panel report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shafer, D.S.

1997-05-01

When members were first canvassed for participation in the Vadose Zone Expert Panel the stated purpose for convening the Panel was to review a controversial draft report, the SX Tank Farm Report. This report was produced by a DOE Grand Junction Project Office (GJPO) contractor, RUST Geotech, now MACTEC-ERS, for the DOE Richland Office (DOERL). Three meetings were planned for June, July and August, 1995 to review the draft report and to complete a Panel report by mid-September. The Expert Panel has found its efforts confounded by various non-technical issues. The Expert Panel has chosen to address some of themore » non-technical issues in this Preface rather than to dilute the technical discussion that follows in the body of this independent expert panel status report (Panel Report). Rather than performing a straightforward manuscript review, the Panel was asked to resolve conflicting interpretations of gamma-ray logging measurements performed in vadose zone boreholes (drywells) surrounding the high-level radioactive wastes of the SX tank farm. There are numerous and complex technical issues that must be evaluated before the vertical and radial extent of contaminant migration at the SX tank farm can be accurately assessed. When the Panel first met in early June, 1996, it quickly became apparent that the scientific and technical issues were obscured by policy and institutional affairs which have polarized discussion among various segments of the Hanford organization. This situation reflects the kinds of institutional problems described separately in reports by the National Research Council of the National Academy of Sciences (NAS/NRC), The Hanford Tanks Environmental Impacts and Policy Choices and BmTiers to Science: Technical Management of the Department of Energy Environmental Remediation Program. The Vadose Zone Characterization Program, appears to be caught between conflicting pressures and organizational mandates, some imposed from outside DOE-RL and some self

Wildfire effects on vadose zone hydrology in forested boreal peatland microforms

NASA Astrophysics Data System (ADS)

Thompson, Dan K.; Waddington, James M.

2013-04-01

SummaryPeatland vulnerability to wildfire disturbance has been shown to vary as a function of hummock and hollow microforms and vadose zone hydrology, with low-lying hollow microforms most susceptible to deep combustion of peat. To better understand how this microform induced pattern of burning alters vadose water storage, pore-water pressure, and water table relationships, we examined a paired burned and unburned peatland in the boreal plain region of north central Alberta. Water table response to rain events increased significantly after wildfire, resulting in a more variable unsaturated zone thickness that was more responsive to smaller rain events. Water storage losses in the vadose zone occurred primarily at depths greater than 15 cm. Large peat surface water loss occurred in hummock microforms in the early spring due to the presence of unsaturated frozen peat at depth, likely a result of a vapour gradient from the unfrozen peat into the frozen peat underneath. During this period, the loss of water storage in the vadose zone satisfied up to 25% of daily evaporative demand, compared to only 3-5% during ice-free periods. A similar but less severe drying was observed late in summer, with burned hummocks the most vulnerable with high pore-water pressures. The enhanced surface drying observed is a precursor to high pore-water pressure conditions that inhibit Sphagnum regeneration. Our observations point to a paradox where the hummocks, being most resistant to combustion, are themselves most prone to high pore-water pressures following wildfire. The harsher hummock environment may contribute to the observed delay in post-fire Sphagnum regeneration in hummocks compared to hollows.

Vadose Zone Monitoring as a Key to Groundwater Protection from Pollution Hazard

NASA Astrophysics Data System (ADS)

Dahan, Ofer

2016-04-01

Minimization subsurface pollution is much dependent on the capability to provide real-time information on the chemical and hydrological properties of the percolating water. Today, most monitoring programs are based on observation wells that enable data acquisitions from the saturated part of the subsurface. Unfortunately, identification of pollutants in well water is clear evidence that the contaminants already crossed the entire vadose-zone and accumulated in the aquifer water to detectable concentration. Therefore, effective monitoring programs that aim at protecting groundwater from pollution hazard should include vadose zone monitoring technologies that are capable to provide real-time information on the chemical composition of the percolating water. Obviously, identification of pollution process in the vadose zone may provide an early warning on potential risk to groundwater quality, long before contaminates reach the water-table and accumulate in the aquifers. Since productive agriculture must inherently include down leaching of excess lower quality water, understanding the mechanisms controlling transport and degradation of pollutants in the unsaturated is crucial for water resources management. A vadose-zone monitoring system (VMS), which was specially developed to enable continuous measurements of the hydrological and chemical properties of percolating water, was used to assess the impact of various agricultural setups on groundwater quality, including: (a) intensive organic and conventional greenhouses, (b) citrus orchard and open field crops , and (c) dairy farms. In these applications frequent sampling of vadose zone water for chemical and isotopic analysis along with continuous measurement of water content was used to assess the link between agricultural setups and groundwater pollution potential. Transient data on variation in water content along with solute breakthrough at multiple depths were used to calibrate flow and transport models. These models

Atrazine retention and degradation in the vadose zone at a till plain site in central Indiana

USGS Publications Warehouse

Bayless, E.R.

2001-01-01

The vadose zone was examined as an environmental compartment where significant quantities of atrazine and its degradation compounds may be stored and transformed. The vadose zone was targeted because regional studies in the White River Basin indicated a large discrepancy between the mass of atrazine applied to fields and the amount of the pesticide and its degradation compounds that are measured in ground and surface water. A study site was established in a rotationally cropped field in the till plain of central Indiana. Data were gathered during the 1994 growing season to characterize the site hydrogeology and the distribution of atrazine, desethylatrazine, deisopropylatrazine, didealkylatrazine and hydroxyatrazine in runoff, pore water, and ground water. The data indicated that atrazine and its degradation compounds were transported from land surface to a depth of 1.5 m within 60 days of application, but were undetected in the saturated zone at nearby monitoring wells. A numerical model was developed, based on the field data, to provide information about processes that could retain and degrade atrazine in the vadose zone. Simulations indicated that evapotranspiration is responsible for surface directed soil-moisture flow during much of the growing season. This process causes retention and degradation of atrazine in the vadose zone. Increased residence time in the vadose zone leads to nearly complete transformation of atrazine and its degradation products to unquantified degradation compounds. As a result of mascropore flow, small quantities of atrazine and its degradation compounds may reach the saturated zone.

Vadose Zone Transport Field Study: Detailed Test Plan for Simulated Leak Tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Anderson L.; Gee, Glendon W.

2000-06-23

This report describes controlled transport experiments at well-instrumented field tests to be conducted during FY 2000 in support of DOE?s Vadose Zone Transport Field Study (VZTFS). The VZTFS supports the Groundwater/Vadose Zone Integration Project Science and Technology Initiative. The field tests will improve understanding of field-scale transport and lead to the development or identification of efficient and cost-effective characterization methods. These methods will capture the extent of contaminant plumes using existing steel-cased boreholes. Specific objectives are to 1) identify mechanisms controlling transport processes in soils typical of the hydrogeologic conditions of Hanford?s waste disposal sites; 2) reduce uncertainty in conceptualmore » models; 3) develop a detailed and accurate data base of hydraulic and transport parameters for validation of three-dimensional numerical models; and 4) identify and evaluate advanced, cost-effective characterization methods with the potential to assess changing conditions in the vadose zone, particularly as surrogates of currently undetectable high-risk contaminants. Pacific Northwest National Laboratory (PNNL) manages the VZTFS for DOE.« less

Estimating the Impact of Vadose Zone Sources on Groundwater to Support Performance Assessment of Soil Vapor Extraction

EPA Science Inventory

Soil vapor extraction (SVE) is a prevalent remediation approach for volatile contaminants in the vadose zone. To support selection of an appropriate endpoint for the SVE remedy, an evaluation is needed to determine whether vadose zone contamination has been diminished sufficient...

Soil Moisture Flow and Nitrate Movement Simulation through Deep and Heterogeneous Vadose Zone using Dual-porosity Approach

NASA Astrophysics Data System (ADS)

Yadav, B. K.; Tomar, J.; Harter, T.

2014-12-01

We investigate nitrate movement from non-point sources in deep, heterogeneous vadose zones, using multi-dimensional variably saturated flow and transport simulations. We hypothesize that porous media heterogeneity causes saturation variability that leads to preferential flow systems such that a significant portion of the vadose zone does not significantly contribute to flow. We solve Richards' equation and the advection-dispersion equation to simulate soil moisture and nitrate transport regimes in plot-scale experiments conducted in the San Joaquin Valley, California. We compare equilibrium against non-equilibrium (dual-porosity) approaches. In the equilibrium approach we consider each soil layer to have unique hydraulic properties as a whole, while in the dual-porosity approach we assume that large fractions of the porous flow domain are immobile. However we consider exchange of water and solute between mobile and immobile zone using the appropriate mass transfer terms. The results indicate that flow and transport in a nearly 16 m deep stratified vadose zone comprised of eight layers of unconsolidated alluvium experiences highly non-uniform, localized preferential flow and transport patterns leading to accelerated nitrate transfer. The equilibrium approach largely under-predicted the leaching of nitrate to groundwater while the dual-porosity approach showed higher rates of nitrate leaching, consistent with field observations. The dual-porosity approach slightly over-predicted nitrogen storage in the vadose zone, which may be the result of limited matrix flow or denitrification not accounted for in the model. Results of this study may be helpful to better predict fertilizer and pesticide retention times in deep vadose zone, prior to recharge into the groundwater flow system. Keywords: Nitrate, Preferential flow, Heterogeneous vadose zone, Dual-porosity approach

CMI Remedy Selection for HE- and Barium-Contaminated Vadose Zone and Alluvium at LANL

NASA Astrophysics Data System (ADS)

Hickmott, D.; Reid, K.; Pietz, J.; Ware, D.

2008-12-01

A high explosives (HE) machining building outfall at Los Alamos National Laboratory's Technical Area 16 discharged millions of gallons of HE- and barium-contaminated water into the Canon de Valle watershed. The effluent contaminated surface soils, the alluvial aquifer, vadose zone waters, and deep-perched and regional groundwaters with HE and barium, frequently at levels greater than regulatory standards. Site characterization studies began in 1995 and included extensive monitoring of surface water, groundwater, soils, and subsurface solid media. Hydrogeologic and geophysical studies were conducted to help understand contaminant transport mechanisms and pathways. Results from the characterization studies were used to develop a site conceptual model. In 2000 the principal source area was removed. The ongoing Corrective Measure Study (CMS) and Corrective Measure Implementation (CMI) focus on residual vadose zone contamination and on the contaminated alluvial system. Regulators recently selected a CMI remedy that combined: 1) augmented source removal; 2) grouting of an HE- contaminated surge bed; 3) deployment of Stormwater Management System (SMS) stormfilters in contaminated springs; and 4) permeable reactive barriers (PRBs) in contaminated alluvium. The hydrogeologic conceptual model for the vadose zone and alluvial system as well as the status of the canyon as habitat for the Mexican Spotted Owl were key factors in selection of these minimal-environmental-impact remedies. The heterogeneous vadose zone, characterized by flow and contaminant transport in fractures and in surge beds, requires contaminant treatment at a point of discharge. The canyon PRB is being installed to capture water and contaminants prior to infiltration into the vadose zone. Pilot-scale testing of the SMS and lab-scale batch and column tests of a range of media suggest that granular activated carbon, zeolite, and gypsum may be effective media for removal of HE and/or barium from contaminated

Evaluating Contaminant Flux from the Vadose Zone to the Groundwater in the Hanford Central Plateau. SX Tank Farms Case Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Oostrom, Martinus; Last, George V.

At the DOE Hanford Site, contaminants were discharged to the subsurface through engineered waste sites in the Hanford Central Plateau. Additional waste was released through waste storage tank leaks. Much of the contaminant inventory is still present within the unsaturated vadose zone sediments. The nature and extent of future groundwater contaminant plumes and the growth or decline of current groundwater plumes beneath the Hanford Central Plateau are a function of the contaminant flux from the vadose zone to the groundwater. In general, contaminant transport is slow through the vadose zone and it is difficult to directly measure contaminant flux inmore » the vadose zone. Predictive analysis, supported by site characterization and monitoring data, was applied using a structured, systems-based approach to estimate the future contaminant flux to groundwater in support of remediation decisions for the vadose zone and groundwater (Truex and Carroll 2013). The SX Tank Farm was used as a case study because of the existing contaminant inventory in the vadose zone, observations of elevated moisture content in portions of the vadose zone, presence of a limited-extent groundwater plume, and the relatively large amount and wide variety of data available for the site. Although the SX Tank Farm case study is most representative of conditions at tank farm sites, the study has elements that are also relevant to other types of disposal sites in the Hanford Central Plateau.« less

Deep arid system hydrodynamics 1. Equilibrium states and response times in thick desert vadose zones

USGS Publications Warehouse

Walvoord, Michelle Ann; Plummer, Mitchell A.; Phillips, Fred M.; Wolfsberg, Andrew V.

2002-01-01

Quantifying moisture fluxes through deep desert soils remains difficult because of the small magnitude of the fluxes and the lack of a comprehensive model to describe flow and transport through such dry material. A particular challenge for such a model is reproducing both observed matric potential and chloride profiles. We propose a conceptual model for flow in desert vadose zones that includes isothermal and nonisothermal vapor transport and the role of desert vegetation in supporting a net upward moisture flux below the root zone. Numerical simulations incorporating this conceptual model match typical matric potential and chloride profiles. The modeling approach thereby reconciles the paradox between the recognized importance of plants, upward driving forces, and vapor flow processes in desert vadose zones and the inadequacy of the downward‐only liquid flow assumption of the conventional chloride mass balance approach. Our work shows that water transport in thick desert vadose zones at steady state is usually dominated by upward vapor flow and that long response times, of the order of 104–105 years, are required to equilibrate to existing arid surface conditions. Simulation results indicate that most thick desert vadose zones have been locked in slow drying transients that began in response to a climate shift and establishment of desert vegetation many thousands of years ago.

Depth of the vadose zone controls aquifer biogeochemical conditions and extent of anthropogenic nitrogen removal

USGS Publications Warehouse

Szymczycha, Beata; Kroeger, Kevin D.; Crusius, John; Bratton, John F.

2017-01-01

We investigated biogeochemical conditions and watershed features controlling the extent of nitrate removal through microbial dinitrogen (N2) production within the surficial glacial aquifer located on the north and south shores of Long Island, NY, USA. The extent of N2 production differs within portions of the aquifer, with greatest N2 production observed at the south shore of Long Island where the vadose zone is thinnest, while limited N2production occurred under the thick vadose zones on the north shore. In areas with a shallow water table and thin vadose zone, low oxygen concentrations and sufficient DOC concentrations are conducive to N2production. Results support the hypothesis that in aquifers without a significant supply of sediment-bound reducing potential, vadose zone thickness exerts an important control of the extent of N2 production. Since quantification of excess N2 relies on knowledge of equilibrium N2concentration at recharge, calculated based on temperature at recharge, we further identify several features, such as land use and cover, seasonality of recharge, and climate change that should be considered to refine estimation of recharge temperature, its deviation from mean annual air temperature, and resulting deviation from expected equilibrium gas concentrations.

Approach to the vadose zone monitoring in hazardous and solid waste disposal facilities

NASA Astrophysics Data System (ADS)

Twardowska, Irena

2004-03-01

In the solid waste (SW)disposal sites, in particular at the unlined facilities, at the remediated or newly-constructed units equipped with novel protective/reactive permeable barriers or at lined facilities with leachate collection systems that are prone to failure, the vadose zone monitoring should comprise besides the natural soil layer beneath the landfill, also the anthropogenic vadose zone, i.e. the waste layer and pore solutions in the landfill. The vadose zone screening along the vertical profile of SW facilities with use of direct invasive soil-core and soil-pore liquid techniques shows vertical downward redistribution of inorganic (macroconstituents and heavy metals) and organic (PAHs) contaminant loads in water infiltrating through the waste layer. These loads can make ground water down-gradient of the dump unfit for any use. To avoid damage of protective/reactive permeable barriers and liners, an installation of stationary monitoring systems along the waste layer profile during the construction of a landfill, which are amenable to generate accurate data and information in a near-real time should be considered including:(i) permanent samplers of pore solution, with a periodic pump-induced transport of collected solution to the surface, preferably with instant field measurements;(ii)chemical sensors with continuous registration of critical parameters. These techniques would definitely provide an early alert in case when the chemical composition of pore solution percolating downward the waste profile shows unfavorable transformations, which indicate an excessive contaminant load approaching ground water. The problems concerning invasive and stationary monitoring of the vadose zone in SW disposal facilities will be discussed at the background of results of monitoring data and properties of permeable protective/reactive barriers considered for use.

The Mojave vadose zone: a subsurface biosphere analogue for Mars.

PubMed

Abbey, William; Salas, Everett; Bhartia, Rohit; Beegle, Luther W

2013-07-01

If life ever evolved on the surface of Mars, it is unlikely that it would still survive there today, but as Mars evolved from a wet planet to an arid one, the subsurface environment may have presented a refuge from increasingly hostile surface conditions. Since the last glacial maximum, the Mojave Desert has experienced a similar shift from a wet to a dry environment, giving us the opportunity to study here on Earth how subsurface ecosystems in an arid environment adapt to increasingly barren surface conditions. In this paper, we advocate studying the vadose zone ecosystem of the Mojave Desert as an analogue for possible subsurface biospheres on Mars. We also describe several examples of Mars-like terrain found in the Mojave region and discuss ecological insights that might be gained by a thorough examination of the vadose zone in these specific terrains. Examples described include distributary fans (deltas, alluvial fans, etc.), paleosols overlain by basaltic lava flows, and evaporite deposits.

Measurement and partitioning of evapotranspiration for application to vadose zone studies

USDA-ARS?s Scientific Manuscript database

Partitioning evapotranspiration (ET) into its constituent components, soil evaporation (E) and plant transpiration (T), is important for vadose zone studies because E and T are often parameterized separately. However, partitioning ET is challenging, and many longstanding approaches have significant ...

Effect of soil moisture on the sorption of trichloroethene vapor to vadose-zone soil at picatinny arsenal, New Jersey

USGS Publications Warehouse

Smith, J.A.; Chiou, C.T.; Kammer, J.A.; Kile, D.E.

1990-01-01

This report presents data on the sorption of trichloroethene (TCE) vapor to vadose-zone soil above a contaminated water-table aquifer at Picatinny Arsenal in Morris County, NJ. To assess the impact of moisture on TCE sorption, batch experiments on the sorption of TCE vapor by the field soil were carried out as a function of relative humidity. The TCE sorption decreases as soil moisture content increases from zero to saturation soil moisture content (the soil moisture content in equilibrium with 100% relative humidity). The moisture content of soil samples collected from the vadose zone was found to be greater than the saturation soil-moisture content, suggesting that adsorption of TCE by the mineral fraction of the vadose-zone soil should be minimal relative to the partition uptake by soil organic matter. Analyses of soil and soil-gas samples collected from the field indicate that the ratio of the concentration of TCE on the vadose-zone soil to its concentration in the soil gas is 1-3 orders of magnitude greater than the ratio predicted by using an assumption of equilibrium conditions. This apparent disequilibrium presumably results from the slow desorption of TCE from the organic matter of the vadose-zone soil relative to the dissipation of TCE vapor from the soil gas.

Deep Vadose Zone Treatability Test for the Hanford Central Plateau: Interim Post-Desiccation Monitoring Results, Fiscal Year 2014

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Strickland, Christopher E.; Johnson, Christian D.

Over decades of operation, the U.S. Department of Energy (DOE) and its predecessors have released nearly 2 trillion L (450 billion gal.) of liquid into the vadose zone at the Hanford Site. Much of this discharge of liquid waste into the vadose zone occurred in the Central Plateau, a 200 km 2 (75 mi 2) area that includes approximately 800 waste sites. Some of the inorganic and radionuclide contaminants in the deep vadose zone at the Hanford Site are at depths below the limit of direct exposure pathways, but may need to be remediated to protect groundwater. The Tri-Party Agenciesmore » (DOE, U.S. Environmental Protection Agency, and Washington State Department of Ecology) established Milestone M 015 50, which directed DOE to submit a treatability test plan for remediation of technetium-99 (Tc-99) and uranium in the deep vadose zone. These contaminants are mobile in the subsurface environment and have been detected at high concentrations deep in the vadose zone, and at some locations have reached groundwater. Testing technologies for remediating Tc-99 and uranium will also provide information relevant for remediating other contaminants in the vadose zone. A field test of desiccation is being conducted as an element of the DOE test plan published in March 2008 to meet Milestone M 015 50. The active desiccation portion of the test has been completed. Monitoring data have been collected at the field test site during the post-desiccation period and are reported herein. This is an interim data summary report that includes about 3 years of post-desiccation monitoring data. The DOE field test plan proscribes a total of 5 years of post-desiccation monitoring.« less

Time lag estimates for nitrate travel through the vadose zone in Southland, New Zealand

NASA Astrophysics Data System (ADS)

Wilson, Scott; Chanut, Pierre; Ledgard, George; Rissmann, Clint

2014-05-01

A regional-scale study was carried out to calculate the travel time of a nitrate particle from the ground surface into shallow groundwater. The aim of the study was to obtain preliminary answers to two questions. Firstly, if leaching limits are set, how long would it take to see an improvement in shallow groundwater quality? Secondly, have groundwater nitrate concentrations reached equilibrium from recent dairy expansion in the region, or could we expect future increases? We applied a methodology that provides a balance between the detail and generalisation that is required for a regional-scale study. Steady-state advective transport through the vadose zone was modelled with water retention curves. These curves enable an estimate of the average volumetric water content of the vadose zone. The percentage saturation can then be used to calculate the vadose zone transit time if effective porosity, depth to the water table and annual average soil drainage are known. A time for mixing in the uppermost part of the aquifer has also been calculated. Two different vadose zone water retention curve models were used for comparison, the Brooks-Corey (1964), and the Van Genuchten (1980) methods. The water retention curves were parameterised by sediment texture via the Rawls and Brakensiek (1985) pedotransfer functions. Hydraulic properties were derived by positioning sediment textural descriptions on the Folk textural triangle, estimates of effective porosity from literature, and hydraulic conductivity values from aquifer tests. Uncertainty of parameter estimates was included by assigning standard deviations and appropriate probability distributions. Vadose zone saturation was modelled at 6,450 sites across the region with a Monte Carlo simulation involving 10,000 realisations. This generated a probability distribution of saturation for each site. Average volumetric water content of the vadose zone ranged from 8.5 to 40.7 % for the Brooks-Corey model and 12.9 to 36.3% for the

COLLOID-FACILITATED TRANSPORT OF RADIONUCLIDES THROUGH THE VADOSE ZONE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flury, Markus

2003-09-14

Contaminants have leaked into the vadose zone at the USDOE Hanford reservation. It is important to understand the fate and transport of these contaminants to design remediation strategies and long-term waste management plans at the Hanford reservation. Colloids may play an important role in fate and transport of strongly sorbing contaminants, such as Cs or Pu. This project seeks to improve the basic understanding of colloid and colloid-facilitated transport of contaminants in the vadose zone. The specific objectives addressed are: (1) Determine the structure, composition, and surface charge characteristics of colloidal particles formed under conditions similar to those occurring duringmore » leakage of waste typical of Hanford tank supernatants into soils and sediments surrounding the tanks. (2) Characterize the mutual interactions between colloids, contaminant, and soil matrix in batch experiments under various ionic strength and pH conditions. We will investigate the nature of the solid-liquid interactions and the kinetics of the reactions. (3) Evaluate mobility of colloids through soil under different degrees of water saturation and solution chemistry (ionic strength and pH). (4) Determine the potential of colloids to act as carriers to transport the contaminant through the vadose zone and verify the results through comparison with field samples collected under leaking tanks. (5) Improve conceptual characterization of colloid-contaminant-soil interactions and colloid-facilitated transport for implementation into reactive chemical transport models. This project was in part supported by an NSF-IGERT grant to Washington State University. The IGERT grant provided funding for graduate student research and education, and two graduate students were involved in the EMSP project. The IGERT program also supported undergraduate internships. The project is part of a larger EMSP program to study fate and transport of contaminants under leaking Hanford waste tanks. The

Transport and degradation of perchlorate in deep vadose zone: implications from direct observations during bioremediation treatment

NASA Astrophysics Data System (ADS)

Dahan, Ofer; Katz, Idan; Avishai, Lior; Ronen, Zeev

2017-08-01

An in situ bioremediation experiment of a deep vadose zone ( ˜ 40 m) contaminated with a high concentration of perchlorate (> 25 000 mg L-1) was conducted through a full-scale field operation. Favourable environmental conditions for microbiological reduction of perchlorate were sought by infiltrating an electron donor-enriched water solution using drip irrigation underlying an airtight sealing liner. A vadose zone monitoring system (VMS) was used for real-time tracking of the percolation process, the penetration depth of dissolved organic carbon (DOC), and the variation in perchlorate concentration across the entire soil depth. The experimental conditions for each infiltration event were adjusted according to insight gained from data obtained by the VMS in previous stages. Continuous monitoring of the vadose zone indicated that in the top 13 m of the cross section, perchlorate concentration is dramatically reduced from thousands of milligrams per litre to near-detection limits with a concurrent increase in chloride concentration. Nevertheless, in the deeper parts of the vadose zone (< 17 m), perchlorate concentration increased, suggesting its mobilization down through the cross section. Breakthrough of DOC and bromide at different depths across the unsaturated zone showed limited migration capacity of biologically consumable carbon and energy sources due to their enhanced biodegradation in the upper soil layers. Nevertheless, the increased DOC concentration with concurrent reduction in perchlorate and increase in the chloride-to-perchlorate ratio in the top 13 m indicate partial degradation of perchlorate in this zone. There was no evidence of improved degradation conditions in the deeper parts where the initial concentrations of perchlorate were significantly higher.

Borehole Time Domain Reflectometry in Layered Sandstone: Impact of Measurement Technique on Vadose Zone Process Identification

NASA Astrophysics Data System (ADS)

West, J.; Truss, S. W.

2004-12-01

An investigation is reported into the hydraulic behaviour of the vadose zone of a layered sandstone aquifer using borehole-based Time Domain Reflectometry (TDR). TDR has been widely applied to shallow soils but has seen limited application at greater depth and in cemented lithologies due to the difficulty of installing conventional TDR probes in rock and from boreholes. Here, flat TDR probes that are simply in contact with, rather than inserted within the medium under investigation, have been developed and applied in a field study. Both a commercially available portable packer TDR system (TRIME-B3L Borehole Packer Probe) and specially designed TDR probes, permanently installed in boreholes on grouted-in packers were used to monitor seasonal fluctuations in moisture content in the vadose zone of a layered sandstone over one year under natural rainfall loading. The data show that the vadose zone contains seasonal perched water tables that form when downward percolating moisture reaches layers of fine grained sandstone and siltstone and causes local saturation. The formation of perched water tables is likely to lead to lateral flow bypassing the less permeable, finer layers. This contrasts with behaviour inferred from previous studies of the same aquifer that used borehole radar and resistivity, which suggested its vadose zone behaviour was characterized by uniform downwards migration of wetting fronts. To investigate the impact of measurement technique on observed response, the TDR data reported here were used to produce simulated zero offset profile (ZOP) borehole radar responses. This simulation confirmed the limited ability of ZOP borehole radar to detect key vadose zone processes, because the phenomenon of critical refraction minimizes the sensitivity of the results to high moisture content layers. The study illustrates that inappropriate technique selection results in hydrological process mis-identification, with serious consequences for the usefulness of data

Water recharge and solute transport through the vadose zone of fractured chalk under desert conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nativ, R.; Dahan, O.; Adar, E.

In the present study the inferred mechanism of groundwater recharge and contamination was studied using tracer concentrations in the fractured vadose zone of the Avdat chalk. The results of this study are important for an evaluation of groundwater contamination from existing and planned facilities in the northern Negev desert in Israel. This study focused on the vicinity of the Ramat Hovav industrial chemical complex in the northern Negev, which also includes the national site for hazardous waste. Water recharge and solute migration rates were examined in five core holes and one borehole which penetrate the entire vadose zone and enabledmore » the collection of rock samples for chemical and isotopic analyses, and an observation of fracture distribution with depth. Tritium profiles were used to estimate water percolation rates through the vadose zone, chloride profiles were used to assess the migration rate of nonreactive solutes, and bromide profiles were also used to evaluate the migration rate of nonreactive contaminants. Deuterium and oxygen 18 profiles were used to assess the evaporation of the infiltrating water at and near land surface.« less

Application of Vadose Zone Monitoring Technology for Characterization of Leachate Generation in Landfills

NASA Astrophysics Data System (ADS)

aharoni, imri; dahan, ofer

2016-04-01

Ground water contamination due to landfill leachate percolation is considered the most severe environmental threat related to municipal solid waste landfills. Natural waste degradation processes in landfills normally produce contaminated leachates up to decades after the waste has been buried. Studies have shown that understanding the mechanisms which govern attenuation processes and the fate of pollutants in the waste and in the underlying unsaturated zone is crucial for evaluation of environmental risks and selection of a restoration strategy. This work focuses on a closed landfill in the coastal plain of Israel that was active until 2002 without any lining infrastructure. A vadose zone monitoring system (VMS) that was implemented at the site enables continuous measurements across the waste body (15 m thick) and underlying sandy vadose zone (16 m thick). Data collected by the VMS included continuous measurements of water content as well as chemical composition of the leachates across the entire waste and vadose zone cross section. Results indicated that winter rain percolated through the waste, generating wetting waves which were observed across the waste and unsaturated sediment from land surface until groundwater at 31 m bls. Quick percolation and high fluxes were observed in spite of the clay cover that was implemented at the site as part of the rehabilitation scheme. The results show that the flow pattern is controlled by a preferential mechanism within the waste body. Specific sections showed rapid fluxes in response to rain events, while other sections remained unaffected. In the underlying sandy vadose zone the flow pattern exhibited characteristics of matrix flow. Yet, some sections received higher fluxes due to the uneven discharge of leachates from the overlying waste body. Water samples collected from the waste layer indicate production of highly polluted leachates over 14 years after the landfill was closed. The chemical composition within the waste

Vadose zone controls on damping of climate-induced transient recharge fluxes in U.S. agroecosystems

NASA Astrophysics Data System (ADS)

Gurdak, Jason

2017-04-01

Understanding the physical processes in the vadose zone that link climate variability with transient recharge fluxes has particular relevance for the sustainability of groundwater-supported irrigated agriculture and other groundwater-dependent ecosystems. Natural climate variability on interannual to multidecadal timescales has well-documented influence on precipitation, evapotranspiration, soil moisture, infiltration flux, and can augment or diminish human stresses on water resources. Here the behavior and damping depth of climate-induced transient water flux in the vadose zone is explored. The damping depth is the depth in the vadose zone that the flux variation damps to 5% of the land surface variation. Steady-state recharge occurs when the damping depth is above the water table, and transient recharge occurs when the damping depth is below the water table. Findings are presented from major agroecosystems of the United States (U.S.), including the High Plains, Central Valley, California Coastal Basin, and Mississippi Embayment aquifer systems. Singular spectrum analysis (SSA) is used to identify quasi-periodic signals in precipitation and groundwater time series that are coincident with the Arctic Oscillation (AO) (6-12 mo cycle), Pacific/North American oscillation (PNA) (<1-4 yr cycle), El Niño/Southern Oscillation (ENSO) (2-7 yr cycle), North Atlantic Oscillation (NAO) (3-6 yr cycle), Pacific Decadal Oscillation (PDO) (15-30 yr cycle), and Atlantic Multidecadal Oscillation (AMO) (50-70 yr cycle). SSA results indicate that nearly all of the quasi-periodic signals in the precipitation and groundwater levels have a statistically significant lag correlation (95% confidence interval) with the AO, PNA, ENSO, NAO, PDO, and AMO indices. Results from HYDRUS-1D simulations indicate that transient water flux through the vadose zone are controlled by highly nonlinear interactions between mean infiltration flux and infiltration period related to the modes of climate

Hydraulic and geochemical framework of the Idaho National Engineering and Environmental Laboratory vadose zone

USGS Publications Warehouse

Nimmo, John R.; Rousseau, Joseph P.; Perkins, Kim S.; Stollenwerk, Kenneth G.; Glynn, Pierre D.; Bartholomay, Roy C.; Knobel, LeRoy L.

2004-01-01

Questions of major importance for subsurface contaminant transport at the Idaho National Engineering and Environmental Laboratory (INEEL) include (i) travel times to the aquifer, both average or typical values and the range of values to be expected, and (ii) modes of contaminant transport, especially sorption processes. The hydraulic and geochemical framework within which these questions are addressed is dominated by extreme heterogeneity in a vadose zone and aquifer consisting of interbedded basalts and sediments. Hydraulically, major issues include diverse possible types of flow pathways, extreme anisotropy, preferential flow, combined vertical and horizontal flow, and temporary saturation or perching. Geochemically, major issues include contaminant mobility as influenced by redox conditions, the concentration of organic and inorganic complexing solutes and other local variables, the interaction with infiltrating waters and with the contaminant source environment, and the aqueous speciation of contaminants such as actinides. Another major issue is the possibility of colloid transport, which inverts some of the traditional concepts of mobility, as sorbed contaminants on mobile colloids may be transported with ease compared with contaminants that are not sorbed. With respect to the goal of minimizing aquifer concentrations of contaminants, some characteristics of the vadose zone are essentially completely favorable. Examples include the great thickness (200 m) of the vadose zone, and the presence of substantial quantities of fine sediments that can retard contaminant transport both hydraulically and chemically. Most characteristics, however, have both favorable and unfavorable aspects. For example, preferential flow, as promoted by several notable features of the vadose zone at the INEEL, can provide fast, minimally sorbing pathways for contaminants to reach the aquifer easily, but it also leads to a wide dispersal of contaminants in a large volume of subsurface

Vadose zone attenuation of organic compounds at a crude oil spill site - interactions between biogeochemical reactions and multicomponent gas transport.

PubMed

Molins, S; Mayer, K U; Amos, R T; Bekins, B A

2010-03-01

Contaminant attenuation processes in the vadose zone of a crude oil spill site near Bemidji, MN have been simulated with a reactive transport model that includes multicomponent gas transport, solute transport, and the most relevant biogeochemical reactions. Dissolution and volatilization of oil components, their aerobic and anaerobic degradation coupled with sequential electron acceptor consumption, ingress of atmospheric O(2), and the release of CH(4) and CO(2) from the smear zone generated by the floating oil were considered. The focus of the simulations was to assess the dynamics between biodegradation and gas transport processes in the vadose zone, to evaluate the rates and contributions of different electron accepting processes towards vadose zone natural attenuation, and to provide an estimate of the historical mass loss. Concentration distributions of reactive (O(2), CH(4), and CO(2)) and non-reactive (Ar and N(2)) gases served as key constraints for the model calibration. Simulation results confirm that as of 2007, the main degradation pathway can be attributed to methanogenic degradation of organic compounds in the smear zone and the vadose zone resulting in a contaminant plume dominated by high CH(4) concentrations. In accordance with field observations, zones of volatilization and CH(4) generation are correlated to slightly elevated total gas pressures and low partial pressures of N(2) and Ar, while zones of aerobic CH(4) oxidation are characterized by slightly reduced gas pressures and elevated concentrations of N(2) and Ar. Diffusion is the most significant transport mechanism for gases in the vadose zone; however, the simulations also indicate that, despite very small pressure gradients, advection contributes up to 15% towards the net flux of CH(4), and to a more limited extent to O(2) ingress. Model calibration strongly suggests that transfer of biogenically generated gases from the smear zone provides a major control on vadose zone gas distributions

Vadose zone attenuation of organic compounds at a crude oil spill site - Interactions between biogeochemical reactions and multicomponent gas transport

USGS Publications Warehouse

Molins, S.; Mayer, K.U.; Amos, R.T.; Bekins, B.A.

2010-01-01

Contaminant attenuation processes in the vadose zone of a crude oil spill site near Bemidji, MN have been simulated with a reactive transport model that includes multicomponent gas transport, solute transport, and the most relevant biogeochemical reactions. Dissolution and volatilization of oil components, their aerobic and anaerobic degradation coupled with sequential electron acceptor consumption, ingress of atmospheric O2, and the release of CH4 and CO2 from the smear zone generated by the floating oil were considered. The focus of the simulations was to assess the dynamics between biodegradation and gas transport processes in the vadose zone, to evaluate the rates and contributions of different electron accepting processes towards vadose zone natural attenuation, and to provide an estimate of the historical mass loss. Concentration distributions of reactive (O2, CH4, and CO2) and non-reactive (Ar and N2) gases served as key constraints for the model calibration. Simulation results confirm that as of 2007, the main degradation pathway can be attributed to methanogenic degradation of organic compounds in the smear zone and the vadose zone resulting in a contaminant plume dominated by high CH4 concentrations. In accordance with field observations, zones of volatilization and CH4 generation are correlated to slightly elevated total gas pressures and low partial pressures of N2 and Ar, while zones of aerobic CH4 oxidation are characterized by slightly reduced gas pressures and elevated concentrations of N2 and Ar. Diffusion is the most significant transport mechanism for gases in the vadose zone; however, the simulations also indicate that, despite very small pressure gradients, advection contributes up to 15% towards the net flux of CH4, and to a more limited extent to O2 ingress. Model calibration strongly suggests that transfer of biogenically generated gases from the smear zone provides a major control on vadose zone gas distributions and vadose zone carbon

Evaluating Transport and Attenuation of Inorganic Contaminants in the Vadose Zone for Aqueous Waste Disposal Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Oostrom, Martinus; Tartakovsky, Guzel D.

An approach was developed for evaluating vadose zone transport and attenuation of aqueous wastes containing inorganic (non-volatile) contaminants that were disposed of at the land surface (i.e., directly to the ground in cribs, trenches, tile fields, etc.) and their effect on the underlying groundwater. The approach provides a structured method for estimating transport of contaminants through the vadose zone and the resulting temporal profile of groundwater contaminant concentrations. The intent of the approach is also to provide a means for presenting and explaining the results of the transport analysis in the context of the site-specific waste disposal conditions and sitemore » properties, including heterogeneities and other complexities. The document includes considerations related to identifying appropriate monitoring to verify the estimated contaminant transport and associated predictions of groundwater contaminant concentrations. While primarily intended for evaluating contaminant transport under natural attenuation conditions, the approach can also be applied to identify types of, and targets for, mitigation approaches in the vadose zone that would reduce the temporal profile of contaminant concentrations in groundwater, if needed.« less

Limited hydrologic response to Pleistocene climate change in deep vadose zones - Yucca Mountain, Nevada

USGS Publications Warehouse

Paces, J.B.; Neymark, L.A.; Whelan, J.F.; Wooden, J.L.; Lund, S.P.; Marshall, B.D.

2010-01-01

Understanding the movement of water through thick vadose zones, especially on time scales encompassing long-term climate change, is increasingly important as societies utilize semi-arid environments for both water resources and sites viewed as favorable for long-term disposal or storage of hazardous waste. Hydrologic responses to Pleistocene climate change within a deep vadose zone in the eastern Mojave Desert at Yucca Mountain, Nevada, were evaluated by uranium-series dating of finely layered hyalitic opal using secondary ion mass spectrometry. Opal is present within cm-thick secondary hydrogenic mineral crusts coating floors of lithophysal cavities in fractured volcanic rocks at depths of 200 to 300 m below land surface. Uranium concentrations in opal fluctuate systematically between 5 and 550 μg/g. Age-calibrated profiles of uranium concentration correlate with regional climate records over the last 300,000 years and produce time-series spectral peaks that have distinct periodicities of 100- and 41-ka, consistent with planetary orbital parameters. These results indicate that the chemical compositions of percolating solutions varied in response to near-surface, climate-driven processes. However, slow (micrometers per thousand years), relatively uniform growth rates of secondary opal and calcite deposition spanning several glacial–interglacial climate cycles imply that water fluxes in the deep vadose zone remained low and generally buffered from the large fluctuations in available surface moisture during different climates.

Aquifer recharge with stormwater runoff in urban areas: Influence of vadose zone thickness on nutrient and bacterial transfers from the surface of infiltration basins to groundwater.

PubMed

Voisin, Jérémy; Cournoyer, Benoit; Vienney, Antonin; Mermillod-Blondin, Florian

2018-10-01

Stormwater infiltration systems (SIS) have been built in urban areas to reduce the environmental impacts of stormwater runoff. Infiltration basins allow the transfer of stormwater runoff to aquifers but their abilities to retain contaminants depend on vadose zone properties. This study assessed the influence of vadose zone thickness (VZT) on the transfer of inorganic nutrients (PO 4 3- , NO 3 - , NH 4 + ), dissolved organic carbon (total -DOC- and biodegradable -BDOC-) and bacteria. A field experiment was conducted on three SIS with a thin vadose zone (<3 m) and three SIS with a thick vadose zone (>10 m). Water samples were collected at three times during a rainy period of 10 days in each infiltration basin (stormwater runoff), in the aquifer impacted by infiltration (impacted groundwater) and in the same aquifer but upstream of the infiltration area (non-impacted groundwater). Inorganic nutrients, organic matter, and dissolved oxygen (DO) were measured on all water samples. Bacterial community structures were investigated on water samples through a next-generation sequencing (NGS) scheme of 16S rRNA gene amplicons (V5-V6). The concentrations of DO and phosphate measured in SIS-impacted groundwaters were significantly influenced by VZT due to distinct biogeochemical processes occurring in the vadose zone. DOC and BDOC were efficiently retained in the vadose zone, regardless of its thickness. Bacterial transfers to the aquifer were overall low, but data obtained on day 10 indicated a significant bacterial transfer in SIS with a thin vadose zone. Water transit time and water saturation of the vadose zone were found important parameters for bacterial transfers. Most bacterial taxa (>60%) from impacted groundwaters were not detected in stormwater runoff and in non-impacted groundwaters, indicating that groundwater bacterial communities were significantly modified by processes associated with infiltration (remobilization of bacteria from vadose zone and/or species

Conceptual Model of Uranium in the Vadose Zone for Acidic and Alkaline Wastes Discharged at the Hanford Site Central Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Szecsody, James E.; Qafoku, Nikolla

2014-09-01

Historically, uranium was disposed in waste solutions of varying waste chemistry at the Hanford Site Central Plateau. The character of how uranium was distributed in the vadose zone during disposal, how it has continued to migrate through the vadose zone, and the magnitude of potential impacts on groundwater are strongly influenced by geochemical reactions in the vadose zone. These geochemical reactions can be significantly influenced by the disposed-waste chemistry near the disposal location. This report provides conceptual models and supporting information to describe uranium fate and transport in the vadose zone for both acidic and alkaline wastes discharged at amore » substantial number of waste sites in the Hanford Site Central Plateau. The conceptual models include consideration of how co-disposed acidic or alkaline fluids influence uranium mobility in terms of induced dissolution/precipitation reactions and changes in uranium sorption with a focus on the conditions near the disposal site. This information, when combined with the extensive information describing uranium fate and transport at near background pH conditions, enables focused characterization to support effective fate and transport estimates for uranium in the subsurface.« less

Evidence of linked biogeochemical and hydrological processes in homogeneous and layered vadose zone systems

NASA Astrophysics Data System (ADS)

McGuire, J. T.; Hansen, D. J.; Mohanty, B. P.

2010-12-01

Understanding chemical fate and transport in the vadose zone is critical to protect groundwater resources and preserve ecosystem health. However, prediction can be challenging due to the dynamic hydrologic and biogeochemical nature of the vadose zone. Additional controls on hydrobiogeochemical processes are added by subsurface structural heterogeneity. This study uses repacked soil column experiments to quantify linkages between microbial activity, geochemical cycling and hydrologic flow. Three “short” laboratory soil columns were constructed to evaluate the effects of soil layering: a homogenized medium-grained sand, homogenized organic-rich loam, and a sand-over-loam layered column. In addition, two “long” columns were constructed using either gamma-irradiated (sterilized) or untreated sediments to evaluate the effects of both soil layers and the presence of microorganisms. The long columns were packed identically; a medium-grained sand matrix with two vertically separated and horizontally offset lenses of organic-rich loam. In all 5 columns, downward and upward infiltration of water was evaluated to simulate rainfall and rising water table events respectively. In-situ colocated probes were used to measure soil water content, matric potential, Eh, major anions, ammonium, Fe2+, and total sulfide. Enhanced biogeochemical cycling was observed in the short layered column versus the short, homogeneous columns, and enumerations of iron and sulfate reducing bacteria were 1-2 orders of magnitude greater. In the long columns, microbial activity caused mineral bands and produced insoluble gases that impeded water flow through the pores of the sediment. Capillary barriers, formed around the lenses due to soil textural differences, retarded water flow rates through the lenses. This allowed reducing conditions to develop, evidenced by the production of Fe2+ and S2-. At the fringes of the lenses, Fe2+ oxidized to form Fe(III)-oxide bands that further retarded water

Changes in water and solute fluxes in the vadose zone after switching crops

NASA Astrophysics Data System (ADS)

Turkeltaub, Tuvia; Dahan, Ofer; Kurtzman, Daniel

2015-04-01

Switching crop type and therefore changing irrigation and fertilization regimes leads to alternation in deep percolation and concentrations of solutes in pore water. Changes of fluxes of water, chloride and nitrate under a commercial greenhouse due to a change from tomato to green spices were observed. The site, located above the a coastal aquifer, was monitored for the last four years. A vadose-zone monitoring system (VMS) was implemented under the greenhouse and provided continuous data on both the temporal variation in water content and the chemical composition of pore water at multiple depths in the deep vadose zone (~20 m). Chloride and nitrate profiles, before and after the crop type switching, indicate on a clear alternation in soil water solutes concentrations. Before the switching of the crop type, the average chloride profile ranged from ~130 to ~210, while after the switching, the average profile ranged from ~34 to ~203 mg L-1, 22% reduction in chloride mass. Counter trend was observed for the nitrate concentrations, the average nitrate profile before switching ranged from ~11 to ~44 mg L-1, and after switching, the average profile ranged from ~500 to ~75 mg L-1, 400% increase in nitrate mass. A one dimensional unsaturated water flow and chloride transport model was calibrated to transient deep vadose zone data. A comparison between the simulation results under each of the surface boundary conditions of the vegetables and spices cultivation regime, clearly show a distinct alternation in the quantity and quality of groundwater recharge.

Impact of CO2 Intrusion into USDWs, the Vadose Zone, and Indoor Air

EPA Science Inventory

The U.S. Environmental Protection Agency’s (EPA) Water Research Program in the Office of Research and Development is conducting research to better detect and quantify leakage into USDWs, the vadose zone, the atmosphere, and buildings. Research in this initiative is focused in thr...

EVALUATION OF VADOSE ZONE TREATMENT TECHNOLOGIES TO IMMOBILIZE TECHNETIUM-99

DOE Office of Scientific and Technical Information (OSTI.GOV)

PETERSEN, S.W.

2006-03-15

The Hanford Site End State Vision document (DOE/RL-2003-59) states: ''There should be an aggressive plan to develop technology for remediation of the contamination that could get to the groundwater (particularly the technetium [{sup 99}Tc])''. In addition, there is strong support from the public and regulatory agencies for the above statement, with emphasis on investigation of treatment alternatives. In July 2004, PNNL completed a preliminary evaluation of remediation technologies with respect to their effectiveness and implementability for immobilization of {sup 99}Tc beneath the BC Cribs in the 200 West Area (Truex, 2004). As a result of this evaluation, PNNL recommended treatabilitymore » testing of in situ soil desiccation, because it has the least uncertainty of those technologies evaluated in July 2004 (Treatability Test Outline, September 30, 2004). In 2005, DOE-RL and Fluor Hanford convened an independent technical panel to review alternative remediation technologies, including desiccation, at a three-day workshop in Richland, Washington. The panel was composed of experts in vadose-zone transport, infiltration control, hydrology, geochemistry, environmental engineering, and geology. Their backgrounds include employment in academia, government laboratories, industry, and consulting. Their review, presented in this document, is based upon written reports from Hanford, oral presentations from Hanford staff, and each panel members' years of experience in their particular field of expertise. The purpose of this report is to document the panel's evaluation of various treatment alternatives with potential for minimizing contaminant migration in the deep vadose zone at the Department of Energy Hanford Site. The panel was tasked with assessing the most viable and practical approach and making recommendations for testing. The evaluation of vadose-zone treatment alternatives was conducted to be broadly applicable at a variety of locations at Hanford. However

Imaging groundwater infiltration dynamics in the karst vadose zone with long-term ERT monitoring

NASA Astrophysics Data System (ADS)

Watlet, Arnaud; Kaufmann, Olivier; Triantafyllou, Antoine; Poulain, Amaël; Chambers, Jonathan E.; Meldrum, Philip I.; Wilkinson, Paul B.; Hallet, Vincent; Quinif, Yves; Van Ruymbeke, Michel; Van Camp, Michel

2018-03-01

Water infiltration and recharge processes in karst systems are complex and difficult to measure with conventional hydrological methods. In particular, temporarily saturated groundwater reservoirs hosted in the vadose zone can play a buffering role in water infiltration. This results from the pronounced porosity and permeability contrasts created by local karstification processes of carbonate rocks. Analyses of time-lapse 2-D geoelectrical imaging over a period of 3 years at the Rochefort Cave Laboratory (RCL) site in south Belgium highlight variable hydrodynamics in a karst vadose zone. This represents the first long-term and permanently installed electrical resistivity tomography (ERT) monitoring in a karst landscape. The collected data were compared to conventional hydrological measurements (drip discharge monitoring, soil moisture and water conductivity data sets) and a detailed structural analysis of the local geological structures providing a thorough understanding of the groundwater infiltration. Seasonal changes affect all the imaged areas leading to increases in resistivity in spring and summer attributed to enhanced evapotranspiration, whereas winter is characterised by a general decrease in resistivity associated with a groundwater recharge of the vadose zone. Three types of hydrological dynamics, corresponding to areas with distinct lithological and structural features, could be identified via changes in resistivity: (D1) upper conductive layers, associated with clay-rich soil and epikarst, showing the highest variability related to weather conditions; (D2) deeper and more resistive limestone areas, characterised by variable degrees of porosity and clay contents, hence showing more diffuse seasonal variations; and (D3) a conductive fractured zone associated with damped seasonal dynamics, while showing a great variability similar to that of the upper layers in response to rainfall events. This study provides detailed images of the sources of drip

Monitoring the Vadose Zone Moisture Regime Below a Surface Barrier

NASA Astrophysics Data System (ADS)

Zhang, Z. F.; Strickland, C. E.; Field, J. G.

2009-12-01

A 6000 m2 interim surface barrier has been constructed over a portion of the T Tank Farm in the Depart of Energy’s Hanford site. The purpose of using a surface barrier was to reduce or eliminate the infiltration of meteoric precipitation into the contaminated soil zone due to past leaks from Tank T-106 and hence to reduce the rate of movement of the plume. As part of the demonstration effort, vadose zone moisture is being monitored to assess the effectiveness of the barrier on the reduction of soil moisture flow. A vadose zone monitoring system was installed to measure soil water conditions at four horizontal locations (i.e., instrument Nests A, B, C, and D) outside, near the edge of, and beneath the barrier. Each instrument nest consists of a capacitance probe with multiple sensors, multiple heat-dissipation units, and a neutron probe access tube used to measure soil-water content and soil-water pressure. Nest A serves as a control by providing subsurface conditions outside the influence of the surface barrier. Nest B provides subsurface measurements to assess barrier edge effects. Nests C and D are used to assess the impact of the surface barrier on soil-moisture conditions beneath it. Monitoring began in September 2006 and continues to the present. To date, the monitoring system has provided high-quality data. Results show that the soil beneath the barrier has been draining from the shallower depth. The lack of climate-caused seasonal variation of soil water condition beneath the barrier indicates that the surface barrier has minimized water exchange between the soil and the atmosphere.

Model Fit to Experimental Data for Foam-Assisted Deep Vadose Zone Remediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roostapour, A.; Lee, G.; Zhong, Lirong

2014-01-15

Foam has been regarded as a promising means of remeidal amendment delivery to overcome subsurface heterogeneity in subsurface remediation processes. This study investigates how a foam model, developed by Method of Characteristics and fractional flow analysis in the companion paper of Roostapour and Kam (2012), can be applied to make a fit to a set of existing laboratory flow experiments (Zhong et al., 2009) in an application relevant to deep vadose zone remediation. This study reveals a few important insights regarding foam-assisted deep vadose zone remediation: (i) the mathematical framework established for foam modeling can fit typical flow experiments matchingmore » wave velocities, saturation history , and pressure responses; (ii) the set of input parameters may not be unique for the fit, and therefore conducting experiments to measure basic model parameters related to relative permeability, initial and residual saturations, surfactant adsorption and so on should not be overlooked; and (iii) gas compressibility plays an important role for data analysis, thus should be handled carefully in laboratory flow experiments. Foam kinetics, causing foam texture to reach its steady-state value slowly, may impose additional complications.« less

Automated Passive Capillary Lysimeters for Estimating Water Drainage in the Vadose Zone

NASA Astrophysics Data System (ADS)

Jabro, J.; Evans, R.

2009-04-01

In this study, we demonstrated and evaluated the performance and accuracy of an automated PCAP lysimeters that we designed for in-situ continuous measuring and estimating of drainage water below the rootzone of a sugarbeet-potato-barley rotation under two irrigation frequencies. Twelve automated PCAPs with sampling surface dimensions of 31 cm width * 91 cm long and 87 cm in height were placed 90 cm below the soil surface in a Lihen sandy loam. Our state-of-the-art design incorporated Bluetooth wireless technology to enable an automated datalogger to transmit drainage water data simultaneously every 15 minutes to a remote host and had a greater efficiency than other types of lysimeters. It also offered a significantly larger coverage area (2700 cm2) than similarly designed vadose zone lysimeters. The cumulative manually extracted drainage water was compared with the cumulative volume of drainage water recorded by the datalogger from the tipping bucket using several statistical methods. Our results indicated that our automated PCAPs are accurate and provided convenient means for estimating water drainage in the vadose zone without the need for costly and manually time-consuming supportive systems.

An Experimental Study of Diffusivity of Technetium-99 in Hanford Vadose Zone Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mattigod, Shas V.; Bovaird, Chase C.; Wellman, Dawn M.

2012-11-01

One of the methods being considered at the Hanford site in Washington for safely disposing of low-level radioactive wastes (LLW) is to encase the waste in concrete and entomb the packages in the Hanford vadose zone sediments. The current plan for waste isolation consists of stacking low-level waste packages on a trench floor, surrounding the stacks with reinforced steel, and encasing these packages with concrete. Any failure of the concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. The mobilized radionuclides may escape from the encased concrete by mass flow and/or diffusion andmore » move into the surrounding subsurface sediments. It is therefore necessary to conduct an assessment of the performance of the concrete encasement structure and the surrounding soil’s ability to retard radionuclide migration. The retardation factors for radionuclides contained in the waste packages can be determined from measurements of diffusion coefficients for these contaminants through concrete and fill material. Because of their anionic nature in aqueous solutions, the radionuclides, 99Tc and 129I were identified as long-term dose contributors in LLW. The leachability and/or diffusion of these radionuclide species must be measured in order to assess the long-term performance of waste grouts when contacted with vadose-zone porewater or groundwater. To measure the diffusivity, a set of experiments were conducted using 99Tc-spiked concrete (with 0 and 4% metallic iron additions) in contact with unsaturated soil half-cells that reflected the typical moisture contents of Hanford vadose zone sediments. The 99Tc diffusion profiles in the soil half cells were measured after a time lapse of ~1.9 yr. Using the concentration profiles, the 99Tc diffusivity coefficients were calculated based on Fick’s Second Law.« less

Remediation of Deep Vadose Zone Radionuclide and Metal Contamination: Status and Issues

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dresel, P. Evan; Truex, Michael J.; Cantrell, Keri

2008-12-30

This report documents the results of a PNNL literature review to report on the state of maturity of deep vadose zone remediation technologies for metal contaminants including some radionuclides. Its recommendations feed into decisionmakers need for scientific information and cost-effective in situ remediation technlogies needed under DOE's Environmental Management initiative Enhanced Remediation Methods: Scientific & Technical Basis for In Stu Treatment Systems for Metals and Radionuclides.

ESTIMATION OF INFILTRATION RATE IN THE VADOSE ZONE: COMPILATION OF SIMPLE MATHEMATICAL MODELS - VOLUME I

EPA Science Inventory

The unsaturated or vadose zone provides a complex system for the simulation of water movement and contaminant transport and fate. Numerous models are available for performing simulations related to the movement of water. There exists extensive documentation of these models. Ho...

Vadose zone process that control landslide initiation and debris flow propagation

NASA Astrophysics Data System (ADS)

Sidle, Roy C.

2015-04-01

Advances in the areas of geotechnical engineering, hydrology, mineralogy, geomorphology, geology, and biology have individually advanced our understanding of factors affecting slope stability; however, the interactions among these processes and attributes as they affect the initiation and propagation of landslides and debris flows are not well understood. Here the importance of interactive vadose zone processes is emphasized related to the mechanisms, initiation, mode, and timing of rainfall-initiated landslides that are triggered by positive pore water accretion, loss of soil suction and increase in overburden weight, and long-term cumulative rain water infiltration. Both large- and small-scale preferential flow pathways can both contribute to and mitigate instability, by respectively concentrating and dispersing subsurface flow. These mechanisms are influenced by soil structure, lithology, landforms, and biota. Conditions conducive to landslide initiation by infiltration versus exfiltration are discussed relative to bedrock structure and joints. The effects of rhizosphere processes on slope stability are examined, including root reinforcement of soil mantles, evapotranspiration, and how root structures affect preferential flow paths. At a larger scale, the nexus between hillslope landslides and in-channel debris flows is examined with emphasis on understanding the timing of debris flows relative to chronic and episodic infilling processes, as well as the episodic nature of large rainfall and related stormflow generation in headwater streams. The hydrogeomorphic processes and conditions that determine whether or not landslides immediately mobilize into debris flows is important for predicting the timing and extent of devastating debris flow runout in steep terrain. Given the spatial footprint of individual landslides, it is necessary to assess vadose zone processes at appropriate scales to ascertain impacts on mass wasting phenomena. Articulating the appropriate

Impact of Heterogeneity on Vadose Zone Drainage During Pumping: Numerical Simulations of the Borden Aquifer

NASA Astrophysics Data System (ADS)

Bunn, M. I.; Jones, J.; Endres, A. L.

2009-05-01

Unconfined aquifers are in direct contact with the earth's surface; hence, they are an important focus in groundwater recharge and contaminant transport studies. While pumping tests have long been used to quantify aquifer properties, the contribution of drainage from the vadose zone during pumping has been the subject of debate for decades. In 2001, a highly detailed data set was collected during a seven-day pumping test in the unconfined aquifer at CFB Borden, Ontario (Bevan et al., 2005). The frequent observation of moisture content profiles during the test has initiated a closer examination of the vadose zone response to pumping. The moisture profiles collected during the test were obtained using a neutron probe. The neutron data depicts a capillary fringe thickness that increases with both proximity to the pumping well and duration of pumping. This capillary fringe extension results in delayed drainage that persists to the end of the seven-day test with the shape of the transition zone remaining constant (Bevan et al., 2005). Simulations of the pumping test were conducted using Hydrogeosphere (Therrien et al., 2006). Initial simulations were completed based on the conceptual model of a homogeneous and slightly anisotropic aquifer. The simulation results replicated the observed piezometric response, but were unable to produce any change in the thickness of the capillary fringe. It was hypothesized that the discrepancy between observations and simulation results may be the result of assumptions such as the homogeneity of the hydraulic conductivity field. In an effort to replicate this potential mechanism for the observed extension, the conceptual model was updated to better reflect the mildly heterogeneous hydraulic conductivity field of the Borden aquifer. Conductivity fields were generated using the statistical description of the Borden aquifer given by Sudicky (1986) with an adjusted mean log conductivity to better approximate the observed piezometric response

ESTIMATION OF INFILTRATION RATE IN THE VADOSE ZONE: APPLICATION OF SELECTED MATHEMATICAL MODELS - VOLUME II

EPA Science Inventory

Movement of water into and through the vadose zone is of great importance to the assessment of contaminant fate and transport, agricultural management, and natural resource protection. The process of water movement is very dynamic, changing dramatically over time and space. Inf...

Geochemical Processes Data Package for the Vadose Zone in the Single-Shell Tank Waste Management Areas at the Hanford Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantrell, Kirk J.; Zachara, John M.; Dresel, P. Evan

This data package discusses the geochemistry of vadose zone sediments beneath the single-shell tank farms at the U.S. Department of Energy’s (DOE’s) Hanford Site. The purpose of the report is to provide a review of the most recent and relevant geochemical process information available for the vadose zone beneath the single-shell tank farms and the Integrated Disposal Facility. Two companion reports to this one were recently published which discuss the geology of the farms (Reidel and Chamness 2007) and groundwater flow and contamination beneath the farms (Horton 2007).

Performance Evaluation of Automated Passive Capillary Sampler for Estimating Water Drainage in the Vadose Zone

USDA-ARS?s Scientific Manuscript database

Passive capillary samplers (PCAPs) are widely used to monitor, measure and sample drainage water under saturated and unsaturated soil conditions in the vadose zone. The objective of this study was to evaluate the performance and accuracy of automated passive capillary sampler for estimating drainage...

Aerosol Delivery for Amendment Distribution in Contaminated Vadose Zones

NASA Astrophysics Data System (ADS)

Hall, R. J.; Murdoch, L.; Riha, B.; Looney, B.

2011-12-01

Remediation of contaminated vadose zones is often hindered by an inability to effectively distribute amendments. Many amendment-based approaches have been successful in saturated formations, however, have not been widely pursued when treating contaminated unsaturated materials due to amendment distribution limitations. Aerosol delivery is a promising new approach for distributing amendments in contaminated vadose zones. Amendments are aerosolized and injected through well screens. During injection the aerosol particles are transported with the gas and deposited on the surfaces of soil grains. Resulting distributions are radially and vertically broad, which could not be achieved by injecting pure liquid-phase solutions. The objectives of this work were A) to characterize transport and deposition behaviors of aerosols; and B) to develop capabilities for predicting results of aerosol injection scenarios. Aerosol transport and deposition processes were investigated by conducting lab-scale injection experiments. These experiments involved injection of aerosols through a 2m radius, sand-filled wedge. A particle analyzer was used to measure aerosol particle distributions with time, and sand samples were taken for amendment content analysis. Predictive capabilities were obtained by constructing a numerical model capable of simulating aerosol transport and deposition in porous media. Results from tests involving vegetable oil aerosol injection show that liquid contents appropriate for remedial applications could be readily achieved throughout the sand-filled wedge. Lab-scale tests conducted with aqueous aerosols show that liquid accumulation only occurs near the point of injection. Tests were also conducted using 200 g/L salt water as the aerosolized liquid. Liquid accumulations observed during salt water tests were minimal and similar to aqueous aerosol results. However, particles were measured, and salt deposited distal to the point of injection. Differences between

Experimental and modeling of the unsaturated transports of S-metolachlor and its metabolites in glaciofluvial vadose zone solids.

PubMed

Sidoli, Pauline; Lassabatere, Laurent; Angulo-Jaramillo, Rafael; Baran, Nicole

2016-07-01

The transport of pesticides to groundwater is assumed to be impacted by flow processes and geochemical interactions occurring in the vadose zone. In this study, the transport of S-metolachlor (SMOC) and its two metabolites ESA-metolachlor (MESA) and OXA-metolachlor (MOXA) in vadose zone materials of a glaciofluvial aquifer is studied at laboratory scale. Column experiments are used to study the leaching of a conservative tracer (bromide) and SMOC, MESA and MOXA under unsaturated conditions in two lithofacies, a bimodal gravel (Gcm,b) and a sand (S-x). Tracer experiments showed water fractionation into mobile and immobile compartments more pronounced in bimodal gravel columns. In both lithofacies columns, SMOC outflow is delayed (retardation factor>2) and mass balance reveals depletion (mass balance of 0.59 and 0.77 in bimodal gravel and sand, respectively). However, complete mass elution associated with retardation factors close to unity shows that there is no adsorption of MESA and MOXA in either lithofacies. SMOC transport is characterized by non-equilibrium sorption and sink term in both bimodal gravel and sand columns. Batch experiments carried out using agitation times consistent with column water residence times confirmed a time-dependence of SMOC sorption and high adsorption rates (>80%) of applied concentrations. Desorption experiments confirm the irreversibility of a major part of the SMOC adsorption onto particles, corresponding to the sink term in columns. In the bimodal gravel column, SMOC adsorption occurs mainly on reactive particles in contact with mobile water because of flow regionalization whereas in the sand column, there is pesticide diffusion to the immobile water. Such results clearly show that sorption mechanisms in the vadose zone solids below the soil are both solute and contact-time-dependent and are impacted by hydrodynamic conditions. The more rapid transport of MESA and MOXA to the aquifer would be controlled mainly by water flow

Vertical Extent of 100 Area Vadose Zone Contamination of Metals at the Hanford Site

NASA Astrophysics Data System (ADS)

Khaleel, R.; Mehta, S.

2012-12-01

The 100 Area is part of the U.S. Department of Energy Hanford Site in southeastern Washington and borders the Columbia River. The primary sources of contamination in the area are associated with the operation of nine former production reactors, the last one shutting down in 1988. The area is undergoing a CERCLA remedial investigation (RI) that will provide data to support final cleanup decisions. During reactor operations, cooling water contaminated with radioactive and hazardous chemicals was discharged to both the adjacent Columbia River and infiltration cribs and trenches. Contaminated solid wastes were disposed of in burial grounds; the estimated Lead-Cadmium used as "reactor poison" and disposed of in 100 Area burial grounds is 1103 metric tons, of which up to 1059 metric tons are Lead and 44 metric tons are Cadmium. We summarize vadose zone site characterization data for the recently drilled boreholes, including the vertical distribution of concentration profiles for metals (i.e., Lead, Arsenic and Mercury) under the near neutral pH and oxygenated conditions. The deep borehole measurements targeted in the RI work plan were identified with a bias towards locating contaminants throughout the vadose zone and targeted areas at or near the waste sites; i.e., the drilling as well as the sampling was biased towards capturing contamination within the "hot spots." Unlike non-reactive contaminants such as tritium, Arsenic, Mercury and Lead are known to have a higher distribution coefficient (Kd), expected to be relatively immobile, and have a long residence time within the vadose zone. However, a number of sediment samples located close to the water table exceed the background concentrations for Lead and Arsenic. Three conceptual models are postulated to explain the deeper than expected penetration for the metals.

Ion association in water solution of soil and vadose zone of chestnut saline solonetz as a driver of terrestrial carbon sink

NASA Astrophysics Data System (ADS)

Batukaev, Abdul-Malik A.; Endovitsky, Anatoly P.; Andreev, Andrey G.; Kalinichenko, Valery P.; Minkina, Tatiana M.; Dikaev, Zaurbek S.; Mandzhieva, Saglara S.; Sushkova, Svetlana N.

2016-03-01

The assessment of soil and vadose zone as the drains for carbon sink and proper modeling of the effects and extremes of biogeochemical cycles in the terrestrial biosphere are the key components to understanding the carbon cycle, global climate system, and aquatic and terrestrial system uncertainties. Calcium carbonate equilibrium causes saturation of solution with CaCO3, and it determines its material composition, migration and accumulation of salts. In a solution electrically neutral ion pairs are formed: CaCO30, CaSO40, MgCO30, and MgSO40, as well as charged ion pairs CaHCO3+, MgHCO3+, NaCO3-, NaSO4-, CaOH+, and MgOH+. The calcium carbonate equilibrium algorithm, mathematical model and original software to calculate the real equilibrium forms of ions and to determine the nature of calcium carbonate balance in a solution were developed. This approach conducts the quantitative assessment of real ion forms of solution in solonetz soil and vadose zone of dry steppe taking into account the ion association at high ionic strength of saline soil solution. The concentrations of free and associated ion form were calculated according to analytical ion concentration in real solution. In the iteration procedure, the equations were used to find the following: ion material balance, a linear interpolation of equilibrium constants, a method of ionic pairs, the laws of initial concentration preservation, operating masses of equilibrium system, and the concentration constants of ion pair dissociation. The coefficient of ion association γe was determined as the ratio of ions free form to analytical content of ion γe = Cass/Can. Depending on soil and vadose zone layer, concentration and composition of solution in the ionic pair's form are 11-52 % Ca2+; 22.2-54.6 % Mg2+; 1.1-10.5 % Na+; 3.7-23.8 HCO3-, 23.3-61.6 % SO42-, and up to 85.7 % CO32-. The carbonate system of soil and vadose zone water solution helps to explain the evolution of salted soils, vadose and saturation zones, and

Application of vadose-zone monitoring system for real-time characterization of leachate percolation in and under a municipal landfill.

PubMed

Aharoni, Imri; Siebner, Hagar; Dahan, Ofer

2017-09-01

Leachates from solid-waste landfills are considered a severe threat to groundwater quality. The fate of pollutants in the waste and underlying unsaturated zone is crucial for evaluating environmental risks and selecting a restoration strategy. In this study, a vadose-zone monitoring system (VMS) installed in a municipal landfill was used, for the first time, to continuously track leachates percolation dynamics and assess their chemical transformation across the entire thickness of the waste body (15m) and underlying unsaturated zone (16m) to the water table. Winter rains were found to quickly infiltrate through the waste and underlying vadose zone despite a clay cover that was implemented as part of a restoration and leachate-prevention strategy. Within the waste body, the flow pattern was controlled by preferential flow paths, which changed frequently. It is hypothesized that ongoing decomposition of the waste creates dynamic variations in the waste's physical structure and flow pattern. Water samples collected from the waste layer indicated the formation of highly polluted leachates. The chemical composition in the waste body showed extreme variability between sampling points with respect to DOC (407-31,464mg/L), BOD/COD ratios (0.07-0.55), Fe 2+ (6.8-1154mg/L), ammonium (68-2924mg/L) and heavy metal concentrations. Environmental hot spots creating concentrated, aggressive, "acid-phase" leachates still exist in the waste more than 13years after closing the landfill. However, continuous changes in the flow pattern and moisture distribution affected the creation and decay of such environments. In the underlying sandy vadose zone, some sections repeatedly exhibited stronger and faster flow characteristics than others. These local fluxes of concentrated leachates rapidly transported heavy contaminant loads toward the groundwater. However results showed evidence of continual attenuation processes in the deep vadose zone, with the anaerobic digestion of organic matter

AN EXACT SOLUTION FOR THE ASSESSMENT OF NONEQUILIBRIUM SORPTION OF RADIONUCLIDES IN THE VADOSE ZONE

EPA Science Inventory

In a report on model evaluation, the authors ran the HYDRUS Code, among other transport codes, to evaluate the impacts of nonequilibrium sorption sites on the time-evolution of 99Tc and 90Sr through the vadose zone. Since our evaluation was based on a rather low, annual recharge...

Scale-Up Information for Gas-Phase Ammonia Treatment of Uranium in the Vadose Zone at the Hanford Site Central Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Szecsody, James E.; Zhong, Lirong

Uranium is present in the vadose zone at the Hanford Central Plateau and is of concern for protection of groundwater. The Deep Vadose Zone Treatability Test Plan for the Hanford Central Plateau identified gas-phase treatment and geochemical manipulation as potentially effective treatment approaches for uranium and technetium in the Hanford Central Plateau vadose zone. Based on laboratory evaluation, use of ammonia vapor was selected as the most promising uranium treatment candidate for further development and field testing. While laboratory tests have shown that ammonia treatment effectively reduces the mobility of uranium, additional information is needed to enable deployment of thismore » technology for remediation. Of importance for field applications are aspects of the technology associated with effective distribution of ammonia to a targeted treatment zone, understanding the fate of injected ammonia and its impact on subsurface conditions, and identifying effective monitoring approaches. In addition, information is needed to select equipment and operational parameters for a field design. As part of development efforts for the ammonia technology for remediation of vadose zone uranium contamination, field scale-up issues were identified and have been addressed through a series of laboratory and modeling efforts. This report presents a conceptual description for field application of the ammonia treatment process, engineering calculations to support treatment design, ammonia transport information, field application monitoring approaches, and a discussion of processes affecting the fate of ammonia in the subsurface. The report compiles this information from previous publications and from recent research and development activities. The intent of this report is to provide technical information about these scale-up elements to support the design and operation of a field test for the ammonia treatment technology.« less

Foam, a promising vehicle to deliver nanoparticles for vadose zone remediation.

PubMed

Shen, Xin; Zhao, Lin; Ding, Yuanzhao; Liu, Bo; Zeng, Hui; Zhong, Lirong; Li, Xiqing

2011-02-28

Foam delivery of remedial amendments for in situ immobilization of deep vadose zone contaminants can overcome the intrinsic problems associated with solution-based delivery, such as preferential flow and contaminant mobilization. In this work, the feasibility of using foam to deliver nanoparticles in unsaturated porous media was investigated. Carboxyl-modified polystyrene latex microspheres were used as surrogates for nanoparticles of remediation purposes. Foams generated from the solutions of six commonly available surfactants all had excellent abilities to carry the microspheres. The presence of the microspheres did not reduce the stabilities of the foams. When microsphere-laden foam was injected through the unsaturated columns, the fractions of microspheres exiting the column were much higher than that when the microsphere water suspensions were injected through the columns. The enhanced microsphere transport implies that foam delivery could significantly increase the radius of influence of injected nanoparticles of remediation purposes. Reduced tension at air-water interfaces by the surfactant and increased driving forces imparted on the microspheres at the interfaces by the flowing foam bubbles may have both contributed to the enhanced transport. Preliminary tests also demonstrated that foam can carry significant fractions of zero valent iron nanoparticles at concentrations relevant to field remediation conditions (up to 5.3 g L(-1)). As such, this study demonstrates that surfactant foam is potentially a promising vehicle to deliver nanoparticles for vadose zone remediation. Copyright © 2010 Elsevier B.V. All rights reserved.

Analysing the mechanisms of soil water and vapour transport in the desert vadose zone of the extremely arid region of northern China

NASA Astrophysics Data System (ADS)

Du, Chaoyang; Yu, Jingjie; Wang, Ping; Zhang, Yichi

2018-03-01

The transport of water and vapour in the desert vadose zone plays a critical role in the overall water and energy balances of near-surface environments in arid regions. However, field measurements in extremely dry environments face many difficulties and challenges, so few studies have examined water and vapour transport processes in the desert vadose zone. The main objective of this study is to analyse the mechanisms of soil water and vapour transport in the desert vadose zone (depth of ∼350 cm) by using measured and modelled data in an extremely arid environment. The field experiments are implemented in an area of the Gobi desert in northwestern China to measure the soil properties, daily soil moisture and temperature, daily water-table depth and temperature, and daily meteorological records from DOYs (Days of Year) 114-212 in 2014 (growing season). The Hydrus-1D model, which simulates the coupled transport of water, vapour and heat in the vadose zone, is employed to simulate the layered soil moisture and temperature regimes and analyse the transport processes of soil water and vapour. The measured results show that the soil water and temperatures near the land surface have visible daily fluctuations across the entire soil profile. Thermal vapour movement is the most important component of the total water flux and the soil temperature gradient is the major driving factor that affects vapour transport in the desert vadose zone. The most active water and heat exchange occurs in the upper soil layer (depths of 0-25 cm). The matric potential change from the precipitation mainly re-draws the spatio-temporal distribution of the isothermal liquid water in the soil near the land surface. The matric potential has little effect on the isothermal vapour and thermal liquid water flux. These findings offer new insights into the liquid water and vapour movement processes in the extremely arid environment.

Preferential Flow and Transport of Cryptosporidium Parvum Oocysts Through Vadose Zone: Experiments and Modeling

NASA Astrophysics Data System (ADS)

Darnault, C. J.; Darnault, C. J.; Garnier, P.; Kim, Y.; Oveson, K.; Jenkins, M.; Ghiorse, W.; Baveye, P.; Parlange, J.; Steenhuis, T.

2001-12-01

Oocysts of the protozoan Cryptosporidium parvum, when they contaminate drinking water supplies, can cause outbreaks of Cryptosporidiosis, a common waterborne disease. Of the different pathways by which oocysts can wind up in drinking water, one has received very little attention to date; because soils are often considered to be perfect filters, the transport of oocysts through the subsoil to groundwater by preferential flow is generally ignored. To evaluate its significance, three set of laboratory experiments investigated transport of oocysts through vadose zone. Experiment set I was carried out in a vertical 50 cm-long column filled with silica sand, under conditions known to foster fingered flow. Experiment set II investigates the effect of gas-water interfaces by modifying the hydrodynamical conditions in the sand columns with water-repellent sand barriers. Experiment III involved undisturbed soil columns subjected to macropores flow. The sand and soil columns were subjected to artificial rainfall and were allowed to reach steady-state. At that point, feces of contaminated calves were applied at the surface, along with a known amount of KCl to serve as tracer, and rainfall was continued at the same rate. The breakthrough of oocysts and Cl-, monitored in the effluent, demonstrate the importance of preferential flow - fingered flow and macropore flow - on the transport of oocysts through vadose zone. Peak oocyst concentrations were not appreciably delayed, compared to Cl-, and in some cases, occurred even before the Cl- peak. However, the numbers of oocysts present in the effluents were still orders of magnitude higher than the 5 to 10 oocysts per liter that are considerable sufficient to cause cryptosporidiosis in healthy adults. The transport of oocysts was simulated based on a partitioning the soil profile in both a distribution zone and a preferential zone, In particular, the model simulates accurately the markedly asymmetric breakthrough patterns, and the

An isotopic view of water and nitrate transport through the vadose zone in Oregon's southern Willamette Valley's Groundwater Management Area

NASA Astrophysics Data System (ADS)

Brooks, J. R.; Pearlstein, S.; Hutchins, S.; Faulkner, B. R.; Rugh, W.; Willard, K.; Coulombe, R.; Compton, J.

2017-12-01

Groundwater nitrate contamination affects thousands of households in Oregon's southern Willamette Valley and many more across the USA. The southern Willamette Valley Groundwater Management Area (GWMA) was established in 2004 due to nitrate levels in the groundwater exceeding the human health standard of 10 mg nitrate-N L-1. Much of the nitrogen (N) inputs to the GWMA comes from agricultural fertilizers, and thus efforts to reduce N inputs to groundwater are focused upon improving N management. However, the effectiveness of these improvements on groundwater quality is unclear because of the complexity of nutrient transport through the vadose zone and long groundwater residence times. Our objective was to focus on vadose zone transport and understand the dynamics and timing of N and water movement below the rooting zone in relation to N management and water inputs. Stable isotopes are a powerful tool for tracking water movement, and understanding N transformations. In partnership with local farmers and state agencies, we established lysimeters and groundwater wells in multiple agricultural fields in the GWMA, and have monitored nitrate, nitrate isotopes, and water isotopes weekly for multiple years. Our results indicate that vadose zone transport is highly complex, and the residence time of water collected in lysimeters was much longer than expected. While input precipitation water isotopes were highly variable over time, lysimeter water isotopes were surprisingly consistent, more closely resembling long-term precipitation isotope means rather than recent precipitation isotopic signatures. However, some particularly large precipitation events with unique isotopic signatures revealed high spatial variability in transport, with some lysimeters showing greater proportions of recent precipitation inputs than others. In one installation where we have groundwater wells and lysimeters at multiple depths, nitrate/nitrite concentrations decreased with depth. N concentrations

The role of fluid mobility in the development of shale weathering profiles: Direct observations from a vadose zone monitoring system

NASA Astrophysics Data System (ADS)

Druhan, J. L.; Wang, J.; Cargill, S.; Murphy, C.; Tune, A. K.; Dietrich, W. E.; Rempe, D.

2017-12-01

Extensive effort has focused on resolving the contribution of weathering reactions to the transfer of mass over scales ranging from individual hillslope weathering profiles, across local watersheds, to continental drainage networks. A persistent limitation in quantifying these fluxes is the variability in fluid flowpaths through the subsurface, which may alter the extent of chemical weathering relative to that expected from idealized homogenous conditions. In the past decade, the consequence of fluid travel time on solute flux has been recognized as a key complexity in the interpretation of solute concentrations, particularly in upland watersheds characterized by fracture flowpaths, as is typical of shale-dominated landscapes. Though recent studies have suggested a variety of models for solute generation in such dual (matrix and fracture flow) domain systems, a central impediment to advancing prediction is the lack of direct observations. Here, we report solute chemistry as a function of depth across an 18 m thick vadose zone of weathered argillite (shale) in the Eel River Critical Zone Observatory (ERCZO) using novel sub-horizontal distributed samplers (Vadose Zone Monitoring System). We contrast a year of major and trace ion chemistry obtained from water samples collected approximately biweekly using two complementary sampling systems, one applying active pressure to extract matrix-bound pore fluid, and the other using a passive collection method to extract freely draining water. Precipitation falling during the winter rainy season passes through this vadose zone, causing increased rock moisture that is subsequently depleted by transpiring trees. Solute concentrations reflect these seasonal changes, and, surprisingly, normalized ion ratios span the full range of values reported for the world's largest rivers. Notably, for some major cations, freely draining water is consistently less concentrated than matrix-bound water, and the composition of vadose zone water

Engineering report single-shell tank farms interim measures to limit infiltration through the vadose zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

HAASS, C.C.

1999-10-14

Identifies, evaluates and recommends interim measures for reducing or eliminating water sources and preferential pathways within the vadose zone of the single-shell tank farms. Features studied: surface water infiltration and leaking water lines that provide recharge moisture, and wells that could provide pathways for contaminant migration. An extensive data base, maps, recommended mitigations, and rough order of magnitude costs are included.

Vadose zone processes delay groundwater nitrate reduction response to BMP implementation as observed in paired cultivated vs. uncultivated potato rotation fields

NASA Astrophysics Data System (ADS)

Jiang, Y.; Nyiraneza, J.; Murray, B. J.; Chapman, S.; Malenica, A.; Parker, B.

2017-12-01

Nitrate leaching from crop production contributes to groundwater contamination and subsequent eutrophication of the receiving surface water. A study was conducted in a 7-ha potato-grain-forages rotation field in Prince Edward Island (PEI), Canada during 2011-2016 to link potato rotation practices and groundwater quality. The field consists of fine sandy loam soil and is underlain by 7-9 m of glacial till, which overlies the regional fractured ;red-bed; sandstone aquifer. The water table is generally located in overburden close to the bedrock interface. Field treatments included one field zone taken out of production in 2011 with the remaining zones kept under a conventional potato rotation. Agronomy data including crop tissue, soil, and tile-drain water quality were collected. Hydrogeology data including multilevel monitoring of groundwater nitrate and hydraulic head and data from rock coring for nitrate distribution in overburden and bedrock matrix were also collected. A significant amount of nitrate leached below the soil profile after potato plant kill (referred to as topkill) in 2011, most of it from fertilizer N. A high level of nitrate was also detected in the till vadose zone through coring in December 2012 and through multilevel groundwater sampling from January to May 2014 in both cultivated and uncultivated field zones. Groundwater nitrate concentrations increased for about 2.5 years after the overlying potato field was removed from production. Pressure-driven uniform flow processes dominate water and nitrate transport in the vadose zone, producing an apparently instant water table response but a delayed groundwater quality response to nitrate leaching events. These data suggest that the uniform flow dominated vadose zone in agricultural landscapes can cause the accumulation of a significant amount of nitrate originated from previous farming activities, and the long travel time of this legacy nitrate in the vadose zone can result in substantially delayed

Are faults preferential flow paths through semiarid and arid vadose zones?

NASA Astrophysics Data System (ADS)

Sigda, John M.; Wilson, John L.

2003-08-01

Numerous faults crosscut the poorly lithified, basin-fill sands found in New Mexico's Rio Grande rift and in other extensional regimes. The deformational processes that created these faults sharply reduced both fault porosity and fault saturated hydraulic conductivity by altering grains and pores, particularly in structures referred to as deformation bands. The resulting pore distribution changes, which create barriers to saturated flow, should enhance fault unsaturated flow relative to parent sand under the relatively dry conditions of the semiarid southwest. We report the first measurements of unsaturated hydraulic properties for undisturbed fault materials, using samples from a small-displacement normal fault and parent sands in the Bosque del Apache Wildlife Refuge, central New Mexico. Fault samples were taken from a narrow zone of deformation bands. The unsaturated flow apparatus (UFA) centrifuge system was used to measure both relative permeability and moisture retention curves. We compared these relations and fitted hydraulic conductivity-matric potential models to test whether the fault has significantly different unsaturated hydraulic properties than its parent sand. Saturated conductivity is 3 orders of magnitude less in the fault than the undeformed sand. As matric potential decreases from 0 to -200 cm, unsaturated conductivity decreases roughly 1 order of magnitude in the fault but 5-6 orders of magnitude in undeformed sands. Fault conductivity is greater by 2-6 orders of magnitude at matric potentials between -200 and -1000 cm, which are typical potentials for semiarid and arid vadose zones. Fault deformation bands have much higher air-entry matric potential values than parent sands and remain close to saturation well after the parent sands have begun to approach residual moisture content. Under steady state, one-dimensional, gravity-driven flow conditions, moisture transport and solute advection is 102-106 times larger in the fault material than

Natural analogues for processes affecting disposal of high-level radioactive waste in the vadose zone

NASA Astrophysics Data System (ADS)

Stuckless, J. S.

2003-04-01

Natural analogues can contribute to understanding and predicting the performance of subsystems and processes affecting a mined geologic repository for high-level radioactive waste in several ways. Most importantly, analogues provide tests for various aspects of systems of a repository at dimensional scales and time spans that cannot be attained by experimental study. In addition, they provide a means for the general public to judge the predicted performance of a potential high-level nuclear waste repository in familiar terms such that the average person can assess the anticipated long-term performance and other scientific conclusions. Hydrologists working on the Yucca Mountain Project (currently the U.S. Department of Energy's Office of Repository Development) have modeled the flow of water through the vadose zone at Yucca Mountain, Nevada and particularly the interaction of vadose-zone water with mined openings. Analogues from both natural and anthropogenic examples confirm the prediction that most of the water moving through the vadose zone will move through the host rock and around tunnels. This can be seen both quantitatively where direct comparison between seepage and net infiltration has been made and qualitatively by the excellent degree of preservation of archaeologic artifacts in underground openings. The latter include Paleolithic cave paintings in southwestern Europe, murals and artifacts in Egyptian tombs, painted subterranean Buddhist temples in India and China, and painted underground churches in Cappadocia, Turkey. Natural analogues also suggest that this diversion mechanism is more effective in porous media than in fractured media. Observations from natural analogues are also consistent with the modeled decrease in the percentage of infiltration that becomes seepage with a decrease in amount of infiltration. Finally, analogues, such as tombs that have ben partially filled by mud flows, suggest that the same capillary forces that keep water in the

SCREENING MODEL FOR NONAQUEOUS PHASE-LIQUID TRANSPORT IN THE VADOSE ZONE USING GREEN-AMPT AND KINEMATIC WAVE THEORY

EPA Science Inventory

In this paper, a screening model for flow of a nonaqueous phase liquid (NAPL) and associated chemical transport in the vadose zone is developed. he model is based on kinematic approximation of the governing equations for both the NAPL and a partitionable chemical constituent. he ...

Delivery and Establishing Slow Release Carbon Source to the Hanford Vadose Zone Using Colloidal Silica Suspension Injection and Subsequent Gelation - Laboratory Study

NASA Astrophysics Data System (ADS)

Zhong, L.; Lee, M. H.; Lee, B.; Yang, S.

2016-12-01

Delivery of nutrient to and establish a slow release carbon source in the vadose zone and capillary fringe zone is essential for setting up of a long-lasting bioremediation of contaminations in those zones. Conventional solution-based injection and infiltration approaches are facing challenges to achieve the delivery and remedial goals. Aqueous silica suspensions undergo a delayed gelation process under favorite geochemical conditions. The delay in gelation provides a time window for the injection of the suspension into the subsurface; and the gelation of the amendment-silica suspension enables the amendment-laden gel to stay in the target zone and slowly release the constituents for contaminant remediation. This approach can potentially be applied to deliver bio-nutrients to the vadose zone and capillary fringe zone for enhanced bioremediation and achieve remedial goals. This research was conducted to demonstrate delayed gelation of colloidal silica suspensions when carbon sources were added and to prove the gelation occurs in sediments under vadose conditions. Sodium lactate, vegetable oil, ethanol, and molasses were tested as the examples of carbon source (or nutrient) amendments. The rheological properties of the silica suspensions during the gelation were characterized. The influence of silica, salinity, nutrient concentrations, and the type of nutrients was studied. The kinetics of nutrient release from silica-nutrient gel was quantified using molasses as the example, and the influence of suspension gelation time was evaluated. The injection behavior of the suspensions was investigated by monitoring their viscosity changes and the injection pressures when the suspensions were delivered into sediment columns.

A vadose zone water fluxmeter with divergence control

NASA Astrophysics Data System (ADS)

Gee, G. W.; Ward, A. L.; Caldwell, T. G.; Ritter, J. C.

2002-08-01

Unsaturated water flux densities are needed to quantify water and contaminant transfer within the vadose zone. However, water flux densities are seldom measured directly and often are predicted with uncertainties of an order or magnitude or more. A water fluxmeter was designed, constructed, and tested to directly measure drainage fluxes in field soils. The fluxmeter was designed to minimize divergence. It concentrates flow into a narrow sensing region filled with a fiberglass wick. The wick applies suction, proportional to its length, and passively drains the meter. The meter can be installed in an augured borehole at almost any depth below the root zone. Water flux through the meter is measured with a self-calibrating tipping bucket, with a sensitivity of ~4 mL tip-1. For our meter this is equivalent to detection limit of ~0.1 mm. Passive-wick devices previously have not properly corrected for flow divergence. Laboratory measurements supported predictions of a two-dimensional (2-D) numerical model, which showed that control of the collector height H and knowledge of soil hydraulic properties are required for improving divergence control, particularly at fluxes below 1000 mm yr-1. The water fluxmeter is simple in concept, is inexpensive, and has the capability of providing continuous and reliable monitoring of unsaturated water fluxes ranging from less than 1 mm yr-1 to more than 1000 mm yr-1.

Groundwater response to leakage of surface water through a thick vadose zone in the middle reaches area of Heihe River Basin, in China

NASA Astrophysics Data System (ADS)

Wang, X.-S.; Ma, M.-G.; Li, X.; Zhao, J.; Dong, P.; Zhou, J.

2009-12-01

The behavior of groundwater response to leakage of surface water in the middle reaches area of Heihe River Basin is significantly influenced by a thick vadose zone. The variation of groundwater level is a result of two recharge events corresponding to leakage of Heihe River and irrigation water with different delay time. A nonlinear leakage model is developed to calculate the monthly leakage of Heihe River in considering changes of streamflow, river stage and agricultural water utilization. Numerical modeling of variable saturated flow is carried out to investigate the general behaviors of leakage-recharge conversion through a thick vadose zone. It is found that the variable recharge can be approximated by simple reservoir models for both leakage under a river and leakage under an irrigation district but with different delay-time and recession coefficient. A triple-reservoir model of relationship between surface water, vadose zone and groundwater is developed. It reproduces the in situ water table movement during 1989-2006 with variable streamflow of Heihe River and agricultural water utilization. The model is applied to interpret groundwater dynamics during 2007-2008 that observed in the Watershed Airborne Telemetry Experimental Research (WATER).

Groundwater response to leakage of surface water through a thick vadose zone in the middle reaches area of Heihe River Basin, in China

NASA Astrophysics Data System (ADS)

Wang, X.-S.; Ma, M.-G.; Li, X.; Zhao, J.; Dong, P.; Zhou, J.

2010-04-01

The behavior of groundwater response to leakage of surface water in the middle reaches area of Heihe River Basin is significantly influenced by a thick vadose zone. The groundwater regime is a result of two recharge events due to leakage of Heihe River and irrigation water with different delay time. A nonlinear leakage model is developed to calculate the monthly leakage of Heihe River in considering changes of streamflow, river stage and agricultural water utilization. Numerical modeling of variable saturated flow is carried out to investigate the general behaviors of leakage-recharge conversion through a thick vadose zone. It is found that the recharge pattern can be approximated by simple reservoir models of leakages under a river and under an irrigation district with different delay-time and recession coefficient. A triple-reservoir model of relationship between surface water, vadose zone and groundwater is developed. It reproduces the groundwater regime during 1989-2006 with variable streamflow of Heihe River and agricultural water utilization. The model is applied to interpret changes of groundwater level during 2007-2008 that observed in the Watershed Airborne Telemetry Experimental Research (WATER).

Vadose Zone Monitoring of Dairy Green Water Lagoons using Soil Solution Samplers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brainard, James R.; Coplen, Amy K

2005-11-01

Over the last decade, dairy farms in New Mexico have become an important component to the economy of many rural ranching and farming communities. Dairy operations are water intensive and use groundwater that otherwise would be used for irrigation purposes. Most dairies reuse their process/green water three times and utilize lined lagoons for temporary storage of green water. Leakage of water from lagoons can pose a risk to groundwater quality. Groundwater resource protection infrastructures at dairies are regulated by the New Mexico Environment Department which currently relies on monitoring wells installed in the saturated zone for detecting leakage of wastemore » water lagoon liners. Here we present a proposal to monitor the unsaturated zone beneath the lagoons with soil water solution samplers to provide early detection of leaking liners. Early detection of leaking liners along with rapid repair can minimize contamination of aquifers and reduce dairy liability for aquifer remediation. Additionally, acceptance of vadose zone monitoring as a NMED requirement over saturated zone monitoring would very likely significantly reduce dairy startup and expansion costs. Acknowledgment Funding for this project was provided by the Sandia National Laboratories Small Business Assistance Program« less

Linking river, floodplain, and vadose zone hydrology to improve restoration of a coastal river affected by saltwater intrusion.

PubMed

Kaplan, D; Muñoz-Carpena, R; Wan, Y; Hedgepeth, M; Zheng, F; Roberts, R; Rossmanith, R

2010-01-01

Floodplain forests provide unique ecological structure and function, which are often degraded or lost when watershed hydrology is modified. Restoration of damaged ecosystems requires an understanding of surface water, groundwater, and vadose (unsaturated) zone hydrology in the floodplain. Soil moisture and porewater salinity are of particular importance for seed germination and seedling survival in systems affected by saltwater intrusion but are difficult to monitor and often overlooked. This study contributes to the understanding of floodplain hydrology in one of the last bald cypress [Taxodium distichum (L.) Rich.] floodplain swamps in southeast Florida. We investigated soil moisture and porewater salinity dynamics in the floodplain of the Loxahatchee River, where reduced freshwater flow has led to saltwater intrusion and a transition to salt-tolerant, mangrove-dominated communities. Twenty-four dielectric probes measuring soil moisture and porewater salinity every 30 min were installed along two transects-one in an upstream, freshwater location and one in a downstream tidal area. Complemented by surface water, groundwater, and meteorological data, these unique 4-yr datasets quantified the spatial variability and temporal dynamics of vadose zone hydrology. Results showed that soil moisture can be closely predicted based on river stage and topographic elevation (overall Nash-Sutcliffe coefficient of efficiency = 0.83). Porewater salinity rarely exceeded tolerance thresholds (0.3125 S m(-1)) for bald cypress upstream but did so in some downstream areas. This provided an explanation for observed vegetation changes that both surface water and groundwater salinity failed to explain. The results offer a methodological and analytical framework for floodplain monitoring in locations where restoration success depends on vadose zone hydrology and provide relationships for evaluating proposed restoration and management scenarios for the Loxahatchee River.

SCREENING MODEL FOR NONAQUEOUS PHASE LIQUID TRANS- PORT IN THE VADOSE ZONE USING GREEN-AMPT AND KINEMATIC WAVE THEORY

EPA Science Inventory

In this paper, a screening model for flow of a nonaqueous phase liquid (NAPL) and associated chemical transport in the vadose zone is developed. The model is based on kinematic approximation of the governing equations for both the NAPL and a partitionable chemical constituent. Th...

Interfacial Reduction-Oxidation Mechanisms Governing Fate and Transport of Contaminants in the Vadose Zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Principal Investigator: Baolin Deng, University of Missouri, Columbia, MO; Co-Principal Investigator: Silvia Sabine Jurisson, University of Missouri, Columbia, MO; Co-Principal Investigator: Edward C. Thornton, Pacific Northwest National Laboratory Richland, WA

2008-05-12

There are many soil contamination sites at the Department of Energy (DOE) installations that contain radionuclides and toxic metals such as uranium (U), technetium (Tc), and chromium (Cr). Since these contaminants are the main 'risk drivers' at the Hanford site (WA) and some of them also pose significant risk at other DOE facilities (e.g., Oak Ridge Reservation - TN; Rocky Flats - CO), development of technologies for cost effective site remediation is needed. Current assessment indicates that complete removal of these contaminants for ex-situ disposal is infeasible, thus in-situ stabilization through reduction to insoluble species is considered one of themore » most important approaches for site remediation. In Situ Gaseous Reduction (ISGR) is a technology developed by Pacific Northwest National Laboratory (PNNL) for vadose zone soil remediation. The ISGR approach uses hydrogen sulfide (H{sub 2}S) for reductive immobilization of contaminants that show substantially lower mobility in their reduced forms (e.g., Tc, U, and Cr). The technology can be applied in two ways: (i) to immobilize or stabilize pre-existing contaminants in the vadose zone soils by direct H{sub 2}S treatment, or (ii) to create a permeable reactive barrier (PRB) that prevents the migration of contaminants. Direct treatment involves reduction of the contaminants by H{sub 2}S to less mobile species. Formation of a PRB is accomplished through reduction of ferric iron species in the vadose zone soils by H{sub 2}S to iron sulfides (e.g., FeS), which provides a means for capturing the contaminants entering the treated zone. Potential future releases may occur during tank closure activities. Thus, the placement of a permeable reactive barrier by ISGR treatment can be part of the leak mitigation program. Deployment of these ISGR approaches, however, requires a better understanding of the immobilization kinetics and mechanisms, and a better assessment of the long-term effectiveness of treatment. The

A vadose zone water fluxmeter with divergence control

USGS Publications Warehouse

Gee, G.W.; Ward, A.L.; Caldwell, T.G.; Ritter, J.C.

2002-01-01

Unsaturated water flux densities are needed to quantify water and contaminant transfer within the vadose zone. However, water flux densities are seldom measured directly and often are predicted with uncertainties of an order or magnitude or more. A water fluxmeter was designed, constructed, and tested to directly measure drainage fluxes in field soils. The fluxmeter was designed to minimize divergence. It concentrates flow into a narrow sensing region filled with a fiberglass wick. The wick applies suction, proportional to its length, and passively drains the meter. The meter can be installed in an augured borehole at almost any depth below the root zone. Water flux through the meter is measured with a self‐calibrating tipping bucket, with a sensitivity of ∼4 mL tip−1. For our meter this is equivalent to detection limit of ∼0.1 mm. Passive‐wick devices previously have not properly corrected for flow divergence. Laboratory measurements supported predictions of a two‐dimensional (2‐D) numerical model, which showed that control of the collector height H and knowledge of soil hydraulic properties are required for improving divergence control, particularly at fluxes below 1000 mm yr−1. The water fluxmeter is simple in concept, is inexpensive, and has the capability of providing continuous and reliable monitoring of unsaturated water fluxes ranging from less than 1 mm yr−1 to more than 1000 mm yr−1.

Surface and subsurface continuous gravimetric monitoring of groundwater recharge processes through the karst vadose zone at Rochefort Cave (Belgium)

NASA Astrophysics Data System (ADS)

Watlet, A.; Van Camp, M. J.; Francis, O.; Poulain, A.; Hallet, V.; Triantafyllou, A.; Delforge, D.; Quinif, Y.; Van Ruymbeke, M.; Kaufmann, O.

2017-12-01

Ground-based gravimetry is a non-invasive and integrated tool to characterize hydrological processes in complex environments such as karsts or volcanoes. A problem in ground-based gravity measurements however concerns the lack of sensitivity in the first meters below the topographical surface, added to limited infiltration below the gravimeter building (umbrella effect). Such limitations disappear when measuring underground. Coupling surface and subsurface gravity measurements therefore allow isolating hydrological signals occurring in the zone between the two gravimeters. We present a coupled surface/subsurface continuous gravimetric monitoring of 2 years at the Rochefort Cave Laboratory (Belgium). The gravity record includes surface measurements of a GWR superconducting gravimeter and subsurface measurements of a Micro-g LaCoste gPhone gravimeter, installed in a cave 35 m below the surface station. The recharge of karstic aquifers is extremely complex to model, mostly because karst hydrological systems are composed of strongly heterogeneous flows. Most of the problem comes from the inadequacy of conventional measuring tools to correctly sample such heterogeneous media, and particularly the existence of a duality of flow types infiltrating the vadose zone: from rapid flows via open conduits to slow seepage through porous matrix. Using the surface/subsurface gravity difference, we were able to identify a significant seasonal groundwater recharge within the karst vadose zone. Seasonal or perennial perched reservoirs have already been proven to exist in several karst areas due to the heterogeneity of the porosity and permeability gradient in karstified carbonated rocks. Our gravimetric experiment allows assessing more precisely the recharge processes of such reservoirs. The gravity variations were also compared with surface and in-cave hydrogeological monitoring (i.e. soil moisture, in-cave percolating water discharges, water levels of the saturated zone). Combined

An alternative tensiometer design for deep vadose zone monitoring

NASA Astrophysics Data System (ADS)

Moradi, A. B.; Kandelous, M. M.; Hopmans, J. W.

2015-12-01

The conventional tensiometer is among the most accurate devices for soil water matric potential measurements, as well as for estimations of soil water flux from soil water potential gradients. Uncertainties associated with conventional tensiometers such as caused by ambient temperature effects and the draining of the tensiometer tube, as well as their limitation for deep soil monitoring has prevented their widespread use for vadose zone monitoring, despite their superior accuracy, in general. We introduce an alternative tensiometer design that offers the accuracy of the conventional tensiometer, while minimizing afore-mentioned uncertainties and limitations. The proposed alternative tensiometer largely eliminates temperature-induced diurnal fluctuations and uncertainties associated with the draining of the tensiometer tube, and removes the limitation in installation depth. In addition, the manufacturing costs of this alternative tensiometer design is close to that of the conventional tensiometer, while it is especially suited for monitoring of soil water potential gradients as required for soil water flux measurements.

THE DOE COMPLEX-WIDE VADOSE ZONE SCIENCE AND TECHNOLOGY ROADMAP: CHARACTERIZATION MODELING AND SIMULATION OF SUBSURFACE CONTAMINANT FATE AND TRANSPORT

EPA Science Inventory

The Idaho National Engineering & Environmental Lab (INEEL) was charged by DOE EM to develop a complex-wide science and technology roadmap for the characterization, modeling and simulation of the fate and transport of contamination in the vadose zone. Various types of hazardous, r...

Coupled effects of solution chemistry and hydrodynamics on the mobility and transport of quantum dot nanomaterials in the Vadose Zone

USDA-ARS?s Scientific Manuscript database

To investigate the coupled effects of solution chemistry and vadose zone processes on the mobility of quantum dot (QD) nanoparticles, laboratory scale transport experiments were performed. The complex coupled effects of ionic strength, size of QD aggregates, surface tension, contact angle, infiltrat...

Managed aquifer recharge of treated wastewater: water quality changes resulting from infiltration through the vadose zone.

PubMed

Bekele, Elise; Toze, Simon; Patterson, Bradley; Higginson, Simon

2011-11-01

Secondary treated wastewater was infiltrated through a 9 m-thick calcareous vadose zone during a 39 month managed aquifer recharge (MAR) field trial to determine potential improvements in the recycled water quality. The water quality improvements of the recycled water were based on changes in the chemistry and microbiology of (i) the recycled water prior to infiltration relative to (ii) groundwater immediately down-gradient from the infiltration gallery. Changes in the average concentrations of several constituents in the recycled water were identified with reductions of 30% for phosphorous, 66% for fluoride, 62% for iron and 51% for total organic carbon when the secondary treated wastewater was infiltrated at an applied rate of 17.5 L per minute with a residence time of approximately four days in the vadose zone and less than two days in the aquifer. Reductions were also noted for oxazepam and temazepam among the pharmaceuticals tested and for a range of microbial pathogens, but reductions were harder to quantify as their magnitudes varied over time. Total nitrogen and carbamazepine persisted in groundwater down-gradient from the infiltration galleries. Infiltration does potentially offer a range of water quality improvements over direct injection to the water table without passage through the unsaturated zone; however, additional treatment options for the non-potable water may still need to be considered, depending on the receiving environment or the end use of the recovered water. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

The vadose zone as a geoindicator of environmental change and groundwater quality in water-scarce areas

NASA Astrophysics Data System (ADS)

Edmunds, W. M.; Baba Goni, I.; Gaye, C. B.; Jin, L.

2013-12-01

Inert and reactive tracers in moisture profiles provide considerable potential for the vadose zone to be used as an indicator of rapid environmental change. This indicator is particularly applicable in areas of water stress where long term (decade to century) scale records may be found in deep unsaturated zones in low rainfall areas and provide insights into recent recharge, climate variation and water-rock interactions which generate groundwater quality. Unsaturated zone Cl records obtained by elutriation of moisture are used widely for estimating recharge and water balance studies; isotope profiles (3H, δ2H, δ18O) from total water extraction procedures are used for investigation of residence times and hydrological processes. Apart from water taken using lysimeters, little work has been conducted directly on the geochemistry of pore fluids. This is mainly due to the difficulties of extraction of moisture from unsaturated material with low water contents (typically 2-6 wt%) and since dilution methods can create artifacts. Using immiscible liquid displacement techniques it is now possible to directly investigate the geochemistry of moisture from unsaturated zone materials. Profiles up to 35m from Quaternary sediments from dryland areas of the African Sahel (Nigeria, Senegal) as well as Inner Mongolia, China are used to illustrate the breadth of information obtainable from vadose zone profiles. Using pH, major and trace elements and comparing with isotopic data, a better understanding is gained of timescales of water movement, aquifer recharge, environmental records and climate history as well as water-rock interaction and contaminant behaviour. The usefulness of tritium as residence time indicator has now expired following cessation of atmospheric thermonuclear testing and through radioactive decay. Providing the rainfall Cl, moisture contents and bulk densities of the sediments are known, then Cl accumulation can be substituted to estimate timescales. Profiles

Trace Metals in Groundwater & Vadose Zone Calcite: In Situ Containment & Stabilization of Stronthium-90 & Other Divalent Metals & Radionuclides at Arid West DOE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Robert W.

2005-06-01

Radionuclide and metal contaminants such as strontium-90 are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center [INTEC] at the Idaho National Laboratory [INL]). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., strontium-90) by their facilitated co-precipitation with calcium carbonate (primarily calcite) in groundwater and vadosemore » zone systems. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by (a) increasing pH and alkalinity and (b) liberating cations from the aquifer matrix by cation exchange reactions. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which is produced in situ by native urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from the aqueous phase over the long term. We are currently conducting field based activities at both the INL Vadose Zone Research Park (VZRP), an uncontaminated surrogate site for the strontium-90 contaminated vadose zone at INTEC and at the strontium-90 contaminated aquifer of 100-N area of the Hanford site.« less

Three-dimensional modeling of nitrate-N transport in vadose zone: Roles of soil heterogeneity and groundwater flux.

PubMed

Akbariyeh, Simin; Bartelt-Hunt, Shannon; Snow, Daniel; Li, Xu; Tang, Zhenghong; Li, Yusong

2018-04-01

Contamination of groundwater from nitrogen fertilizers in agricultural lands is an important environmental and water quality management issue. It is well recognized that in agriculturally intensive areas, fertilizers and pesticides may leach through the vadose zone and eventually reach groundwater. While numerical models are commonly used to simulate fate and transport of agricultural contaminants, few models have considered a controlled field work to investigate the influence of soil heterogeneity and groundwater flow on nitrate-N distribution in both root zone and deep vadose zone. In this work, a numerical model was developed to simulate nitrate-N transport and transformation beneath a center pivot-irrigated corn field on Nebraska Management System Evaluation area over a three-year period. The model was based on a realistic three-dimensional sediment lithology, as well as carefully controlled irrigation and fertilizer application plans. In parallel, a homogeneous soil domain, containing the major sediment type of the site (i.e. sandy loam), was developed to conduct the same water flow and nitrate-N leaching simulations. Simulated nitrate-N concentrations were compared with the monitored nitrate-N concentrations in 10 multi-level sampling wells over a three-year period. Although soil heterogeneity was mainly observed from top soil to 3 m below the surface, heterogeneity controlled the spatial distribution of nitrate-N concentration. Soil heterogeneity, however, has minimal impact on the total mass of nitrate-N in the domain. In the deeper saturated zone, short-term variations of nitrate-N concentration correlated with the groundwater level fluctuations. Copyright © 2018 Elsevier B.V. All rights reserved.

Three-dimensional modeling of nitrate-N transport in vadose zone: Roles of soil heterogeneity and groundwater flux

NASA Astrophysics Data System (ADS)

Akbariyeh, Simin; Bartelt-Hunt, Shannon; Snow, Daniel; Li, Xu; Tang, Zhenghong; Li, Yusong

2018-04-01

Contamination of groundwater from nitrogen fertilizers in agricultural lands is an important environmental and water quality management issue. It is well recognized that in agriculturally intensive areas, fertilizers and pesticides may leach through the vadose zone and eventually reach groundwater. While numerical models are commonly used to simulate fate and transport of agricultural contaminants, few models have considered a controlled field work to investigate the influence of soil heterogeneity and groundwater flow on nitrate-N distribution in both root zone and deep vadose zone. In this work, a numerical model was developed to simulate nitrate-N transport and transformation beneath a center pivot-irrigated corn field on Nebraska Management System Evaluation area over a three-year period. The model was based on a realistic three-dimensional sediment lithology, as well as carefully controlled irrigation and fertilizer application plans. In parallel, a homogeneous soil domain, containing the major sediment type of the site (i.e. sandy loam), was developed to conduct the same water flow and nitrate-N leaching simulations. Simulated nitrate-N concentrations were compared with the monitored nitrate-N concentrations in 10 multi-level sampling wells over a three-year period. Although soil heterogeneity was mainly observed from top soil to 3 m below the surface, heterogeneity controlled the spatial distribution of nitrate-N concentration. Soil heterogeneity, however, has minimal impact on the total mass of nitrate-N in the domain. In the deeper saturated zone, short-term variations of nitrate-N concentration correlated with the groundwater level fluctuations.

H51E-1535: Biogeochemical factors influencing the transport and fate of colloids and colloid-associated contaminants in the vadose zone

USDA-ARS?s Scientific Manuscript database

The vadose zone exhibits large spatial and temporal variability in many physical, chemical, and biological factors that strongly influence the transport and fate of colloids (e.g., microbes, nanoparticles, clays, and dissolved organic matter) and colloid-associated contaminants (e.g., heavy metals, ...

Water movement and solute transport in deep vadose zone under four irrigated agricultural land-use types in the North China Plain

NASA Astrophysics Data System (ADS)

Min, Leilei; Shen, Yanjun; Pei, Hongwei; Wang, Ping

2018-04-01

Groundwater-fed agriculture has caused water table declines and groundwater quality degradation in the North China Plain. Based on sediment sampling in deep vadose zone (with a maximum depth of 11.0 m), groundwater recharge, seepage velocity, solute inventory and transport under four typical irrigated agricultural land-use types (winter wheat and summer maize, WM; pear orchards, PO; outdoor vegetables, VE; and cotton, CO) were investigated in this study. The results reveal that there are many solutes stored in the vadose zone. Nitrate storage per unit depth in the vadose zone is highest under PO (1703 kg/ha), followed by VE (970 kg/ha), WM (736 kg/ha) and CO (727 kg/ha). However, the amount of annual leached nitrate under the four land-use types results in a different order (VE, 404 kg/ha; WM, 108 kg/ha; PO, 23 kg/ha; CO, 13 kg/ha). The estimated average recharge rates are 180 mm/yr for WM, 27 mm/yr for CO, 320 mm/yr for VE and 49 mm/yr for PO. The seepage velocity under VE (2.22 m/yr) exceeds the values under the other three land-use types (WM, 0.85 m/yr; PO, 0.49 m/yr; CO, 0.09 m/yr). The highest seepage velocity under VE caused significant nitrate contamination in groundwater, whereas the other two land-use types (WM and PO) had no direct influence on groundwater quality. The results of this work could be used for groundwater resources management.

Influence of colloids on the attenuation and transport of phosphorus in alluvial gravel aquifer and vadose zone media.

PubMed

Pang, Liping; Lafogler, Mark; Knorr, Bastian; McGill, Erin; Saunders, Darren; Baumann, Thomas; Abraham, Phillip; Close, Murray

2016-04-15

Phosphorous (P) leaching (e.g., from effluents, fertilizers) and transport in highly permeable subsurface media can be an important pathway that contributes to eutrophication of receiving surface waters as groundwater recharges the base-flow of surface waters. Here we investigated attenuation and transport of orthophosphate-P in gravel aquifer and vadose zone media in the presence and absence of model colloids (Escherichia coli, kaolinite, goethite). Experiments were conducted using repacked aquifer media in a large column (2m long, 0.19m in diameter) and intact cores (0.4m long, 0.24m in diameter) of vadose zone media under typical field flow rates. In the absence of the model colloids, P was readily traveled through the aquifer media with little attenuation (up to 100% recovery) and retardation, and P adsorption was highly reversible. Conversely, addition of the model colloids generally resulted in reduced P concentration and mass recovery (down to 28% recovery), and increased retardation and adsorption irreversibility in both aquifer and vadose zone media. The degree of colloid-assisted P attenuation was most significant in the presence of fine material and Fe-containing colloids at low flow rate but was least significant in the presence of coarse gravels and E. coli at high flow rate. Based on the experimental results, setback distances of 49-53m were estimated to allow a reduction of P concentrations in groundwater to acceptable levels in the receiving water. These estimates were consistent with field observations in the same aquifer media. Colloid-assisted P attenuation can be utilized to develop mitigation strategies to better manage effluent applications in gravelly soils. To efficiently retain P within soil matrix and reduce P leaching to groundwater, it is recommended to select soils that are rich in iron oxides, to periodically disturb soil preferential flow paths by tillage, and to apply a low irrigation rate. Copyright © 2016 Elsevier B.V. All rights

E-Area Low-Level Waste Facility Vadose Zone Model: Confirmation of Water Mass Balance for Subsidence Scenarios

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dyer, J. A.

In preparation for the next revision of the E-Area Low-Level Waste Facility (LLWF) Performance Assessment (PA), a mass balance model was developed in Microsoft Excel to confirm correct implementation of intact- and subsided-area infiltration profiles for the proposed closure cap in the PORFLOW vadose-zone model. The infiltration profiles are based on the results of Hydrologic Evaluation of Landfill Performance (HELP) model simulations for both intact and subsided cases.

Alternative Methods for Assessing Contaminant Transport from the Vadose Zone to Indoor Air

NASA Astrophysics Data System (ADS)

Baylor, K. J.; Lee, A.; Reddy, P.; Plate, M.

2010-12-01

Vapor intrusion, which is the transport of contaminant vapors from groundwater and the vadose zone to indoor air, has emerged as a significant human health risk near hazardous waste sites. Volatile organic compounds (VOCs) such as trichloroethylene (TCE) and tetrachloroethylene (PCE) can volatilize from groundwater and from residual sources in the vadose zone and enter homes and commercial buildings through cracks in the slab, plumbing conduits, or other preferential pathways. Assessment of the vapor intrusion pathway typically requires collection of groundwater, soil gas, and indoor air samples, a process which can be expensive and time-consuming. We evaluated three alternative vapor intrusion assessment methods, including 1) use of radon as a surrogate for vapor intrusion, 2) use of pressure differential measurements between indoor/outdoor and indoor/subslab to assess the potential for vapor intrusion, and 3) use of passive, longer-duration sorbent methods to measure indoor air VOC concentrations. The primary test site, located approximately 30 miles south of San Francisco, was selected due to the presence of TCE (10 - 300 ug/L) in shallow groundwater (5 to 10 feet bgs). At this test site, we found that radon was not a suitable surrogate to asses vapor intrusion and that pressure differential measurements are challenging to implement and equipment-intensive. More significantly, we found that the passive, longer-duration sorbent methods are easy to deploy and compared well quantitatively with standard indoor air sampling methods. The sorbent technique is less than half the cost of typical indoor air methods, and also provides a longer duration sample, typically 3 to 14 days rather than 8 to 24 hours for standard methods. The passive sorbent methods can be a reliable, cost-effective, and easy way to sample for TCE, PCE and other VOCs as part of a vapor intrusion investigation.

Role of the sedimentary structure of the urban vadose zone (URVAZO) on the transfer of heavy metals of an urban stormwater basin

NASA Astrophysics Data System (ADS)

Angulo-Jaramillo, R.; Winiarski, T.; Goutaland, D.; Lassabatere, L.

2009-12-01

Stormwater infiltration basins have become a common alternative practice to traditional stormwater pipe networks in urban areas. They are often built in permeable subsurface soils (Urban Vadose Zone, URVAZO), such as alluvial deposits. These sedimentary deposits are highly heterogeneous and generate preferential flow paths that may cause either rapid or non-uniform transport of contaminants at great depths. The understanding of how subsurface vadose zone heterogeneities transfer contaminant and fluid flow to the aquifer still remains a challenge in urban hydrology. Indeed, urban stormwater may contain pollutants that can contaminate either soil or groundwater. The aim of this study is to evaluate the role of the lithological heterogeneity of a glaciofluvial deposit underlying an urban infiltration basin on the link between water flow and heavy metals retention. A trench wall (14m length x 3m depth) was exposed by excavating the glaciofluvial formation. By a hydrogeophysical approach based on a sedimentary structural units and in situ hydraulic characterization (Beerkan tests), a realistic hydrostratigraphic 2D model was defined. The trench was sampled on nine vertical sections of 1.5m length, with ten samples per vertical section following each lithofacies. A total of 90 samples were analyzed. Coarse (mechanical sieving) and fine (laser diffraction) particle size distribution analysis, as well as the concentration of three replicates of Pb, Cu, Zn and organic matter (OM) was measured for each sample. The principal component analysis shows a strong correlation between metal concentration and the lithofacies. This hydrostratigraphic model was implemented in the finite element program Hydrus2D. The soil heterogeneity exerts an impact on the heterogeneity of the water content field under slightly saturated conditions, as they induce capillary barrier effects. These capillary barrier effects may generate water accumulation in some lithofacies overlying matrix

Which key properties controls the preferential transport in the vadose zone under transient hydrological conditions

NASA Astrophysics Data System (ADS)

Groh, J.; Vanderborght, J.; Puetz, T.; Gerke, H. H.; Rupp, H.; Wollschlaeger, U.; Stumpp, C.; Priesack, E.; Vereecken, H.

2015-12-01

Understanding water flow and solute transport in the unsaturated zone is of great importance for an appropriate land use management strategy. The quantification and prediction of water and solute fluxes through the vadose zone can help to improve management practices in order to limit potential risk on our fresh water resources. Water related solute transport and residence time is strongly affected by preferential flow paths in the soil. Water flow in soils depends on soil properties and site factors (climate or experiment conditions, land use) and are therefore important factors to understand preferential solute transport in the unsaturated zone. However our understanding and knowledge of which on-site properties or conditions define and enhance preferential flow and transport is still poor and mostly limited onto laboratory experimental conditions (small column length and steady state boundary conditions). Within the TERENO SOILCan lysimeter network, which was designed to study the effects of climate change on soil functions, a bromide tracer was applied on 62 lysimeter at eight different test sites between Dec. 2013 and Jan. 2014. The TERENO SOILCan infrastructure offers the unique possibility to study the occurrence of preferential flow and transport of various soil types under different natural transient hydrological conditions and land use (crop, bare and grassland) at eight TERENO SOILCan observatories. Working with lysimeter replicates at each observatory allows defining the spatial variability of preferential transport and flow. Additionally lysimeters in the network were transferred within and between observatories in order to subject them to different rainfall and temperature regimes and enable us to relate the soil type susceptibility of preferential flow and transport not only to site specific physical and land use properties, but also to different transient boundary conditions. Comparison and statistical analysis between preferential flow indicators 5

Spatially resolved U(VI) partitioning and speciation: implications for plume scale behavior of contaminant U in the Hanford vadose zone.

PubMed

Wan, Jiamin; Kim, Yongman; Tokunaga, Tetsu K; Wang, Zheming; Dixit, Suvasis; Steefel, Carl I; Saiz, Eduardo; Kunz, Martin; Tamura, Nobumichi

2009-04-01

A saline-alkaline brine containing high concentration of U(VI) was accidentally spilled at the Hanford Site in 1951, introducing 10 tons of U into sediments under storage tank BX-102. U concentrations in the deep vadose zone and groundwater plumes increase with time, yet how the U has been migrating is not fully understood. We simulated the spill event in laboratory soil columns, followed by aging, and obtained spatially resolved U partitioning and speciation along simulated plumes. We found after aging, at apparent steady state, that the pore aqueous phase U concentrations remained surprisingly high (up to 0.022 M), in close agreement with the recently reported high U concentrations (up to 0.027 M) in the vadose zone plume (1). The pH values of aged pore liquids varying from 10 to 7, consistent with the measured pH of the field borehole sediments varying from 9.5 to 7.4 (2), from near the plume source to the plume front. The direct measurements of aged pore liquids together with thermodynamic calculations using a Pitzer approach revealed that UO2(CO3)3(4-) is the dominant aqueous U species within the plume body (pH 8-10), whereas Ca2UO2(CO3)3 and CaUO2(CO3)32- are also significant in the plume frontvicinity (pH 7-8), consistent with that measured from field borehole pore-waters (3). U solid phase speciation varies at different locations along the plume flow path and even within single sediment grains, because of location dependent pore and micropore solution chemistry. Our results suggest that continuous gravity-driven migration of the highly stable U02(CO3)34 in the residual carbonate and sodium rich tank waste solution is likely responsible for the detected growing U concentrations in the vadose zone and groundwater.

Plutonium Particle Migration in the Shallow Vadose Zone: The Nevada Test Site as an Analog Site

NASA Astrophysics Data System (ADS)

Hunt, J. R.; Smith, D. K.

2004-12-01

The upper meter of the vadose zone in desert environments is the horizon where wastes have been released and human exposure is determined through dermal, inhalation, and food uptake pathways. This region is also characterized by numerous coupled processes that determine contaminant transport, including precipitation infiltration, evapotranspiration, daily and annual temperature cycling, dust resuspension, animal burrowing, and geochemical weathering reactions. While there is considerable interest in colloidal transport of minerals, pathogenic organisms, and contaminants in the vadose zone, there are limited field sites where the actual occurrence of contaminant migration can be quantified over the appropriate spatial and temporal scales of interest. At the US Department of Energy Nevada Test Site, there have been numerous releases of radionuclides since the 1950's that have become field-scale tracer tests. One series of tests was the four safety shots conducted in an alluvial valley of Area 11 in the 1950's. These experiments tested the ability of nuclear materials to survive chemical explosions without initiating fission reactions. Four above-ground tests were conducted and they released plutonium and uranium on the desert valley floor with only one of the tests undergoing some fission. Shortly after the tests, the sites were surveyed for radionuclide distribution on the land surface using aerial surveys and with depth. Additional studies were conducted in the 1970's to better understand the fate of plutonium in the desert that included studies of depth distribution and dust resuspension. More recently, plutonium particle distribution in the soil profile was detected using autoradiography. The results to date demonstrate the vertical migration of plutonium particles to depths in excess of 30 cm in this arid vadose zone. While plutonium migration at the Nevada Test Site has been and continues to be a concern, these field experiments have become analog sites for the

A BENCHMARKING ANALYSIS FOR FIVE RADIONUCLIDE VADOSE ZONE MODELS (CHAIN, MULTIMED_DP, FECTUZ, HYDRUS, AND CHAIN 2D) IN SOIL SCREENING LEVEL CALCULATIONS

EPA Science Inventory

Five radionuclide vadose zone models with different degrees of complexity (CHAIN, MULTIMED_DP, FECTUZ, HYDRUS, and CHAIN 2D) were selected for use in soil screening level (SSL) calculations. A benchmarking analysis between the models was conducted for a radionuclide (99Tc) rele...

Chlorinated solvents in groundwater of the United States

USGS Publications Warehouse

Moran, M.J.; Zogorski, J.S.; Squillace, P.J.

2007-01-01

Four chlorinated solvents-methylene chloride, perchloroethene (PCE), 1,1,1-trichloroethane, and trichloroethene (TCE)-were analyzed in samples of groundwater taken throughout the conterminous United States by the U.S. Geological Survey. The samples were collected between 1985 and 2002 from more than 5,000 wells. Of 55 volatile organic compounds (VOCs) analyzed in groundwater samples, solvents were among the most frequently detected. Mixtures of solvents in groundwater were common and may be the result of common usage of solvents or degradation of one solvent to another. Relative to other VOCs with Maximum Contaminant Levels (MCLs), PCE and TCE ranked high in terms of the frequencies of concentrations greater than or near MCLs. The probability of occurrence of solvents in groundwater was associated with dissolved oxygen content of groundwater, sources such as urban land use and population density, and hydraulic properties of the aquifer. The results reinforce the importance of understanding the redox conditions of aquifers and the hydraulic properties of the saturated and vadose zones in determining the intrinsic susceptibility of groundwater to contamination by solvents. The results also reinforce the importance of controlling sources of solvents to groundwater. ?? 2007 American Chemical Society.

NATURAL ATTENUATION OF FUEL AND SOLVENT SPILLS ON AIR FORCE BASES: BIOSLURPING AND NATURAL BIOVENTING TO REMEDIATE A JET FUEL SPILL. EVALUATE PERFORMANCE OF NEW PUSH PROBES TO ASSAY FOR BIOREMEDIATION

EPA Science Inventory

Frequently both the subsurface vadose zone and underlying aquifer at Air Force Base spill locations are contaminated with fuel hydrocarbons such as benzene and degreasing solvents such as trichloroethene. In many instances these concentrations exceed regulatory limits mandated by...

Modeling non-steady state radioisotope transport in the vadose zone--A case study using uranium isotopes at Pena Blanca, Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ku, T. L.; Luo, S.; Goldstein, S. J.

2009-06-01

Current models using U- and Th-series disequilibria to study radioisotope transport in groundwater systems mostly consider a steady-state situation. These models have limited applicability to the vadose zone (UZ) where the concentration and migratory behavior of radioisotopes in fluid are often transitory. We present here, as a first attempt of its kind, a model simulating the non-steady state, intermittent fluid transport in vadose layers. It provides quantitative constraints on in-situ migration of dissolved and colloidal radioisotopes in terms of retardation factor and rock-water interaction (or water transit) time. For uranium, the simulation predicts that intermittent flushing in the UZ leadsmore » to a linear relationship between reciprocal U concentration and {sup 234}U/{sup 238}U ratio in percolating waters, with the intercept and slope bearing information on the rates of dissolution and {alpha}-recoil of U isotopes, respectively. The general validity of the model appears to be borne out by the measurement of uranium isotopes in UZ waters collected at various times over a period during 1995-2006 from a site in the Pena Blanca mining district, Mexico, where the Nopal I uranium deposit is located. Enhanced {sup 234}U/{sup 238}U ratios in vadose-zone waters resulting from lengthened non-flushing time as prescribed by the model provide an interpretative basis for using {sup 234}U/{sup 238}U in cave calcites to reconstruct the regional changes in hydrology and climate. We also provide a theoretical account of the model's potential applications using radium isotopes.« less

A New Method to Grow SiC: Solvent-Laser Heated Floating Zone

NASA Technical Reports Server (NTRS)

Woodworth, Andrew A.; Neudeck, Philip G.; Sayir, Ali

2012-01-01

The solvent-laser heated floating zone (solvent-LHFZ) growth method is being developed to grow long single crystal SiC fibers. The technique combines the single crystal fiber growth ability of laser heated floating zone with solvent based growth techniques (e.g. traveling solvent method) ability to grow SiC from the liquid phase. Initial investigations reported in this paper show that the solvent-LHFZ method readily grows single crystal SiC (retains polytype and orientation), but has a significant amount of inhomogeneous strain and solvent rich inclusions.

Vapor-phase transport of trichloroethene in an intermediate-scale vadose-zone system: retention processes and tracer-based prediction.

PubMed

Costanza-Robinson, Molly S; Carlson, Tyson D; Brusseau, Mark L

2013-02-01

Gas-phase transport experiments were conducted using a large weighing lysimeter to evaluate retention processes for volatile organic compounds (VOCs) in water-unsaturated (vadose-zone) systems, and to test the utility of gas-phase tracers for predicting VOC retardation. Trichloroethene (TCE) served as a model VOC, while trichlorofluoromethane (CFM) and heptane were used as partitioning tracers to independently characterize retention by water and the air-water interface, respectively. Retardation factors for TCE ranged between 1.9 and 3.5, depending on water content. The results indicate that dissolution into the bulk water was the primary retention mechanism for TCE under all conditions studied, contributing approximately two-thirds of the total measured retention. Accumulation at the air-water interface comprised a significant fraction of the observed retention for all experiments, with an average contribution of approximately 24%. Sorption to the solid phase contributed approximately 10% to retention. Water contents and air-water interfacial areas estimated based on the CFM and heptane tracer data, respectively, were similar to independently measured values. Retardation factors for TCE predicted using the partitioning-tracer data were in reasonable agreement with the measured values. These results suggest that gas-phase tracer tests hold promise for characterizing the retention and transport of VOCs in the vadose-zone. Copyright © 2012 Elsevier B.V. All rights reserved.

Using the natural biodegradation potential of shallow soils for in-situ remediation of deep vadose zone and groundwater.

PubMed

Avishai, Lior; Siebner, Hagar; Dahan, Ofer; Ronen, Zeev

2017-02-15

In this study, we examined the ability of top soil to degrade perchlorate from infiltrating polluted groundwater under unsaturated conditions. Column experiments designed to simulate typical remediation operation of daily wetting and draining cycles of contaminated water amended with an electron donor. Covering the infiltration area with bentonite ensured anaerobic conditions. The soil remained unsaturated, and redox potential dropped to less than -200mV. Perchlorate was reduced continuously from ∼1150mg/L at the inlet to ∼300mg/L at the outlet in daily cycles. Removal efficiency was between 60 and 84%. No signs of bioclogging were observed during three operation months although occasional iron reduction observed due to excess electron donor. Changes in perchlorate reducing bacteria numbers were inferred from an increased in pcrA gene abundances from ∼10 5 to 10 7 copied per gram at the end of the experiment indicating the growth of perchlorate-reducing bacteria. We proposed that the topsoil may serve as a bioreactor to treat high concentrations of perchlorate from the contaminated groundwater. The treated water that infiltrates from the topsoil through the vadose zone could be used to flush perchlorate from the deep vadose zone into the groundwater where it is retrieved again for treatment in the topsoil. Copyright © 2016 Elsevier B.V. All rights reserved.

Deep Vadose Zone Treatability Test for the Hanford Central Plateau. Interim Post-Desiccation Monitoring Results, Fiscal Year 2015

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Strickland, Christopher E.; Oostrom, Martinus

A field test of desiccation is being conducted as an element of the Deep Vadose Zone Treatability Test Program. The active desiccation portion of the test has been completed. Monitoring data have been collected at the field test site during the post-desiccation period and are reported herein. This is an interim data summary report that includes about 4 years of post-desiccation monitoring data. The DOE field test plan proscribes a total of 5 years of post-desiccation monitoring.

Assessing the impact of dairy waste lagoons on groundwater quality using a spatial analysis of vadose zone and groundwater information in a coastal phreatic aquifer.

PubMed

Baram, S; Kurtzman, D; Ronen, Z; Peeters, A; Dahan, O

2014-01-01

Dairy waste lagoons are considered to be point sources of groundwater contamination by chloride (Cl(-)), different nitrogen-species and pathogens/microorganisms. The objective of this work is to introduce a methodology to assess the past and future impacts of such lagoons on regional groundwater quality. The method is based on a spatial statistical analysis of Cl(-) and total nitrogen (TN) concentration distributions in the saturated and the vadose (unsaturated) zones. The method provides quantitative data on the relation between the locations of dairy lagoons and the spatial variability in Cl(-) and TN concentrations in groundwater. The method was applied to the Beer-Tuvia region, Israel, where intensive dairy farming has been practiced for over 50 years above the local phreatic aquifer. Mass balance calculations accounted for the various groundwater recharge and abstraction sources and sinks in the entire region. The mass balances showed that despite the small surface area covered by the dairy lagoons in this region (0.8%), leachates from lagoons have contributed 6.0% and 12.6% of the total mass of Cl(-) and TN (mainly as NO3(-)-N) added to the aquifer. The chemical composition of the aquifer and vadose zone water suggested that irrigated agricultural activity in the region is the main contributor of Cl(-) and TN to the groundwater. A low spatial correlation between the Cl(-) and NO3(-)-N concentrations in the groundwater and the on-land location of the dairy farms strengthened this assumption, despite the dairy waste lagoon being a point source for groundwater contamination by Cl(-) and NO3(-)-N. Mass balance calculations, for the vadose zone of the entire region, indicated that drying of the lagoons would decrease the regional groundwater salinization process (11% of the total Cl(-) load is stored under lagoons). A more considerable reduction in the groundwater contamination by NO3(-)-N is expected (25% of the NO3(-)-N load is stored under lagoons). Results

Modeling non-steady state radioisotope transport in the vadose zone - A case study using uranium isotopes at Peña Blanca, Mexico

NASA Astrophysics Data System (ADS)

Ku, T. L.; Luo, S.; Goldstein, S. J.; Murrell, M. T.; Chu, W. L.; Dobson, P. F.

2009-10-01

Current models using U- and Th-series disequilibria to study radioisotope transport in groundwater systems mostly consider a steady-state situation. These models have limited applicability to the vadose zone (UZ) where the concentration and migratory behavior of radioisotopes in fluid are often transitory. We present here, as a first attempt of its kind, a model simulating the non-steady state, intermittent fluid transport in vadose layers. It provides quantitative constraints on in-situ migration of dissolved and colloidal radioisotopes in terms of retardation factor and rock-water interaction (or water transit) time. For uranium, the simulation predicts that intermittent flushing in the UZ leads to a linear relationship between reciprocal U concentration and 234U/ 238U ratio in percolating waters, with the intercept and slope bearing information on the rates of dissolution and α-recoil of U isotopes, respectively. The general validity of the model appears to be borne out by the measurement of uranium isotopes in UZ waters collected at various times over a period during 1995-2006 from a site in the Peña Blanca mining district, Mexico, where the Nopal I uranium deposit is located. Enhanced 234U/ 238U ratios in vadose-zone waters resulting from lengthened non-flushing time as prescribed by the model provide an interpretative basis for using 234U/ 238U in cave calcites to reconstruct the regional changes in hydrology and climate. We also provide a theoretical account of the model's potential applications using radium isotopes.

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

USGS Publications Warehouse

Arai, Y.; Marcus, M.A.; Tamura, N.; Davis, J.A.; Zachara, J.M.

2007-01-01

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (???7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-ray fluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO 4]2??8H2O) and uranophane (Ca[UO 2]2[SiO3(OH)]2?? 5H 2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 ??m size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In ??- and bulk-X-ray absorption structure (??-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the ??- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments. ?? 2007 American Chemical Society.

Modeling vadose zone processes during land application of food-processing waste water in California's Central Valley.

PubMed

Miller, Gretchen R; Rubin, Yoram; Mayer, K Ulrich; Benito, Pascual H

2008-01-01

Land application of food-processing waste water occurs throughout California's Central Valley and may be degrading local ground water quality, primarily by increasing salinity and nitrogen levels. Natural attenuation is considered a treatment strategy for the waste, which often contains elevated levels of easily degradable organic carbon. Several key biogeochemical processes in the vadose zone alter the characteristics of the waste water before it reaches the ground water table, including microbial degradation, crop nutrient uptake, mineral precipitation, and ion exchange. This study used a process-based, multi-component reactive flow and transport model (MIN3P) to numerically simulate waste water migration in the vadose zone and to estimate its attenuation capacity. To address the high variability in site conditions and waste-stream characteristics, four food-processing industries were coupled with three site scenarios to simulate a range of land application outcomes. The simulations estimated that typically between 30 and 150% of the salt loading to the land surface reaches the ground water, resulting in dissolved solids concentrations up to sixteen times larger than the 500 mg L(-1) water quality objective. Site conditions, namely the ratio of hydraulic conductivity to the application rate, strongly influenced the amount of nitrate reaching the ground water, which ranged from zero to nine times the total loading applied. Rock-water interaction and nitrification explain salt and nitrate concentrations that exceed the levels present in the waste water. While source control remains the only method to prevent ground water degradation from saline wastes, proper site selection and waste application methods can reduce the risk of ground water degradation from nitrogen compounds.

Vadose Zone Fate and Transport Simulation of Chemicals Associated with Coal Seam Gas Extraction

NASA Astrophysics Data System (ADS)

Simunek, J.; Mallants, D.; Jacques, D.; Van Genuchten, M.

2017-12-01

The HYDRUS-1D and HYDRUS (2D/3D) computer software packages are widely used finite element models for simulating the one-, and two- or three-dimensional movement of water, heat, and multiple solutes in variably-saturated media, respectively. While the standard HYDRUS models consider only the fate and transport of individual solutes or solutes subject to first-order degradation reactions, several specialized HYDRUS add-on modules can simulate far more complex biogeochemical processes. The objective of this presentation is to provide an overview of the HYDRUS models and their add-on modules, and to demonstrate applications of the software to the subsurface fate and transport of chemicals involved in coal seam gas extraction and water management operations. One application uses the standard HYDRUS model to evaluate the natural soil attenuation potential of hydraulic fracturing chemicals and their transformation products in case of an accidental release. By coupling the processes of retardation, first-order degradation and convective-dispersive transport of the biocide bronopol and its degradation products, we demonstrated how natural attenuation reduces initial concentrations by more than a factor of hundred in the top 5 cm of the vadose zone. A second application uses the UnsatChem module to explore the possible use of coal seam gas produced water for sustainable irrigation. Simulations with different irrigation waters (untreated, amended with surface water, and reverse osmosis treated) provided detailed results regarding chemical indicators of soil and plant health, notably SAR, EC and sodium concentrations. A third application uses the coupled HYDRUS-PHREEQC module to analyze trace metal transport involving cation exchange and surface complexation sorption reactions in the vadose zone leached with coal seam gas produced water following some accidental water release scenario. Results show that the main process responsible for trace metal migration is complexation of

Vadose Zone Nitrate Transport Dynamics Resulting from Agricultural Groundwater Banking

NASA Astrophysics Data System (ADS)

Murphy, N. P.; McLaughlin, S.; Dahlke, H. E.

2017-12-01

In recent years, California's increased reliance on groundwater resources to meet agricultural and municipal demands has resulted in significant overdraft and water quality issues. Agricultural groundwater banking (AGB) has emerged as a promising groundwater replenishment opportunity in California; AGB is a form of managed aquifer recharge where farmland is flooded during the winter using excess surface water in order to recharge the underlying groundwater. Suitable farmland that is connected to water delivery systems is available for AGB throughout the Central Valley. However, questions remain how AGB could be implemented on fertilized agricultural fields such that nitrate leaching from the root zone is minimized. Here, we present results from field and soil column studies that investigate the transport dynamics of nitrogen in the root and deeper vadose zone during flooding events. We are specifically interested in estimating how timing and duration of flooding events affect percolation rates, leaching and nitrification/denitrification processes in three soil types within the Central Valley. Laboratory and field measurements include nitrogen (NO3-, NH4+, NO2-, N2O), redox potentials, total organic carbon, dissolved oxygen, moisture content and EC. Soil cores are collected in the field before and after recharge events up to a depth of 4m, while other sensors monitor field conditions continuously. Preliminary results from the three field sites show that significant portions of the applied floodwater (12-62 cm) infiltrated below the root zone: 96.1% (Delhi), 88.6% (Modesto) and 76.8% (Orland). Analysis of the soil cores indicate that 70% of the residual nitrate was flushed from the sandy soil, while the fine sandy loam showed only a 5% loss and in some cores even an increase in soil nitrate (in the upper 20cm). Column experiments support these trends and indicate that increases in soil nitrate in the upper root zone might be due to organic nitrogen mineralization and

Quasi 3D modeling of water flow and solute transport in vadose zone and groundwater

NASA Astrophysics Data System (ADS)

Yakirevich, A.; Kuznetsov, M.; Weisbrod, N.; Pachepsky, Y. A.

2013-12-01

The complexity of subsurface flow systems calls for a variety of concepts leading to the multiplicity of simplified flow models. One commonly used simplification is based on the assumption that lateral flow and transport in unsaturated zone is insignificant unless the capillary fringe is involved. In such cases the flow and transport in the unsaturated zone above groundwater level can be simulated as a 1D phenomenon, whereas through groundwater they are viewed as 2D or 3D phenomena. A new approach for a numerical scheme for 3D variably saturated flow and transport is presented. A Quasi-3D approach allows representing flow in the 'vadose zone - aquifer' system by a series of 1D Richards' equations solved in variably-saturated zone and by 3D-saturated flow equation in groundwater (modified MODFLOW code). The 1D and 3D equations are coupled at the phreatic surface in a way that aquifer replenishment is calculated using the Richards' equation, and solving for the moving water table does not require definition of the specific yield parameter. The 3D advection-dispersion equation is solved in the entire domain by the MT3D code. Using implicit finite differences approximation to couple processes in the vadose zone and groundwater provides mass conservation and increase of computational efficiency. The above model was applied to simulate the impact of irrigation on groundwater salinity in the Alto Piura aquifer (Northern Peru). Studies on changing groundwater quality in arid and semi-arid lands show that irrigation return flow is one of the major factors contributing to aquifer salinization. Existing mathematical models do not account explicitly for the solute recycling during irrigation on a daily scale. Recycling occurs throughout the unsaturated and saturated zones, as function of the solute mass extracted from pumping wells. Salt concentration in irrigation water is calculated at each time step as a function of concentration of both surface water and groundwater

Emerging organic pollutants in the vadose zone of a soil aquifer treatment system: Pore water extraction using positive displacement.

PubMed

Sopilniak, Alexander; Elkayam, Roy; Rossin, Anna Voloshenko; Lev, Ovadia

2018-01-01

Trace organic compounds in effluents, water streams and aquifers are amply reported. However, the mobile pool of Emerging Organic Contaminants (EOCs) in the deep parts of the vadose zone is hard to estimate, due to difficulties in extraction of sufficient quantity of pore water. Here, we present a new methodology for depth profiling of EOCs in pore water by Positive Displacement Extraction (PDE): Pore water extraction from unsaturated soil samples is carried out by withdrawal of soil cores by direct-push drilling and infiltrating the core by organics free water. We show that EOC concentrations in the water eluted in the plateau region of the inverse breakthrough curve is equal to their pore water concentrations. The method was previously validated for DOC extraction, and here the scope of the methodology is extended to pore water extraction for organic pollutants analysis. Method characteristics and validation were carried out with atrazine, simazine, carbamazepine, venlafaxine, O-desmethylvenlafaxine and caffeine in the concentration range of several ng to several μg/liter. Validation was carried out by laboratory experiments on three different soils (sandy, sandy-clayey and clayey). Field studies in the vadose zone of a SAT system provided 27 m deep EOC profiles with less than 1.5 m spatial resolution. During the percolation treatment, carbamazepine remained persistent, while the other studied EOCs were attenuated to the extent of 50-99%.The highest degradation rate of all studied EOCs was in the aerobic zone. EOC levels based on PDE and extraction by centrifugation were compared, showing a positive bias for centrifugation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Vadose Zone and Surficial Monitoring a Controlled Release of Methane in the Borden Aquifer, Ontario.

NASA Astrophysics Data System (ADS)

Forde, O.; Mayer, K. U.; Cahill, A.; Parker, B. L.; Cherry, J. A.

2015-12-01

Development of shale gas resources and potential impacts on groundwater and fugitive gas emissions necessitates further research on subsurface methane gas (CH4) migration and fate. To address this issue, a controlled release experiment is undertaken at the Borden research aquifer, Ontario, Canada. Due to low solubility, it is expected that the injection will lead to gas exsolution and ebullition. Gas migration is expected to extend to the unsaturated zone and towards the ground surface, and may possibly be affected by CH4 oxidation. The project consists of multiple components targeting the saturated zone, unsaturated zone, and gas emissions at the ground surface. This presentation will focus on the analysis of surficial CO2 and CH4 effluxes and vadose zone gas composition to track the temporal and spatial evolution of fugitive gas. Surface effluxes are measured with flux chambers connected to a laser-based gas analyzer, and subsurface gas samples are being collected via monitoring wells equipped with sensors for oxygen, volumetric water content, electrical conductivity, and temperature to correlate with changes in gas composition. First results indicate rapid migration of CH4 to the ground surface in the vicinity of the injection locations. We will present preliminary data from this experiment and evaluate the distribution and rate of gas migration. This research specifically assesses environmental risks associated with fugitive gas emissions related to shale gas resource development.

Deep Vadose Zone Treatability Test for the Hanford Central Plateau: Interim Post-Desiccation Monitoring Results

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Oostrom, Martinus; Strickland, Christopher E.

2013-09-01

A field test of desiccation is being conducted as an element of the deep vadose zone treatability test program. Desiccation technology relies on removal of water from a portion of the subsurface such that the resultant low moisture conditions inhibit downward movement of water and dissolved contaminants. Previously, a field test report (Truex et al. 2012a) was prepared describing the active desiccation portion of the test and initial post-desiccation monitoring data. Additional monitoring data have been collected at the field test site during the post-desiccation period and is reported herein along with interpretation with respect to desiccation performance. This ismore » an interim report including about 2 years of post-desiccation monitoring data.« less

Formation and transport of deethylatrazine in the soil and vadose zone

USGS Publications Warehouse

Adams, C.D.; Thurman, E.M.

1991-01-01

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) and two degradation products were monitored at seven depths in the soil and vadose zone throughout the growing season in two experimental plots in which corn (Zea mays L.) was grown. The soils in these plots were a Kimo silty clay loam (clayey over loamy, montmorillonitic, mesic, Fluvaquentic Hapludoll) and a Eudora silt loam (course, silty, mixed, mesic, Fluventic Hapludoll). The purpose this field study was to identify and quantify the mobile and persistent degradation products of atrazine that comprise the input, or “source term,” to groundwater resulting from the application of atrazine to the soils. The formation of deethylatrazine (2-amino-4-chloro-6-isopropylamino-s-triazine) and deisopropylatrazine (2-amino-4-chloro-6-ethylamino-s-triazine) was monitored at vurious depths using suction lysimeters to determine the relative proportions at which these compounds enter the aquifer. Deethylatrazine was the major degradation product of atrazine identified in the soil water and appeared to enter the underlying aquifer at a concentration of 5.0 µg/L, which was greater than the concentration of atrazine entering the aquifer. Deisopropylatrazine also was detected in the soil water, bnt only in minor concentrations relative to atrazine and deethylatrazine. Because deethylatrazine was the major degradation product in the unsaturated zone, the deethylatrazine-to-atrazine ratio (DAR) may be a good indicator of transport of atrazine through the soil. The hypothesis is proposed that the DAR may be used to distinguish point-source from nonpoint-source contamination of an aquifer.

Enhanced vadose zone nitrogen removal by poplar during dormancy.

PubMed

Ausland, Hayden; Ward, Adam; Licht, Louis; Just, Craig

2015-01-01

A pilot-scale, engineered poplar tree vadose zone system was utilized to determine effluent nitrate (NO3(-)) and ammonium concentrations resulting from intermittent dosing of a synthetic wastewater onto sandy soils at 4.5°C. The synthetic wastewater replicated that of an industrial food processor that irrigates onto sandy soils even during dormancy which can leave groundwater vulnerable to NO3(-) contamination. Data from a 21-day experiment was used to assess various Hydrus model parameterizations that simulated the impact of dormant roots. Bromide tracer data indicated that roots impacted the hydraulic properties of the packed sand by increasing effective dispersion, water content and residence time. The simulated effluent NO3(-) concentration on day 21 was 1.2 mg-N L(-1) in the rooted treatments compared to a measured value of 1.0 ± 0.72 mg-N L(-1). For the non-rooted treatment, the simulated NO3(-) concentration was 4.7 mg-N L(-1) compared to 5.1 ± 3.5 mg-N L(-1) measured on day 21. The model predicted a substantial "root benefit" toward protecting groundwater through increased denitrification in rooted treatments during a 21-day simulation with 8% of dosed nitrogen converted to N2 compared to 3.3% converted in the non-rooted test cells. Simulations at the 90-day timescale provided similar results, indicating increased denitrification in rooted treatments.

Laboratory investigations of the effects of nitrification-induced acidification on Cr cycling in vadose zone material partially derived from ultramafic rocks

USGS Publications Warehouse

Mills, Christopher T.; Goldhaber, Martin B.

2012-01-01

Sacramento Valley (California, USA) soils and sediments have high concentrations of Cr(III) because they are partially derived from ultramafic material. Some Cr(III) is oxidized to more toxic and mobile Cr(VI) by soil Mn oxides. Valley soils typically have neutral to alkaline pH at which Cr(III) is highly immobile. Much of the valley is under cultivation and is both fertilized and irrigated. A series of laboratory incubation experiments were conducted to assess how cultivation might impact Cr cycling in shallow vadose zone material from the valley. The first experiments employed low (7.1 mmol N per kg soil) and high (35 mmol N kg− 1) concentrations of applied (NH4)2SO4. Initially, Cr(VI) concentrations were up to 45 and 60% greater than controls in low and high incubations, respectively. After microbially-mediated oxidation of all NH4+, Cr(VI) concentrations dropped below control values. Increased nitrifying bacterial populations (estimated by measurement of phospholipid fatty acids) may have increased the Cr(VI) reduction capacity of the vadose zone material resulting in the observed decreases in Cr(VI). Another series of incubations employed vadose zone material from a different location to which low (45 meq kg− 1) and high (128 meq kg− 1) amounts of NH4Cl, KCl, and CaCl2 were applied. All treatments, except high concentration KCl, resulted in mean soil Cr(VI) concentrations that were greater than the control. High concentrations of water-leachable Ba2 + (mean 38 μmol kg− 1) in this treatment may have limited Cr(VI) solubility. A final set of incubations were amended with low (7.1 mmol N kg− 1) and high (35 mmol N kg− 1) concentrations of commercial liquid ammonium polyphosphate (APP) fertilizer which contained high concentrations of Cr(III). Soil Cr(VI) in the low APP incubations increased to a concentration of 1.8 μmol kg− 1 (5 × control) over 109 days suggesting that Cr(III) added with the APP fertilizer was more

Characterization of Vadose Zone Sediment: Borehole 299-E33-46 Near Tank B-110 in the B-BX-BY Waste Management Area.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serne, R. Jeffrey; Bjornstad, Bruce N.; Gee, Glendon W.

2002-12-15

This report presents vadose sediment characterization data that improves understanding of the nature and extent of past releases in the B tank farm. A vertical borehole, located approximately 15 ft (5 m) from the northeast edge of single-shell tank 241-B-110 was drilled to a total depth of 264.4 ft bgs, the groundwater table was encountered at 255.8 ft bgs. During drilling, a total of 3 two-ft long, 4-inch diameter split-spoon core samples were collected between 10 and 254 ft bgs-an average of every 7.5 ft. Grab samples were collected between these core sample intervals to yield near continuous samples tomore » a depth of 78.3 m (257 ft). Geologic logging occurred after each core segment was emptied into an open plastic container, followed by photographing and sub-sampling for physical and chemical characterization. In addition, 54 out of a total of 120 composite grab samples were opened, sub-sampled, logged, and photographed. Immediately following the geologic examination, the core and selected grab samples were sub-sampled for moisture content, gamma-emission radiocounting, tritium and strontium-90 determinations, total carbon and inorganic carbon content, and 8 M nitric acid extracts (which provide a measure of the total leachable sediment content of contaminants) and one-to-one sediment to water extracts (which provide soil pH, electrical conductivity, cation, and anion data and water soluble contaminant data. Later, additional aliquots of selected sleeves or grab samples were removed to measure particle size distribution and mineralogy and to squeeze porewater. Major conclusions follow. Vadose zone contamination levels were lower than generally anticipated prior to the initiation of the field investigation. Strong evidence of extensive vadose zone lateral migration in WMA BBXBY exists. There are indications that such lateral migration may have extended into WMA B-BX-BY from adjacent past practice discharge sites. Ponding of runoff from natural precipitation

Seasonal Variability in Vadose zone biodegradation at a crude oil pipeline rupture site

USGS Publications Warehouse

Sihota, Natasha J.; Trost, Jared J.; Bekins, Barbara; Berg, Andrew M.; Delin, Geoffrey N.; Mason, Brent E.; Warren, Ean; Mayer, K. Ulrich

2016-01-01

Understanding seasonal changes in natural attenuation processes is critical for evaluating source-zone longevity and informing management decisions. The seasonal variations of natural attenuation were investigated through measurements of surficial CO2 effluxes, shallow soil CO2 radiocarbon contents, subsurface gas concentrations, soil temperature, and volumetric water contents during a 2-yr period. Surficial CO2 effluxes varied seasonally, with peak values of total soil respiration (TSR) occurring in the late spring and summer. Efflux and radiocarbon data indicated that the fractional contributions of natural soil respiration (NSR) and contaminant soil respiration (CSR) to TSR varied seasonally. The NSR dominated in the spring and summer, and CSR dominated in the fall and winter. Subsurface gas concentrations also varied seasonally, with peak values of CO2 and CH4 occurring in the fall and winter. Vadose zone temperatures and subsurface CO2 concentrations revealed a correlation between contaminant respiration and temperature. A time lag of 5 to 7 mo between peak subsurface CO2 concentrations and peak surface efflux is consistent with travel-time estimates for subsurface gas migration. Periods of frozen soils coincided with depressed surface CO2 effluxes and elevated CO2 concentrations, pointing to the temporary presence of an ice layer that inhibited gas transport. Quantitative reactive transport simulations demonstrated aspects of the conceptual model developed from field measurements. Overall, results indicated that source-zone natural attenuation (SZNA) rates and gas transport processes varied seasonally and that the average annual SZNA rate estimated from periodic surface efflux measurements is 60% lower than rates determined from measurements during the summer.

Measuring Spatial Variability of Vapor Flux to Characterize Vadose-zone VOC Sources: Flow-cell Experiments

DOE PAGES

Mainhagu, Jon; Morrison, C.; Truex, Michael J.; ...

2014-08-05

A method termed vapor-phase tomography has recently been proposed to characterize the distribution of volatile organic contaminant mass in vadose-zone source areas, and to measure associated three-dimensional distributions of local contaminant mass discharge. The method is based on measuring the spatial variability of vapor flux, and thus inherent to its effectiveness is the premise that the magnitudes and temporal variability of vapor concentrations measured at different monitoring points within the interrogated area will be a function of the geospatial positions of the points relative to the source location. A series of flow-cell experiments was conducted to evaluate this premise. Amore » well-defined source zone was created by injection and extraction of a non-reactive gas (SF6). Spatial and temporal concentration distributions obtained from the tests were compared to simulations produced with a mathematical model describing advective and diffusive transport. Tests were conducted to characterize both areal and vertical components of the application. Decreases in concentration over time were observed for monitoring points located on the opposite side of the source zone from the local–extraction point, whereas increases were observed for monitoring points located between the local–extraction point and the source zone. We found that the results illustrate that comparison of temporal concentration profiles obtained at various monitoring points gives a general indication of the source location with respect to the extraction and monitoring points.« less

CO2 migration in the vadose zone: experimental and numerical modelling of controlled gas injection

NASA Astrophysics Data System (ADS)

gasparini, andrea; credoz, anthony; grandia, fidel; garcia, david angel; bruno, jordi

2014-05-01

The mobility of CO2 in the vadose zone and its subsequent transfer to the atmosphere is a matter of concern in the risk assessment of the geological storage of CO2. In this study the experimental and modelling results of controlled CO2 injection are reported to better understanding of the physical processes affecting CO2 and transport in the vadose zone. CO2 was injected through 16 micro-injectors during 49 days of experiments in a 35 m3 experimental unit filled with sandy material, in the PISCO2 facilities at the ES.CO2 centre in Ponferrada (North Spain). Surface CO2 flux were monitored and mapped periodically to assess the evolution of CO2 migration through the soil and to the atmosphere. Numerical simulations were run to reproduce the experimental results, using TOUGH2 code with EOS7CA research module considering two phases (gas and liquid) and three components (H2O, CO2, air). Five numerical models were developed following step by step the injection procedure done at PISCO2. The reference case (Model A) simulates the injection into a homogeneous soil(homogeneous distribution of permeability and porosity in the near-surface area, 0.8 to 0.3 m deep from the atmosphere). In another model (Model B), four additional soil layers with four specific permeabilities and porosities were included to predict the effect of differential compaction on soil. To account for the effect of higher soil temperature, an isothermal simulation called Model C was also performed. Finally, the assessment of the rainfall effects (soil water saturation) on CO2 emission on surface was performed in models called Model D and E. The combined experimental and modelling approach shows that CO2 leakage in the vadose zone quickly comes out through preferential migration pathways and spots with the ranges of fluxes in the ground/surface interface from 2.5 to 600 g·m-2·day-1. This gas channelling is mainly related to soil compaction and climatic perturbation. This has significant implications to

Parallel inversion of a massive ERT data set to characterize deep vadose zone contamination beneath former nuclear waste infiltration galleries at the Hanford Site B-Complex (Invited)

NASA Astrophysics Data System (ADS)

Johnson, T.; Rucker, D. F.; Wellman, D.

2013-12-01

The Hanford Site, located in south-central Washington, USA, originated in the early 1940's as part of the Manhattan Project and produced plutonium used to build the United States nuclear weapons stockpile. In accordance with accepted industrial practice of that time, a substantial portion of relatively low-activity liquid radioactive waste was disposed of by direct discharge to either surface soil or into near-surface infiltration galleries such as cribs and trenches. This practice was supported by early investigations beginning in the 1940s, including studies by Geological Survey (USGS) experts, whose investigations found vadose zone soils at the site suitable for retaining radionuclides to the extent necessary to protect workers and members of the general public based on the standards of that time. That general disposal practice has long since been discontinued, and the US Department of Energy (USDOE) is now investigating residual contamination at former infiltration galleries as part of its overall environmental management and remediation program. Most of the liquid wastes released into the subsurface were highly ionic and electrically conductive, and therefore present an excellent target for imaging by Electrical Resistivity Tomography (ERT) within the low-conductivity sands and gravels comprising Hanford's vadose zone. In 2006, USDOE commissioned a large scale surface ERT survey to characterize vadose zone contamination beneath the Hanford Site B-Complex, which contained 8 infiltration trenches, 12 cribs, and one tile field. The ERT data were collected in a pole-pole configuration with 18 north-south trending lines, and 18 east-west trending lines ranging from 417m to 816m in length. The final data set consisted of 208,411 measurements collected on 4859 electrodes, covering an area of 600m x 600m. Given the computational demands of inverting this massive data set as a whole, the data were initially inverted in parts with a shared memory inversion code, which

Implementation of Solute Transport in the Vadose Zone into the `HYDRUS Package for MODFLOW'

NASA Astrophysics Data System (ADS)

Simunek, J.; Beegum, S.; Szymkiewicz, A.; Sudheer, K. P.

2017-12-01

The 'HYDRUS package for MODFLOW' was developed by Seo et al. (2007) and Twarakavi et al. (2008) to simultaneously evaluate transient water flow in both unsaturated and saturated zones. The package, which is based on the HYDRUS-1D model (Šimůnek et al., 2016) simulating unsaturated water flow in the vadose zone, was incorporated into MODFLOW (Harbaugh et al., 2000) simulating saturated groundwater flow. The HYDRUS package in the coupled model can be used to represent the effects of various unsaturated zone processes, including infiltration, evaporation, root water uptake, capillary rise, and recharge in homogeneous or layered soil profiles. The coupled model is effective in addressing spatially-variable saturated-unsaturated hydrological processes at the regional scale, allowing for complex layering in the unsaturated zone, spatially and temporarily variable water fluxes at the soil surface and in the root zone, and with alternating recharge and discharge fluxes (Twarakavi et al., 2008). One of the major limitations of the coupled model was that it could not be used to simulate at the same time solute transport. However, solute transport is highly dependent on water table fluctuations due to temporal and spatial variations in groundwater recharge. This is an important concern when the coupled model is used for analyzing groundwater contamination due to transport through the unsaturated zone. The objective of this study is to integrate the solute transport model (the solute transport part of HYDRUS-1D for the unsaturated zone and MT3DMS (Zheng and Wang, 1999; Zheng, 2009) for the saturated zone) into an existing coupled water flow model. The unsaturated zone component of the coupled model can consider solute transport involving many biogeochemical processes and reactions, including first-order degradation, volatilization, linear or nonlinear sorption, one-site kinetic sorption, two-site sorption, and two-kinetic sites sorption (Šimůnek and van Genuchten, 2008

Newly recognized hosts for uranium in the Hanford Site vadose zone

USGS Publications Warehouse

Stubbs, J.E.; Veblen, L.A.; Elbert, D.C.; Zachara, J.M.; Davis, J.A.; Veblen, D.R.

2009-01-01

Uranium contaminated sediments from the U.S. Department of Energy's Hanford Site have been investigated using electron microscopy. Six classes of solid hosts for uranium were identified. Preliminary sediment characterization was carried out using optical petrography, and electron microprobe analysis (EMPA) was used to locate materials that host uranium. All of the hosts are fine-grained and intergrown with other materials at spatial scales smaller than the analytical volume of the electron microprobe. A focused ion beam (FIB) was used to prepare electron-transparent specimens of each host for the transmission electron microscope (TEM). The hosts were identified as: (1) metatorbernite [Cu(UO2)2(PO4)2??8H2O]; (2) coatings on sediment clasts comprised mainly of phyllosilicates; (3) an amorphous zirconium (oxyhydr)oxide found in clast coatings; (4) amorphous and poorly crystalline materials that line voids within basalt lithic fragments; (5) amorphous palagonite surrounding fragments of basaltic glass; and (6) Fe- and Mn-oxides. These findings demonstrate the effectiveness of combining EMPA, FIB, and TEM to identify solid-phase contaminant hosts. Furthermore, they highlight the complexity of U geochemistry in the Hanford vadose zone, and illustrate the importance of microscopic transport in controlling the fate of contaminant metals in the environment. ?? 2008 Elsevier Ltd.

Observation of flow processes in the vadose zone using ERT on different space and time scales: results, obstacles, and suggestions

NASA Astrophysics Data System (ADS)

Noell, Ursula; Ganz, Christina; Lamparter, Axel; Duijnisveld, Wilhelmus; Bachmann, Jörg

2013-04-01

Electrical resistivity tomography (ERT) observes the flow processes in the vadose zone indirectly. ERT has been used to estimate water flow in different soil types and under different flow conditions using active experiments or monitoring the natural process in many cases. Our experiments in sand and loess soil connected ERT with local soil probing using TDR devices and tensiometers in order to proof the reliability of the ERT inversion results in terms of infiltration velocity. Additionally, a colour tracer was used and sections through the infiltration zones were excavated in order to compare the shape of the dye -stained infiltration zone with the results of the ERT inversion. The data revealed the complicated infiltration pattern with a higher transport velocity in sand and a different shape than expected by classical soil hydraulic models. These results indicate the need for independent observations in order to correctly assess the water storage in the vadose zone with its hydrological consequences, the groundwater recharge and the contamination risk caused by rapid movement of water. ERT can be used for this purpose on different spatial- and time scales but for reliable results various obstacles need to be dealt with. Firstly, the ambiguity of the resistivity because soil resistivity depends on both, soil water content and electrical soil/water conductivity. This obstacle is less severe when the infiltration velocity is investigated, because then only the first onset of resistivity change is interpreted as the water arrival time. Our results show that the arrival of the water front as well as the final infiltration depth can be reliably detected. In contrast, this obstacle is very severe when the amount of water stored is observed using conductive tracer. The problem is not critical during a passive experiment when the natural rain fall and the waters fate through the vadose zone is monitored. The second obstacle is the limited resolution of ERT which

Transport Studies at the Vadose Zone Research Park, Idaho National Engineering and Environmental Laboratory: Results of Initial Tests

NASA Astrophysics Data System (ADS)

Roback, R. C.; Jones, C. L.; Hull, L. C.; McLing, T. L.; Baker, K. E.; Abdel-Fattah, A. I.; Adams, J. D.; Nichols, E. M.

2003-12-01

The Vadose Zone Research Park (VZRP) provides a unique opportunity to investigate flow and transport in a thick, fractured and layered vadose zone. The VZRP includes two newly constructed percolation ponds each approximately 160000 square ft in area, which receive roughly 1.0 to 1.5 million gallons/day of uncontaminated process water. Monitoring wells and instrumented boreholes surround the percolation ponds. These are distributed in nested sets that allow continuous monitoring and sample collection along two important hydrologic contacts; one located at roughly 60' bls along a contact between alluvium and basalt and the other at 125' bls, along a sedimentary interbed in basalt. Both of these contacts support perched water zones. Hydraulic data have been collected nearly continuously since the first use of the percolation ponds in August 2002. Samples for geochemical studies were also collected during the first few weeks of discharge to the south pond to observe geochemical trends during initial wetting of the subsurface. During the summer of 2003, two tracer tests were performed. The first test consisted of injecting a conservative tracer (2,4,5-trifluorobenzoic acid) into the south pond, which had been receiving water for almost 10 months prior and for which hydraulic data indicated a steady state hydraulic system. The second tracer test was conducted in the north pond and consisted of simultaneous injection of two conservative tracers with different diffusion coefficients (2,4-difluorobenzoic acid, and Br- ion). Tracer injection coincided with the switching of water from the south to the north pond, which had been dry for 10 months prior. Thus, this test afforded us the opportunity to evaluate transport behavior in a relatively dry vadose zone, and to compare this to observed transport behavior under the earlier steady state, more saturated flow condition. Results from the first tracer test show tracer breakthrough in a shallow well, close to the south pond

System-Scale Model of Aquifer, Vadose Zone, and River Interactions for the Hanford 300 Area - Application to Uranium Reactive Transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rockhold, Mark L.; Bacon, Diana H.; Freedman, Vicky L.

2013-10-01

This report represents a synthesis and integration of basic and applied research into a system-scale model of the Hanford 300 Area groundwater uranium plume, supported by the U.S. Department of Energy’s Richland Operations (DOE-RL) office. The report integrates research findings and data from DOE Office of Science (DOE-SC), Office of Environmental Management (DOE-EM), and DOE-RL projects, and from the site remediation and closure contractor, Washington Closure Hanford, LLC (WCH). The three-dimensional, system-scale model addresses water flow and reactive transport of uranium for the coupled vadose zone, unconfined aquifer, and Columbia River shoreline of the Hanford 300 Area. The system-scale modelmore » of the 300 Area was developed to be a decision-support tool to evaluate processes of the total system affecting the groundwater uranium plume. The model can also be used to address “what if” questions regarding different remediation endpoints, and to assist in design and evaluation of field remediation efforts. For example, the proposed cleanup plan for the Hanford 300 Area includes removal, treatment, and disposal of contaminated sediments from known waste sites, enhanced attenuation of uranium hot spots in the vadose and periodically rewetted zone, and continued monitoring of groundwater with institutional controls. Illustrative simulations of polyphosphate infiltration were performed to demonstrate the ability of the system-scale model to address these types of questions. The use of this model in conjunction with continued field monitoring is expected to provide a rigorous basis for developing operational strategies for field remediation and for defining defensible remediation endpoints.« less

Numerical model of water flow in a fractured basalt vadose zone: Box Canyon Site, Idaho

NASA Astrophysics Data System (ADS)

Doughty, Christine

2000-12-01

A numerical model of a fractured basalt vadose zone has been developed on the basis of the conceptual model described by Faybishenko et al. [[his issue]. The model has been used to simulate a ponded infiltration test in order to investigate infiltration through partially saturated fractured basalt. A key question addressed is how the fracture pattern geometry and fracture connectivity within a single basalt flow of the Snake River Plain basalt affect water infiltration. The two-dimensional numerical model extends from the ground surface to a perched water body 20 m below and uses an unconventional quasi-deterministic approach with explicit but highly simplified representation of major fractures and other important hydrogeologic features. The model adequately reproduces the majority of the field observation and provides insights into the infiltration process that cannot be obtained by data collection alone, demonstrating its value as a component of field studies.

Linking carbon and hydrologic fluxes in the critical zone: Observations from high-frequency monitoring of a weathered bedrock vadose zone

NASA Astrophysics Data System (ADS)

Tune, A. K.; Druhan, J. L.; Wang, J.; Cargill, S.; Murphy, C.; Rempe, D. M.

2017-12-01

A principle challenge in quantifying feedbacks between continental weathering and atmospheric CO2 is to improve understanding of how biogeochemical processes in the critical zone influence the distribution and mobility of organic and inorganic carbon. In particular, in landscapes characterized by thin soils and heterogeneous weathered and fractured bedrock, little data exist to inform and constrain predictive models for carbon dynamics. Here, we present the results of an intensive water and gas sampling campaign across an 18 m thick, variably saturated argillite weathering profile in the Eel River CZO. We monitor water content in situ and regularly collect samples of freely-draining water, tightly-held water, and gas through wet and dry seasons using a novel Vadose-zone Monitoring System (VMS) consisting of sensors and samplers distributed across a 20 m long inclined borehole. This novel approach facilitates the interception of gas and water during transport across the entire variably saturated weathering profile. The data demonstrate that seasonal changes in saturation control the vertical distribution and mobility of carbon in the fractured critical zone. Concentrations of gaseous CO2, O2, and dissolved organic and inorganic carbon fluctuate significantly and repeatably with seasonal additions of water infiltrating the weathered bedrock. A persistent vertical structure in the concentrations of dissolved phases and gas concentrations broadly corresponds to depths associated with unsaturated, seasonally saturated, and chronically saturated zones. Associated variations in the vertical structure of mineralogy and elemental composition, including solid phase organic carbon content, are observed in core obtained during drilling. Together, our observations indicate significant respiration of organic carbon at depths greater than the base of the soil, and thus motivate further investigation of the role of heterogeneous weathered, bedrock environments, which are needed to

Using vadose zone data and spatial statistics to assess the impact of cultivated land and dairy waste lagoons on groundwater contamination

NASA Astrophysics Data System (ADS)

Baram, S.; Ronen, Z.; Kurtzman, D.; Peeters, A.; Dahan, O.

2013-12-01

Land cultivation and dairy waste lagoons are considered to be nonpoint and point sources of groundwater contamination by chloride (Cl-) and nitrate (NO3-). The objective of this work is to introduce a methodology to assess the past and future impacts of such agricultural activities on regional groundwater quality. The method is based on mass balances and on spatial statistical analysis of Cl- and NO3-concentration distributions in the saturated and unsaturated zones. The method enables quantitative analysis of the relation between the locations of pollution point sources and the spatial variability in Cl- and NO3- concentrations in groundwater. The method was applied to the Beer-Tuvia region, Israel, where intensive dairy farming along with land cultivation has been practiced for over 50 years above the local phreatic aquifer. Mass balance calculations accounted for the various groundwater recharge and abstraction sources and sinks in the entire region. The mass balances showed that leachates from lagoons and the cultivated land have contributed 6.0 and 89.4 % of the total mass of Cl- added to the aquifer and 12.6 and 77.4 % of the total mass of NO3-. The chemical composition of the aquifer and vadose zone water suggested that irrigated agricultural activity in the region is the main contributor of Cl- and NO3- to the groundwater. A low spatial correlation between the Cl- and NO3- concentrations in the groundwater and the on-land location of the dairy farms strengthened this assumption, despite the dairy waste lagoon being a point source for groundwater contamination by Cl- and NO3-. Results demonstrate that analyzing vadose zone and groundwater data by spatial statistical analysis methods can significantly contribute to the understanding of the relations between groundwater contaminating sources, and to assessing appropriate remediation steps.

Development and assessment of an efficient vadose zone module solving the 1D Richards' equation and including root extraction by plants

NASA Astrophysics Data System (ADS)

Varado, N.; Braud, I.; Ross, P. J.

2006-05-01

From the non iterative numerical method proposed by [Ross, P.J., 2003. Modeling soil water and solute transport—fast, simplified numerical solutions. Agronomy Journal 95, 1352-1361] for solving the 1D Richards' equation, an unsaturated zone module for large scale hydrological model is developed by the inclusion of a root extraction module and a formulation of interception. Two root water uptake modules, first proposed by [Lai, C.-T. and Katul, G., 2000. The dynamic role of rott-water uptake in coupling potential to actual transpiration. Adv. Water Res. 23: 427-439; Li, K.Y., De Jong, R. and Boisvert, J.B., 2001. An exponential root-water-uptake model with water stress compensation. J. Hydrol. 252: 189-204], were included as the sink term in the Richards' equation. They express root extraction as a linear function of potential transpiration and take into account water stress and compensation mechanism allowing water to be extracted in wetter layers. The vadose zone module is tested in a systematic way with synthetic data sets covering a wide range of soil characteristics, climate forcing, and vegetation cover. A detailed SVAT model providing an accurate solution of the coupled heat and water transfer in the soil and the surface energy balance is used as a reference. The accuracy of the numerical solution using only the SVAT soil module, and the loss of accuracy when using a potential evapotranspiration instead of solving the energy budget are both investigated. The vadose zone module is very accurate with errors of less than a few percent for cumulative transpiration. Soil evaporation is less accurately simulated as it leads to a systematic underestimation of soil evaporation amounts. The [Lai, C.-T. and Katul, G., 2000. The dynamic role of rott-water uptake in coupling potential to actual transpiration. Adv. Water Res. 23: 427-439] module is not adapted for sandy soils, due to a weakness in the compensation term formulation. When using a potential

Hydrologic and geochemical dynamics of vadose zone recharge in a mantled karst aquifer: Results of monitoring drip waters in Mystery Cave, Minnesota

USGS Publications Warehouse

Doctor, Daniel H.; Alexander, E. Calvin; Jameson, Roy A.; Alexander, Scott C.

2015-01-01

Caves provide direct access to flows through the vadose zone that recharge karst aquifers. Although many recent studies have documented the highly dynamic processes associated with vadose zone flows in karst settings, few have been conducted in mantled karst settings, such as that of southeastern Minnesota. Here we present some results of a long-term program of cave drip monitoring conducted within Mystery Cave, Minnesota. In this study, two perennial ceiling drip sites were monitored between 1997 and 2001. The sites were located about 90 m (300 ft) apart along the same cave passage approximately 18 m (60 ft) below the surface; 7 to 9 m (20 to 30 ft) of loess and 12 m (40 ft) of flat-lying carbonate bedrock strata overlie the cave. Records of drip rate, electrical conductivity, and water temperature were obtained at 15 minute intervals, and supplemented with periodic sampling for major ion chemistry and water stable isotopes. Patterns in flow and geochemistry emerged at each of the two drip sites that were repeated year after year. Although one site responded relatively quickly (within 2-7 hours) to surface recharge events while the other responded more slowly (within 2-5 days), thresholds of antecedent moisture needed to be overcome in order to produce a discharge response at both sites. The greatest amount of flow was observed at both sites during the spring snowmelt period. Rainfall events less than 10 mm (0.4 in) during the summer months generally did not produce a drip discharge response, yet rapid drip responses were observed following intense storm events after periods of prolonged rainfall. The chemical data from both sites indicate that reservoirs of vadose zone water with distinct chemical signatures mixed during recharge events, and drip chemistry returned to a baseline composition during low flow periods. A reservoir with elevated chloride and sulfate concentrations impacts the slow-response drip site with each recharge event, but does not similarly

The Influence of a Rotating Magnetic Field on Solidification from a Traveling Solvent Zone

NASA Technical Reports Server (NTRS)

Gillies, Donald C.

1997-01-01

Application of a high frequency rotating magnetic field (50-400Hz) (RMF) with a strength of the order of 1 mT can be used to influence the fluid flow in an electrically conductive melt. The advantage of the RMF during the traveling solvent zone method for growth of semiconductor materials will be discussed. Preliminary modeling results for cadmium telluride growth from a tellurium solvent zone will be discussed.

Evaluating the role of soil variability on groundwater pollution and recharge at regional scale by integrating a process-based vadose zone model in a stochastic approach

NASA Astrophysics Data System (ADS)

Coppola, Antonio; Comegna, Alessandro; Dragonetti, Giovanna; Lamaddalena, Nicola; Zdruli, Pandi

2013-04-01

Interpreting and predicting the evolution of water resources and soils at regional scale are continuing challenges for natural scientists. Examples include non-point source (NPS) pollution of soil and surface and subsurface water from agricultural chemicals and pathogens, as well as overexploitation of groundwater resources. The presence and build up of NPS pollutants may be harmful for both soil and groundwater resources. The accumulation of salts and trace elements in soils can significantly impact crop productivity, while loading of salts, nitrates, trace elements and pesticides into groundwater supplies can deteriorate a source of drinking and irrigation water. Consequently, predicting the spatial distribution and fate of NPS pollutants in soils at applicative scales is now considered crucial for maintaining the fragile balance between crop productivity and the negative environmental impacts of NPS pollutants, which is a basis of sustainable agriculture. Soil scientists and hydrologists are regularly asked to assist state agencies to understand these critical environmental issues. The most frequent inquiries are related to the development of mathematical models needed for analyzing the impacts of alternative land-use and best management use and management of soil and water resources. Different modelling solutions exist, mainly differing on the role of the vadose zone and its horizontal and vertical variability in the predictive models. The vadose zone (the region from the soil surface to the groundwater surface) is a complex physical, chemical and biological ecosystem that controls the passage of NPS pollutants from the soil surface where they have been deposited or accumulated due to agricultural activities, to groundwater. Physically based distributed hydrological models require the internal variability of the vadose zone be explored at a variety of scales. The equations describing fluxes and storage of water and solutes in the unsaturated zone used in these

ENVIRONMENTALMANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACEMETALS INGROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 ANDOTHER DIVALENT METALS AND RADIONUCLIDES AT ARIDWESTERN DOE SITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

2004-06-15

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface ureamore » hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project.« less

Monitoring and Data Analysis for the Vadose Zone Monitoring System (VZMS), McClellan AFB. Quarterly Status Report (2/20/98 - 5/20/98)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zawislanski, P.T.; Mountford, H.S.Monitoring and Data Analysis; for the Vadose Zone Monitoring System

1998-06-18

This report contains information on field and laboratory work performed between February 20th, 1998 and May 20th, 1998, at site S-7 in IC 34, at McClellan AFB. At this location, a Vadose Zone Monitoring System (VZMS) (LBNL, 1996) is currently being used to collect subsurface data including hydraulic potential, soil gas pressure, moisture content, water chemistry, gas chemistry, and temperature. This report describes: moisture content changes, based on neutron logging; gas-phase VOC concentrations; aqueous-phase VOC concentrations; temperature profiles; and installation of new instrument cluster.

Current challenges in quantifying preferential flow through the vadose zone

NASA Astrophysics Data System (ADS)

Koestel, John; Larsbo, Mats; Jarvis, Nick

2017-04-01

In this presentation, we give an overview of current challenges in quantifying preferential flow through the vadose zone. A review of the literature suggests that current generation models do not fully reflect the present state of process understanding and empirical knowledge of preferential flow. We believe that the development of improved models will be stimulated by the increasingly widespread application of novel imaging technologies as well as future advances in computational power and numerical techniques. One of the main challenges in this respect is to bridge the large gap between the scales at which preferential flow occurs (pore to Darcy scales) and the scale of interest for management (fields, catchments, regions). Studies at the pore scale are being supported by the development of 3-D non-invasive imaging and numerical simulation techniques. These studies are leading to a better understanding of how macropore network topology and initial/boundary conditions control key state variables like matric potential and thus the strength of preferential flow. Extrapolation of this knowledge to larger scales would require support from theoretical frameworks such as key concepts from percolation and network theory, since we lack measurement technologies to quantify macropore networks at these large scales. Linked hydro-geophysical measurement techniques that produce highly spatially and temporally resolved data enable investigation of the larger-scale heterogeneities that can generate preferential flow patterns at pedon, hillslope and field scales. At larger regional and global scales, improved methods of data-mining and analyses of large datasets (machine learning) may help in parameterizing models as well as lead to new insights into the relationships between soil susceptibility to preferential flow and site attributes (climate, land uses, soil types).

Summary of Uranium Solubility Studies in Concrete Waste Forms and Vadose Zone Environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Golovich, Elizabeth C.; Wellman, Dawn M.; Serne, R. Jeffrey

2011-09-30

One of the methods being considered for safely disposing of Category 3 low-level radioactive wastes is to encase the waste in concrete. Concrete encasement would contain and isolate the waste packages from the hydrologic environment and act as an intrusion barrier. The current plan for waste isolation consists of stacking low-level waste packages on a trench floor, surrounding the stacks with reinforced steel, and encasing these packages in concrete. These concrete-encased waste stacks are expected to vary in size with maximum dimensions of 6.4 m long, 2.7 m wide, and 4 m high. The waste stacks are expected to havemore » a surrounding minimum thickness of 15 cm of concrete encasement. These concrete-encased waste packages are expected to withstand environmental exposure (solar radiation, temperature variations, and precipitation) until an interim soil cover or permanent closure cover is installed and to remain largely intact thereafter. Any failure of concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. This report presents the results of investigations elucidating the uranium mineral phases controlling the long-term fate of uranium within concrete waste forms and the solubility of these phases in concrete pore waters and alkaline, circum-neutral vadose zone environments.« less

Transport of europium colloids in vadose zone lysimeters at the semiarid Hanford site.

PubMed

Liu, Ziru; Flury, Markus; Zhang, Z Fred; Harsh, James B; Gee, Glendon W; Strickland, Chris E; Clayton, Ray E

2013-03-05

The objective of this study was to quantify transport of Eu colloids in the vadose zone at the semiarid Hanford site. Eu-hydroxy-carbonate colloids, Eu(OH)(CO3), were applied to the surface of field lysimeters, and migration of the colloids through the sediments was monitored using wick samplers. The lysimeters were exposed to natural precipitation (145-231 mm/year) or artificial irrigation (124-348 mm/year). Wick outflow was analyzed for Eu concentrations, supplemented by electron microscopy and energy-dispersive X-ray analysis. Small amounts of Eu colloids (<1%) were detected in the deepest wick sampler (2.14 m depth) 2.5 months after application and cumulative precipitation of only 20 mm. We observed rapid transport of Eu colloids under both natural precipitation and artificial irrigation; that is, the leading edge of the Eu colloids moved at a velocity of 3 cm/day within the first 2 months after application. Episodic infiltration (e.g., Chinook snowmelt events) caused peaks of Eu in the wick outflow. While a fraction of Eu moved consistent with long-term recharge estimates at the site, the main mass of Eu remained in the top 30 cm of the sediments. This study illustrates that, under field conditions, near-surface colloid mobilization and transport occurred in Hanford sediments.

Pedotransfer functions for isoproturon sorption on soils and vadose zone materials.

PubMed

Moeys, Julien; Bergheaud, Valérie; Coquet, Yves

2011-10-01

Sorption coefficients (the linear K(D) or the non-linear K(F) and N(F)) are critical parameters in models of pesticide transport to groundwater or surface water. In this work, a dataset of isoproturon sorption coefficients and corresponding soil properties (264 K(D) and 55 K(F)) was compiled, and pedotransfer functions were built for predicting isoproturon sorption in soils and vadose zone materials. These were benchmarked against various other prediction methods. The results show that the organic carbon content (OC) and pH are the two main soil properties influencing isoproturon K(D) . The pedotransfer function is K(D) = 1.7822 + 0.0162 OC(1.5) - 0.1958 pH (K(D) in L kg(-1) and OC in g kg(-1)). For low-OC soils (OC < 6.15 g kg(-1)), clay and pH are most influential. The pedotransfer function is then K(D) = 0.9980 + 0.0002 clay - 0.0990 pH (clay in g kg(-1)). Benchmarking K(D) estimations showed that functions calibrated on more specific subsets of the data perform better on these subsets than functions calibrated on larger subsets. Predicting isoproturon sorption in soils in unsampled locations should rely, whenever possible, and by order of preference, on (a) site- or soil-specific pedotransfer functions, (b) pedotransfer functions calibrated on a large dataset, (c) K(OC) values calculated on a large dataset or (d) K(OC) values taken from existing pesticide properties databases. Copyright © 2011 Society of Chemical Industry.

Biogeochemical Factors Influencing the Transport and Fate of Colloids and Colloid-Associated Contaminants in the Vadose Zone

NASA Astrophysics Data System (ADS)

Bradford, S. A.

2016-12-01

The vadose zone exhibits large spatial and temporal variability in many physical, chemical, and biological factors that strongly influence the transport and fate of colloids (e.g., microbes, nanoparticles, clays, and dissolved organic matter) and colloid-associated contaminants (e.g., heavy metals, radionuclides, pesticides, and antibiotics). This presentation highlights our research activities to better understand and predict the influence of specific biogeochemical processes on colloid and colloid-facilitated transport. Results demonstrate the sensitivity of colloid transport, retention, release, and clogging to transients in solution chemistry (e.g., ionic strength, pH, cation and anion type, and surfactants), water velocity and saturation, and preferential flow. Mathematical modeling at interface-, pore-, and continuum-scales is shown to be a critical tool to quantify the relative importance and coupling of these biogeochemical factors on colloid and contaminant transport and fate, which otherwise might be experimentally intractable. Existing gaps in knowledge and model limitations are identified.

Effects of agricultural practices and vadose zone stratigraphy on nitrate concentration in ground water in Kansas, USA

USGS Publications Warehouse

Townsend, M.A.; Sleezer, R.O.; Macko, S.A.; ,

1996-01-01

Differences in nitrate-N concentrations in,around water in Kansas can be explained by variations in agricultural practices and vadose-zone stratigraphy. In northwestern Kansas, past use of a local stream for tailwater runoff from irrigation and high fertilizer applications for sugar-beet farming resulted in high nitrate-N concentrations (12-60 mg L-1; in both soil and ground water. Nitrogen isotope values from the soil and ground water range from +4 to +8? which is typical for a fertilizer source. In parts of south-central Kansas, the use of crop rotation and the presence of both continuous fine-textured layers and a reducing ground-water chemistry resulted in ground-water nitrate-N values of 10 mg L-1; in both soil and grounwater. Nitrogen isotope values of +3 to +7? indicate a fertilizer source. Crop rotation decreased nitrate-N values in the shallow ground water (9 m). However, deeper ground water showed increasing nitrate-N concentrations as a result of past farming practices.

Quantifying Seasonal Dynamic Water Storage in a Fractured Bedrock Vadose Zone With Borehole Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Schmidt, L.; Minton, B.; Soto-Kerans, N.; Rempe, D.; Heidari, Z.

2017-12-01

In many uplands landscapes, water is transiently stored in the weathered and fractured bedrock that underlies soils. The timing and spatial pattern of this "rock moisture" has strong implications for ecological and biogeochemical processes that influence global cycling of water and solutes. However, available technologies for direct monitoring of rock moisture are limited. Here, we quantify temporal and spatial changes in rock moisture at the field scale across thick (up to 20 m) fractured vadose zone profiles using a novel narrow diameter borehole nuclear magnetic resonance system (BNMR). Successive BNMR surveys were performed using the Vista Clara Inc. Dart system in a network of boreholes within two steep, intensively hydrologically monitored hillslopes associated with the Eel River Critical Zone Observatory (ERCZO) in Northern California. BNMR data showed agreement with estimates of the temporal and spatial pattern of rock moisture depletion over the dry season via downhole neutron and gamma density surveys, as well as permanently installed continuous time domain reflectometry. Observable shifts in the BNMR-derived T2 distribution over time provide a direct measure of changes in the amount of water held within different pore sizes (large vs. small) in fractured rock. Analysis of both BNMR and laboratory-scale NMR (using a 2MHz benchtop NMR spectrometer) measurements of ERCZO core samples at variable saturation suggest that rock moisture changes associated with summer depletion occur within both large (fracture) and small (matrix) pore sizes. Collectively, our multi-method field- and laboratory- scale measurements highlight the potential for BNMR to improve quantification of rock moisture storage for better understanding of the biogeochemical and ecohydrological implications of rock moisture circulation in the Critical Zone.

Remediation of Uranium in the Hanford Vadose Zone Using Gas-Transported Reactants: Laboratory Scale Experiments in Support of the Deep Vadose Zone Treatability Test Plan for the Hanford Central Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; Truex, Michael J.; Zhong, Lirong

2010-01-04

This laboratory-scale investigation is focused on decreasing mobility of uranium in subsurface contaminated sediments in the vadose zone by in situ geochemical manipulation at low water content. This geochemical manipulation of the sediment surface phases included reduction, pH change (acidic and alkaline), and additions of chemicals (phosphate, ferric iron) to form specific precipitates. Reactants were advected into 1-D columns packed with Hanford 200 area U-contaminated sediment as a reactive gas (for CO2, NH3, H2S, SO2), with a 0.1% water content mist (for NaOH, Fe(III), HCl, PO4) and with a 1% water content foam (for PO4). Uranium is present in themore » sediment in multiple phases that include (in decreasing mobility): aqueous U(VI) complexes, adsorbed U, reduced U(IV) precipitates, rind-carbonates, total carbonates, oxides, silicates, phosphates, and in vanadate minerals. Geochemical changes were evaluated in the ability to change the mixture of surface U phases to less mobile forms, as defined by a series of liquid extractions that dissolve progressively less soluble phases. Although liquid extractions provide some useful information as to the generalized uranium surface phases (and are considered operational definitions of extracted phases), positive identification (by x-ray diffraction, electron microprobe, other techniques) was also used to positively identify U phases and effects of treatment. Some of the changes in U mobility directly involve U phases, whereas other changes result in precipitate coatings on U surface phases. The long-term implication of the U surface phase changes to alter U mass mobility in the vadose zone was then investigated using simulations of 1-D infiltration and downward migration of six U phases to the water table. In terms of the short-term decrease in U mobility (in decreasing order), NH3, NaOH mist, CO2, HCl mist, and Fe(III) mist showed 20% to 35% change in U surface phases. Phosphate addition (mist or foam advected

VAPOR-PHASE TRANSPORT OF TRICHLOROETHENE IN AN INTERMEDIATE-SCALE VADOSE-ZONE SYSTEM: RETENTION PROCESSES AND TRACER-BASED PREDICTION

PubMed Central

Costanza-Robinson, Molly S.; Carlson, Tyson D.; Brusseau, Mark L.

2013-01-01

Gas-phase miscible-displacement experiments were conducted using a large weighing lysimeter to evaluate retention processes for volatile organic compounds (VOCs) in water-unsaturated (vadoze-zone) systems, and to test the utility of gas-phase tracers for predicting VOC retardation. Trichloroethene (TCE) served as a model VOC, while trichlorofluoromethane (CFM) and heptane were used as partitioning tracers to independently characterize retention by water and the air-water interface, respectively. Retardation factors for TCE ranged between 1.9 and 3.5, depending on water content. The results indicate that dissolution into the bulk water was the primary retention mechanism for TCE under all conditions studied, contributing approximately two thirds of the total measured retention. Accumulation at the air-water interface comprised a significant fraction of the observed retention for all experiments, with an average contribution of approximately 24%. Sorption to the solid phase contributed approximately 10% to retention. Water contents and air-water interfacial areas estimated based on the CFM and heptane tracer data, respectively, were similar to independently measured values. Retardation factors for TCE predicted using the partitioning-tracer data were in reasonable agreement with the measured values. These results suggest that gas-phase tracer tests hold promise for characterizing the retention and transport of VOCs in the vadose-zone. PMID:23333418

Vadose zone dynamics governing snowmelt infiltration and groundwater recharge in a seasonally frozen, semi-arid landscape

NASA Astrophysics Data System (ADS)

Mohammed, A.; LeBlanc, F.; Cey, E. E.; Hayashi, M.

2016-12-01

Snowmelt infiltration and vadose zone fluxes in seasonally frozen soils are strongly affected by meteorological and soil moisture dynamics occurring during the preceding fall and winter, and complex processes controlling soil hydraulic and thermal regimes. In order to predict their effects on hydrologic processes such as run-off generation, groundwater recharge and plant-water availability in cold regions, an improved understanding of the mechanisms governing coupled water and heat fluxes in the unsaturated zone is needed. Field and laboratory studies were conducted to investigate snowmelt infiltration and groundwater recharge through partially frozen ground over a range of climate and soil conditions in the Canadian Prairies. Meteorological and subsurface field measurements at three sites were combined with laboratory infiltration experiments on frozen undisturbed soil-columns to provide insights into the hydraulic and thermal processes governing water movement. Analysis reveals that antecedent moisture content and thermal profiles both strongly affect subsurface dynamics during infiltration of snowmelt. Preferential flow is also a critical parameter, as both thermal and hydraulic responses were observed at depth prior to complete ground thaw in the field; as well as drainage outflow from the frozen soil column experiments under certain conditions. Results indicate that both diffuse (matrix) and preferential (macropore) flow play significant roles in the infiltration and redistribution of snowmelt water under frozen soil conditions, and shallow groundwater recharge. This study highlights the critical subsurface factors and processes that control infiltration and groundwater recharge in these seasonally frozen landscapes.

Superfund Record of Decision (EPA Region 9): El Toro Marine Corps Air Station, Operable Unit 2A (Site 24-VOC source area vadose zone), El Toro, CA, September 29, 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

This Interim Record of Decision (ROD) presents the selected remedial action for vadose zone soil at Site 24 at Marine Corps Air Station (MCAS) El Toro, located in El Toro, California. The selected remedy for remediation of soil at Site 24 is soil vapor extraction (SVE), the US EPA presumptive remedy for VOC-contaminated soil. The process uses a vacuum to pull VOC-contaminated vapors from the soil through SVE wells.

Vadose zone monitoring strategies to control water flux dynamics and changes in soil hydraulic properties.

NASA Astrophysics Data System (ADS)

Valdes-Abellan, Javier; Jiménez-Martínez, Joaquin; Candela, Lucila

2013-04-01

For monitoring the vadose zone, different strategies can be chosen, depending on the objectives and scale of observation. The effects of non-conventional water use on the vadose zone might produce impacts in porous media which could lead to changes in soil hydraulic properties, among others. Controlling these possible effects requires an accurate monitoring strategy that controls the volumetric water content, θ, and soil pressure, h, along the studied profile. According to the available literature, different monitoring systems have been carried out independently, however less attention has received comparative studies between different techniques. An experimental plot of 9x5 m2 was set with automatic and non-automatic sensors to control θ and h up to 1.5m depth. The non-automatic system consisted of ten Jet Fill tensiometers at 30, 45, 60, 90 and 120 cm (Soil Moisture®) and a polycarbonate access tube of 44 mm (i.d) for soil moisture measurements with a TRIME FM TDR portable probe (IMKO®). Vertical installation was carefully performed; measurements with this system were manual, twice a week for θ and three times per week for h. The automatic system composed of five 5TE sensors (Decagon Devices®) installed at 20, 40, 60, 90 and 120 cm for θ measurements and one MPS1 sensor (Decagon Devices®) at 60 cm depth for h. Installation took place laterally in a 40-50 cm length hole bored in a side of a trench that was excavated. All automatic sensors hourly recorded and stored in a data-logger. Boundary conditions were controlled with a volume-meter and with a meteorological station. ET was modelled with Penman-Monteith equation. Soil characterization include bulk density, gravimetric water content, grain size distribution, saturated hydraulic conductivity and soil water retention curves determined following laboratory standards. Soil mineralogy was determined by X-Ray difractometry. Unsaturated soil hydraulic parameters were model-fitted through SWRC-fit code and

ENVIRONMENTAL MANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACE METALS IN GROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 AND OTHER DIVALENT METALS AND RADIONUCLIDES AT ARID WESTERN DOE SITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

2004-06-15

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface ureamore » hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project.« less

Vapor-phase interactions and diffusion of organic solvents in the unsaturated zone

USGS Publications Warehouse

Roy, W.R.; Griffin, R.A.

1990-01-01

This article presents an analysis of the interactions and static movement of 37 organic solvents as vapors through the unsaturated soil zone. The physicochemical interactions of the organic vapors with unsaturated soil materials were emphasized with focus on diffusive, and adsorptive interactions. Fick's Law and porous media diffusion coefficients for most of the solvent vapors were either compiled or estimated; coefficients were not available for some of the fluorinated solvents. The adsorption of some of the solvent vapors by silica was concluded to be due to hydrogen bond formation with surface silanol groups. Heats of adsorption data for different adsorbents were also compiled. There were very few data on the adsorption of these solvent vapors by soils, but it appears that the magnitude of adsorption of nonpolar solvents is reduced as the relative humidity of the vapor-solid system is increased. Consequently, the interaction of the vapors may then separated into two processes; (1) gas-water partitioning described by Henry's Law constants, and (2) solid-water adsorption coefficients which may be estimated from liquid-solid partition coefficients (Kd values). ?? 1990 Springer-Verlag New York Inc.

Sr-90 Immobilization by Infiltration of a Ca-Citrate-PO4 Solution into the Hanford 100-N Area Vadose Zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, Jim E.; Fruchter, Jonathan S.; Burns, Carolyn A.

This project was initiated to develop a strategy for infiltration of a Ca-citrate-PO4 solution in order to precipitate apatite [Ca6(PO4)10(OH)2] in desired locations in the vadose zone for Sr-90 remediation. Laboratory experiments have demonstrated that infiltration of a Ca-citrate-PO4 solution into sediments at low and high water saturation results in citrate biodegradation and formation of apatite. The citrate biodegradation rate was relatively uniform, in spite of the spatial variability of sediment microbial biomass, likely because of microbial transport processes that occur during solution infiltration. The precipitate was characterized as hydroxyapatite, and the Sr-90 substitution into apatite was shown to havemore » a half-life of 5.5 to 16 months. 1-D and 2-D laboratory infiltration experiments quantified the spatial distribution of apatite that formed during solution infiltration. Slow infiltration in 2-D experiments at low water saturation show the apatite precipitate concentrated in the upper third of the infiltration zone. More rapid 1-D infiltration studies show the apatite precipitate concentrated at greater depth.« less

Electrical Resistivity Tomography monitoring reveals groundwater storage in a karst vadose zone

NASA Astrophysics Data System (ADS)

Watlet, A.; Kaufmann, O.; Van Camp, M. J.; Triantafyllou, A.; Cisse, M. F.; Quinif, Y.; Meldrum, P.; Wilkinson, P. B.; Chambers, J. E.

2016-12-01

Karst systems are among the most difficult aquifers to characterize, due to their high heterogeneity. In particular, temporary groundwater storage that occurs in the unsaturated zone and the discharge to deeper layers are difficult processes to identify and estimate with in-situ measurements. Electrical Resistivity Tomography (ERT) monitoring is meant to track changes in the electrical properties of the subsurface and has proved to be applicable to evidence and quantify hydrological processes in several types of environments. Applied to karst systems, it has particularly highlighted the challenges in linking electrical resistivity changes to groundwater content with usual approaches of petrophysical relationships, given the high heterogeneity of the subsurface. However, taking up the challenge, we undertook an ERT monitoring at the Rochefort Cave Laboratory (Belgium) lasting from Spring 2014 to Winter 2016. This includes 3 main periods of several months with daily measurements, from which seasonal groundwater content changes in the first meters of the vadose zone were successfully imaged. The monitoring concentrates on a 48 electrodes profile that goes from a limestone plateau to the bottom of a sinkhole. 3D UAV photoscans of the surveyed sinkhole and of the main chamber of the nearby cave were performed. Combined with lithological observations from a borehole drilled next to the ERT profile, the 3D information made it possible to project karstified layers visible in the cave to the surface and assess their potential locations along the ERT profile. Overall, this helped determining more realistic local petrophysical properties in the surveyed area, and improving the ERT data inversion by adding structural constraints. Given a strong air temperature gradient in the sinkhole, we also developed a new approach of temperature correction of the raw ERT data. This goes through the solving (using pyGIMLI package) of the 2D ground temperature field and its temporal

Vapor Intrusion Estimation Tool for Unsaturated Zone Contaminant Sources. User’s Guide

DTIC Science & Technology

2016-08-30

324449 Page Intentionally Left Blank iii Executive Summary Soil vapor extraction (SVE) is a prevalent remediation approach for volatile contaminants...strength and location, vadose zone transport, and a model for estimating movement of soil -gas vapor contamination into buildings. The tool may be...framework for estimating the impact of a vadose zone contaminant source on soil gas concentrations and vapor intrusion into a building

Sr-90 Immobilization by Infiltration of a Ca-Citrate-PO{sub 4} Solution into the Hanford 100-N Area Vadose Zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, J.E.; Fruchter, J.S.; Burns, C.A.

This project was initiated to develop a strategy for infiltration of a Ca-citrate-PO{sub 4} solution in order to precipitate apatite [Ca{sub 6}(PO{sub 4}){sub 10}(OH){sub 2}] in desired locations in the vadose zone for Sr-90 remediation. Laboratory experiments have demonstrated that infiltration of a Ca-citrate-PO{sub 4} solution into sediments at low and high water saturation results in citrate biodegradation and formation of apatite. The citrate biodegradation rate was relatively uniform, in spite of the spatial variability of sediment microbial biomass, likely because of microbial transport processes that occur during solution infiltration. The precipitate was characterized as hydroxyapatite, and the Sr-90 substitutionmore » into apatite was shown to have an incorporation half-life of 5.5 to 16 months. One and two dimensional (1-D and 2-D) laboratory infiltration experiments quantified the spatial distribution of apatite that formed during solution infiltration. Slow infiltration in 2-D experiments at low water saturation show the apatite precipitate concentrated in the upper third of the infiltration zone. More rapid 1-D infiltration studies show the apatite precipitate concentrated at greater depth. (authors)« less

Fate of trace organic compounds during vadose zone soil treatment in an onsite wastewater system

USGS Publications Warehouse

Conn, K.E.; Siegrist, R.L.; Barber, L.B.; Meyer, M.T.

2010-01-01

During onsite wastewater treatment, trace organic compounds are often present in the effluents applied to subsurface soils for advanced treatment during vadose zone percolation and groundwater recharge. The fate of the endocrine-disrupting surfactant metabolites 4-nonylphenol (NP), 4-nonylphenolmonoethoxylate (NP1EO), and 4-nonylphenolmonoethoxycarboxylate (NP1EC), metal-chelating agents ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), antimicrobial agent triclosan, stimulant caffeine, and antibiotic sulfamethoxazole during transport through an unsaturated sandy loam soil was studied at a field-scale test site. To assess the effects of effluent quality and hydraulic loading rate (HLR) on compound fate in the soil profile, two effluents (septic tank or textile biofilter) were applied at two design HLRs (2 or 8 cm/d). Chemical concentrations were determined in the two effluents and soil pore water at 60, 120, and 240 cm below the soil infiltrative surface. Concentrations of trace organic compounds in septic tank effluent were reduced by more than 90% during transport through 240 cm (often within 60 cm) of soil, likely due to sorption and biotransformation. However, the concentration of NP increased with depth in the shallow soil profile. Additional treatment of anaerobic septic tank effluent with an aerobic textile biofilter reduced effluent concentrations of many compounds, but generally did not affect any changes in pore water concentrations. The soil profile receiving septic tank effluent (vs. textile biofilter effluent) generally had greater percent removal efficiencies. EDTA, NP, NP1EC, and sulfamethoxazole were measured in soil pore water, indicating the ability of some trace organic compounds to reach shallow groundwater. Risk is highly dependent on the degree of further treatment in the saturated zone and the types and proximity of uses for the receiving groundwater environment. ?? 2009 SETAC.

Fate of trace organic compounds during vadose zone soil treatment in an onsite wastewater system.

PubMed

Conn, Kathleen E; Siegrist, Robert L; Barber, Larry B; Meyer, Michael T

2010-02-01

During onsite wastewater treatment, trace organic compounds are often present in the effluents applied to subsurface soils for advanced treatment during vadose zone percolation and groundwater recharge. The fate of the endocrine-disrupting surfactant metabolites 4-nonylphenol (NP), 4-nonylphenolmonoethoxylate (NP1EO), and 4-nonylphenolmonoethoxycarboxylate (NP1EC), metal-chelating agents ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), antimicrobial agent triclosan, stimulant caffeine, and antibiotic sulfamethoxazole during transport through an unsaturated sandy loam soil was studied at a field-scale test site. To assess the effects of effluent quality and hydraulic loading rate (HLR) on compound fate in the soil profile, two effluents (septic tank or textile biofilter) were applied at two design HLRs (2 or 8 cm/d). Chemical concentrations were determined in the two effluents and soil pore water at 60, 120, and 240 cm below the soil infiltrative surface. Concentrations of trace organic compounds in septic tank effluent were reduced by more than 90% during transport through 240 cm (often within 60 cm) of soil, likely due to sorption and biotransformation. However, the concentration of NP increased with depth in the shallow soil profile. Additional treatment of anaerobic septic tank effluent with an aerobic textile biofilter reduced effluent concentrations of many compounds, but generally did not affect any changes in pore water concentrations. The soil profile receiving septic tank effluent (vs. textile biofilter effluent) generally had greater percent removal efficiencies. EDTA, NP, NP1EC, and sulfamethoxazole were measured in soil pore water, indicating the ability of some trace organic compounds to reach shallow groundwater. Risk is highly dependent on the degree of further treatment in the saturated zone and the types and proximity of uses for the receiving groundwater environment. Copyright 2009 SETAC.

Water, heat, and vapor flow in a deep vadose zone under arid and hyper-arid conditions: a numerical study.

NASA Astrophysics Data System (ADS)

Madi, Raneem; de Rooij, Gerrit H.

2017-04-01

Groundwater recharge in arid regions is notoriously difficult to quantify. One reason is data scarcity: reliable weather records (rainfall, potential evapotranspiration rate, temperature) are typically lacking, the soil properties over the entire extent of the often very deep vadose zone are usually unknown, and the effect of sparse vegetation, wadis, (biological) soil crusts, and hard pans on infiltration and evaporation is difficult to quantify. Another reason is the difficulty of modeling the intricately coupled relevant processes over extended periods of time: coupled flow of liquid water, water vapor, and heat in a very deep soil in view of considerable uncertainty at the soil surface as indicated above, and over large spatial extents. In view of this myriad of problems, we limited ourselves to the simulation of 1-dimensional coupled flow of water, heat, and vapor in an unvegetated deep vadose zone. The conventional parameterizations of the soil hydraulic properties perform poorly under very dry conditions. We therefore selected an alternative that was developed specifically for dry circumstances and modified another to eliminate the physically implausible residual water content that rendered it of limited use for desert environments. The issue of data scarcity was resolved by using numerically generated rainfall records combined with a simple model for annual and daily temperature fluctuations. The soil was uniform, and the groundwater depth was constant at 100 m depth, which provided the lower boundary condition. The geothermal gradient determined the temperature at the groundwater level. We generated two scenarios with 120 years of weather in an arid and a hyper-arid climate. The initial condition was established by first starting with a somewhat arbitrary unit gradient initial condition corresponding to a small fraction of the annual average rainfall and let the model run through the 120-year atmospheric forcing. The resulting profile of matric potential

An analytical solution to assess the SH seismoelectric response of the vadose zone

NASA Astrophysics Data System (ADS)

Monachesi, L. B.; Zyserman, F. I.; Jouniaux, L.

2018-03-01

We derive an analytical solution of the seismoelectric conversions generated in the vadose zone, when this region is crossed by a pure shear horizontal (SH) wave. Seismoelectric conversions are induced by electrokinetic effects linked to relative motions between fluid and porous media. The considered model assumes a one-dimensional soil constituted by a single layer on top of a half space in contact at the water table, and a shearing force located at the earth's surface as the wave source. The water table is an interface expected to induce a seismoelectric interfacial response (IR). The top layer represents a porous rock which porous space is partially saturated by water and air, while the half-space is completely saturated with water, representing the saturated zone. The analytical expressions for the coseismic fields and the interface responses, both electric and magnetic, are derived by solving Pride's equations with proper boundary conditions. An approximate analytical expression of the solution is also obtained, which is very simple and applicable in a fairly broad set of situations. Hypothetical scenarios are proposed to study and analyse the dependence of the electromagnetic fields on various parameters of the medium. An analysis of the approximate solution is also made together with a comparison to the exact solution. The main result of the present analysis is that the amplitude of the interface response generated at the water table is found to be proportional to the jump in the electric current density, which in turn depends on the saturation contrast, poro-mechanical and electrical properties of the medium and on the amplitude of the solid displacement produced by the source. This result is in agreement with the one numerically obtained by the authors, which has been published in a recent work. We also predict the existence of an interface response located at the surface, and that the electric interface response is several orders of magnitude bigger than

An analytical solution to assess the SH seismoelectric response of the vadose zone

NASA Astrophysics Data System (ADS)

Monachesi, L. B.; Zyserman, F. I.; Jouniaux, L.

2018-06-01

We derive an analytical solution of the seismoelectric conversions generated in the vadose zone, when this region is crossed by a pure shear horizontal (SH) wave. Seismoelectric conversions are induced by electrokinetic effects linked to relative motions between fluid and porous media. The considered model assumes a 1D soil constituted by a single layer on top of a half-space in contact at the water table, and a shearing force located at the earth's surface as the wave source. The water table is an interface expected to induce a seismoelectric interfacial response (IR). The top layer represents a porous rock in which porous space is partially saturated by water and air, while the half-space is completely saturated with water, representing the saturated zone. The analytical expressions for the coseismic fields and the interface responses, both electric and magnetic, are derived by solving Pride's equations with proper boundary conditions. An approximate analytical expression of the solution is also obtained, which is very simple and applicable in a fairly broad set of situations. Hypothetical scenarios are proposed to study and analyse the dependence of the electromagnetic fields on various parameters of the medium. An analysis of the approximate solution is also made together with a comparison to the exact solution. The main result of the present analysis is that the amplitude of the interface response generated at the water table is found to be proportional to the jump in the electric current density, which in turn depends on the saturation contrast, poro-mechanical and electrical properties of the medium and on the amplitude of the solid displacement produced by the source. This result is in agreement with the one numerically obtained by the authors, which has been published in a recent work. We also predict the existence of an interface response located at the surface, and that the electric interface response is several orders of magnitude bigger than the

Long-term tillage and crop rotation effects on residual nitrate in the crop root zone and nitrate accumulation in the intermediate vadose zone

USGS Publications Warehouse

Katupitiya, A.; Eisenhauer, D.E.; Ferguson, R.B.; Spalding, R.F.; Roeth, F.W.; Bobier, M.W.

1997-01-01

Tillage influences the physical and biological environment of soil. Rotation of crops with a legume affects the soil N status. A furrow irrigated site was investigated for long-term tillage and crop rotation effects on leaching of nitrate from the root zone and accumulation in the intermediate vadose zone (IVZ). The investigated tillage systems were disk-plant (DP), ridge-till (RT) and slot-plant (SP). These tillage treatments have been maintained on the Hastings silt loam (Udic Argiustoll) and Crete silt loam (Pachic Argiustoll) soils since 1976. Continuous corn (CC) and corn soybean (CS) rotations were the subtreatments. Since 1984, soybeans have been grown in CS plots in even calendar years. All tillage treatments received the same N rate. The N rate varied annually depending on the root zone residual N. Soybeans were not fertilized with N-fertilizer. Samples for residual nitrate in the root zone were taken in 8 of the 15 year study while the IVZ was only sampled at the end of the study. In seven of eight years, root zone residual soil nitrate-N levels were greater with DP than RT and SP. Residual nitrate-N amounts were similar in RT and SP in all years. Despite high residual nitrate-N with DP and the same N application rate, crop yields were higher in RT and SP except when DP had an extremely high root zone nitrate level. By applying the same N rates on all tillage treatments, DP may have been fertilized in excess of crop need. Higher residual nitrate-N in DP was most likely due to a combination of increased mineralization with tillage and lower yield compared to RT and SP. Because of higher nitrate availability with DP, the potential for nitrate leaching from the root zone was greater with DP as compared to the RT and SP tillage systems. Spring residual nitrate-N contents of DP were larger than RT and SP in both crop rotations. Ridge till and SP systems had greater nitrate-N with CS than CC rotations. Nitrate accumulation in IVZ at the upstream end of the

A chaotic-dynamical conceptual model to describe fluid flow and contaminant transport in a fractured vadose zone. 1997 progress report and presentations at the annual meeting, Ernest Orlando Lawrence Berkeley National Laboratory, December 3--4, 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

Faybishenko, B.; Doughty, C.; Geller, J.

1998-07-01

Understanding subsurface flow and transport processes is critical for effective assessment, decision-making, and remediation activities for contaminated sites. However, for fluid flow and contaminant transport through fractured vadose zones, traditional hydrogeological approaches are often found to be inadequate. In this project, the authors examine flow and transport through a fractured vadose zone as a deterministic chaotic dynamical process, and develop a model of it in these terms. Initially, the authors examine separately the geometric model of fractured rock and the flow dynamics model needed to describe chaotic behavior. Ultimately they will put the geometry and flow dynamics together to developmore » a chaotic-dynamical model of flow and transport in a fractured vadose zone. They investigate water flow and contaminant transport on several scales, ranging from small-scale laboratory experiments in fracture replicas and fractured cores, to field experiments conducted in a single exposed fracture at a basalt outcrop, and finally to a ponded infiltration test using a pond of 7 by 8 m. In the field experiments, they measure the time-variation of water flux, moisture content, and hydraulic head at various locations, as well as the total inflow rate to the subsurface. Such variations reflect the changes in the geometry and physics of water flow that display chaotic behavior, which they try to reconstruct using the data obtained. In the analysis of experimental data, a chaotic model can be used to predict the long-term bounds on fluid flow and transport behavior, known as the attractor of the system, and to examine the limits of short-term predictability within these bounds. This approach is especially well suited to the need for short-term predictions to support remediation decisions and long-term bounding studies. View-graphs from ten presentations made at the annual meeting held December 3--4, 1997 are included in an appendix to this report.« less

Field demonstration of foam injection to confine a chlorinated solvent source zone.

PubMed

Portois, Clément; Essouayed, Elyess; Annable, Michael D; Guiserix, Nathalie; Joubert, Antoine; Atteia, Olivier

2018-05-01

A novel approach using foam to manage hazardous waste was successfully demonstrated under active site conditions. The purpose of the foam was to divert groundwater flow, that would normally enter the source zone area, to reduce dissolved contaminant release to the aquifer. During the demonstration, foam was pre generated and directly injected surrounding the chlorinated solvent source zone. Despite the constraints related to the industrial activities and non-optimal position of the injection points, the applicability and effectiveness of the approach have been highlighted using multiple metrics. A combination of measurements and modelling allowed definition of the foam extent surrounding each injection point, and this appears to be the critical metric to define the success of the foam injection approach. Information on the transport of chlorinated solvents in groundwater showed a decrease of contaminant flux by a factor of 4.4 downstream of the confined area. The effective permeability reduction was maintained over a period of three months. The successful containment provides evidence for consideration of the use of foam to improve traditional flushing techniques, by increasing the targeting of contaminants by remedial agents. Copyright © 2018 Elsevier B.V. All rights reserved.

Chromium(VI) generation in vadose zone soils and alluvial sediments of the southwestern Sacramento Valley, California: a potential source of geogenic Cr(VI) to groundwater

USGS Publications Warehouse

Mills, Christopher T.; Morrison, Jean M.; Goldhaber, Martin B.; Ellefsen, Karl J.

2011-01-01

Concentrations of geogenic Cr(VI) in groundwater that exceed the World Health Organization’s maximum contaminant level for drinking water (50 μg L−1) occur in several locations globally. The major mechanism for mobilization of this Cr(VI) at these sites is the weathering of Cr(III) from ultramafic rocks and its subsequent oxidation on Mn oxides. This process may be occurring in the southern Sacramento Valley of California where Cr(VI) concentrations in groundwater can approach or exceed 50 μg L−1. To characterize Cr geochemistry in the area, samples from several soil auger cores (approximately 4 m deep) and drill cores (approximately 25 m deep) were analyzed for total concentrations of 44 major, minor and trace elements, Cr associated with labile Mn and Fe oxides, and Cr(VI). Total concentrations of Cr in these samples ranged from 140 to 2220 mg per kg soil. Between 9 and 70 mg per kg soil was released by selective extractions that target Fe oxides, but essentially no Cr was associated with the abundant reactive Mn oxides (up to ~1000 mg hydroxylamine-reducible Mn per kg soil was present). Both borehole magnetic susceptibility surveys performed at some of the drill core sites and relative differences between Cr released in a 4-acid digestion versus total Cr (lithium metaborate fusion digestion) suggest that the majority of total Cr in the samples is present in refractory chromite minerals transported from ultramafic exposures in the Coast Range Mountains. Chromium(VI) in the samples studied ranged from 0 to 42 μg kg−1, representing a minute fraction of total Cr. Chromium(VI) content was typically below detection in surface soils (top 10 cm) where soil organic matter was high, and increased with increasing depth in the soil auger cores as organic matter decreased. Maximum concentrations of Cr(VI) were up to 3 times greater in the deeper drill core samples than the shallow auger cores. Although Cr(VI) in these vadose zone soils and sediments was only a

Processes and Parameters Controlling the Extent of Methanogenic Conditions in the Unsaturated Zone of a Crude Oil Spill Site

NASA Astrophysics Data System (ADS)

Molins, S.; Mayer, K.

2007-12-01

Gas concentrations measured in the vadose zone at a crude oil spill site near Bemidji, MN, show that a large area near the oil body is currently dominated by methanogenic conditions. Away from the oil body methane concentrations decrease as it is degraded by methanotrophic bacteria under aerobic conditions. Numerical simulations have been conducted to quantify the contributions of the relevant transport and reaction processes to the production and attenuation of methane in the vadose zone. Methane is generated in the vadose zone by anaerobic degradation of oil and is also added by fluxes from the capillary fringe and the saturated zone. Gas diffusion and advection contribute to the transport of methane in the lateral direction and towards the ground surface. Attenuation of methane concentrations occurs through aerobic oxidation in the presence of methanotrophic bacteria. Critical parameters were varied within bounds provided by field data and previous studies. Simulation results confirm that the layered sediment structure present at the site plays a significant role in explaining the observed distribution of gases in the vadose zone. The presence of a low permeability lens in the area upgradient from the source results in higher moisture contents, limiting diffusion of oxygen into the zone of methane production, and contributes to the spread of methane. Diffusion was identified as the most significant transport mechanism for gases in the vadose zone. However, field-observed zones of depleted and enriched N2 and Ar concentrations could only be explained by the development of advective fluxes induced by reactive processes (methanogenesis and methanotrophy). The zones of gas production are characterized by slightly increased total gas pressures and low concentrations of N2 and Ar, while zones of gas consumption show slightly depressed total gas pressures and high concentrations of N2 and Ar. The simulations suggest that the advective flux that develops between these

Trace Metals in Groundwater & the Vadose Zone Calcite: In Situ Containment & Stabilization of Strontium-90 & Other Divalent Metals & Radionuclides at Arid West DOE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Robert W.

2004-12-01

Radionuclide and metal contaminants such as strontium-90 are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center at the Idaho National Engineering and Environmental Laboratory). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., strontium-90) by their facilitated co-precipitation with calcium carbonate in groundwater and vadose zonemore » systems. Our facilitated approach, shown schematically in Figure 1, relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from the aqueous phase over the long-term. Another advantage of the ureolysis approach is that the ammonium ions produced by the reaction can exchange with radionuclides sorbed to subsurface minerals, thereby enhancing the availability of the radionuclides for re-capture in a more stable solid phase (co-precipitation rather than adsorption).« less

Dependence of shear wave seismoelectrics on soil textures: a numerical study in the vadose zone

NASA Astrophysics Data System (ADS)

Zyserman, F. I.; Monachesi, L. B.; Jouniaux, L.

2017-02-01

In this work, we study seismoelectric conversions generated in the vadose zone, when this region is traversed by a pure SH wave. We assume that the soil is a 1-D partially saturated lossy porous medium and we use the van Genuchten's constitutive model to describe the water saturation profile. Correspondingly, we extend Pride's formulation to deal with partially saturated media. In order to evaluate the influence of different soil textures we perform a numerical analysis considering, among other relevant properties, the electrokinetic coupling, coseismic responses and interface responses (IRs). We propose new analytical transfer functions for the electric and magnetic field as a function of the water saturation, modifying those of Bordes et al. and Garambois & Dietrich, respectively. Further, we introduce two substantially different saturation-dependent functions into the electrokinetic (EK) coupling linking the poroelastic and the electromagnetic wave equations. The numerical results show that the electric field IRs markedly depend on the soil texture and the chosen EK coupling model, and are several orders of magnitude stronger than the electric field coseismic ones. We also found that the IRs of the water table for the silty and clayey soils are stronger than those for the sandy soils, assuming a non-monotonous saturation dependence of the EK coupling, which takes into account the charged air-water interface. These IRs have been interpreted as the result of the jump in the viscous electric current density at the water table. The amplitude of the IR is obtained using a plane SH wave, neglecting both the spherical spreading and the restriction of its origin to the first Fresnel zone, effects that could lower the predicted values. However, we made an estimation of the expected electric field IR amplitudes detectable in the field by means of the analytical transfer functions, accounting for spherical spreading of the SH seismic waves. This prediction yields a value

Effectiveness of Hydraulic Parameterization Strategies for Simulating Moisture Dynamics in a Deep Semi-Arid Vadose Zone

NASA Astrophysics Data System (ADS)

Zhang, Y.; Schaap, M. G.

2012-12-01

Over the past fifteen years, the University of Arizona has carried out four controlled infiltration experiments in a 3600 m2, 15 meter deep vadose zone (Maricopa, Arizona) in which the evolution of moisture content (9 wells, 25 cm resolution), and matric potential (27 locations) was monitored and the subsurface stratigraphy, texture (1042 samples), and bulk density (251 samples) was characterized. In order to simulate the subsurface moisture dynamics it is necessary to define the 3D structure of the subsurface hydraulic characteristics (i.e. moisture retention and hydraulic functions). Several simple to complex strategies are possible ranging from stratigraphy based layering using hydraulic parameters derived from core samples to sophisticated numerical inversions based on 3D geostatistics and site-specific pedotransfer functions. A range of approaches will be evaluated on objective metrics that quantify how well the observed moisture dynamics are matched by simulations. We will evaluate the worth of auxiliary data such as observed matric potentials and quantity the number of texture samples needed to arrive at effective descriptions of subsurface structure. In addition, we will discuss more subjective metrics that evaluate the relative effort involved and estimate monetary cost of each method. While some of the results will only be valid for the studied site, some general conclusions will be possible about the effectiveness of particular methods for other semi-arid sites.

Advective removal of intraparticle uranium from contaminated vadose zone sediments, Hanford, U.S.

PubMed

Ilton, Eugene S; Qafoku, Nikolla P; Liu, Chongxuan; Moore, Dean A; Zachara, John M

2008-03-01

A column study on U(VI)-contaminated vadose zone sediments from the Hanford Site, WA, was performed to investigate U(VI) release kinetics with water advection and variable geochemical conditions. The sediments were collected from an area adjacent to and below tank BX-102 that was contaminated as a result of a radioactive tank waste overfill event. The primary reservoir for U(VI) in the sediments are micrometer-size precipitates composed of nanocrystallite aggregates of a Na-U-Silicate phase, most likely Na-boltwoodite, that nucleated and grew within microfractures of the plagioclase component of sand-sized granitic clasts. Two sediment samples, with different U(VI) concentrations and intraparticle mass transfer properties, were leached with advective flows of three different solutions. The influent solutions were all calcite-saturated and in equilibrium with atmospheric CO2. One solution was prepared from DI water, the second was a synthetic groundwater (SGW) with elevated Na that mimicked groundwater at the Hanford site, and the third was the same SGW but with both elevated Na and Si. The latter two solutions were employed, in part, to test the effect of saturation state on U(VI) release. For both sediments, and all three electrolytes, there was an initial rapid release of U(VI) to the advecting solution followed by slower near steady-state release. U(VI)aq concentrations increased during subsequent stop-flow events. The electrolytes with elevated Na and Si depressed U(VL)aq concentrations in effluent solutions. Effluent U(VI)aq concentrations for both sediments and all three electrolytes were simulated reasonably well by a three domain model (the advecting fluid, fractures, and matrix) that coupled U(VI) dissolution, intraparticle U(VI)aq diffusion, and interparticle advection, where diffusion and dissolution properties were parameterized in a previous batch study.

Analysis of Vadose Hydrology at Jinapsan Cave, Guam, Mariana Islands

NASA Astrophysics Data System (ADS)

Bautista, K. K.; Jenson, J. W.; Lander, M.; Noronha, A. L.; Righetti, T.

2016-12-01

Six years of monthly data were analyzed from an active tropical limestone cave in Guam, the southernmost of the Mariana Islands, in the western Pacific Ocean. The purpose of this study was to characterize vadose processes of aquifer recharge in the Plio-Pleistocene Mariana Limestone, which occupies about 75% of the surface of the Northern Guam Lens Aquifer, which produces 90% of the island's drinking water. This hydrogeologic study was conducted concurrent with paleoclimate research, in which correlative data on CO2 and other cave meteorological parameters are also collected. For this study, a ground survey grid was established on the surface above the cave, a vegetated talus slope at the foot of the >150-m cliff in the Mariana Limestone behind the cave. Cave and vadose zone 3-D models were constructed from the surface survey and an interior cave survey. Cross sections display talus slope features (33°), notational talus grain size distribution, inferred epikarst and vadose layer dimensions, cave slope (-34°) and structural and geomorphic features of the cave, including a brackish sea-level pool at the cave bottom. GIS products include georeferenced cave boundary and cave room shapefiles. A plan-view map displays significant boulder talus and limestone forest trees, cave entrance location and the underlying cave boundary and fractures mapped on the cave ceiling. Thicknesses of the talus and vadose bedrock sections range from 1.3 to 17.0 meters and 1.7 to 46.4 meters, respectively. Drip rate and discharge rate data from 7 cave stations are presented in graphs showing varying responses between percolation and changes in rainfall during wet (Jul-Dec) and dry (Jan-Jun) seasons. Three stations exhibited fast responses to wet season rainfall, which gradually dropped during the dry season. Two of these stations are at separate cave ceiling fractures. The third is indiscernible from its distance (>4m) above the floor. Three stations exhibited slow responses in both wet

Characterization and Extraction of Uranium Contamination Perched within the Deep Vadose Zone at the Hanford Site, Washington State

NASA Astrophysics Data System (ADS)

Williams, B. A.; Rohay, V. J.; Benecke, M. W.; Chronister, G. B.; Doornbos, M. H.; Morse, J.

2012-12-01

A highly contaminated perched water zone has been discovered in the deep vadose zone above the unconfined aquifer during drilling of wells to characterize groundwater contamination within the 200 East Area of the U.S. Department of Energy's Hanford Site in southeast Washington. The perched water, which contains nitrate, uranium, and technetium-99 at concentrations that have exceeded 100,000 μg/L, 70,000 μg/L, and 45,000 pCi/L respectively, is providing contamination to the underlying unconfined aquifer. A perched zone extraction well has been installed and is successfully recovering the contaminated perched water as an early remedial measure to reduce impacts to the unconfined aquifer. The integration and interpretation of various borehole hydrogeologic, geochemical, and geophysical data sets obtained during drilling facilitated the delineation of the perching horizon and determination of the nature and extent of the perched contamination. Integration of the borehole geologic and geophysical logs defined the structural elevation and thickness of the perching low permeability silt interval. Borehole geophysical moisture logs, gamma logs, and sample data allowed detailed determination of the elevation and thickness of the oversaturated zone above the perching horizon, and the extent and magnitude of the radiological uranium contamination within the perching interval. Together, these data sets resolved the nature of the perching horizon and the location and extent of the contaminated perched water within the perching zone, allowing an estimation of remaining contaminant extent. The resulting conceptual model indicates that the contaminated perched water is contained within a localized sand lens deposited in a structural low on top of a semi-regional low-permeability silt layer. The top of the sand lens is approximately 72 m (235 ft) below ground surface; the maximum thickness of the sand lens is approximately 3 m (10 ft). The lateral and vertical extent of the

SP Response to a Line Source Infiltration for Characterizing the Vadose Zone: Forward Modeling and Inversion

NASA Astrophysics Data System (ADS)

Sailhac, P.

2004-05-01

Field estimation of soil water flux has direct application for water resource management. Standard hydrologic methods like tensiometry or TDR are often difficult to apply because of the heterogeneity of the subsurface, and non invasive tools like ERT, NMR or GPR are limited to the estimation of the water content. Electrical Streaming Potential (SP) monitoring can provide a cost-effective tool to help estimate the nature of the hydraulic transfers (infiltration or evaporation) in the vadose zone. Indeed this technique has improved during the last decade and has been shown to be a useful tool for quantitative groundwater flow characterization (see the poster of Marquis et al. for a review). We now account for our latest development on the possibility of using SP for estimating hydraulic parameters of unsaturated soils from in situ SP measurements during infiltration experiments. The proposed method consists in SP profiling perpendicularly to a line source of steady-state infiltration. Analytic expressions for the forward modeling show a sensitivity to six parameters: the electrokinetic coupling parameter at saturation CS, the soil sorptive number α , the ratio of the constant source strength to the hydraulic conductivity at saturation q/KS, the soil effective water saturation prior to the infiltration experiment Se0, Mualem parameter m, and Archie law exponent n. In applications, all these parameters could be constrained by inverting electrokinetic data obtained during a series of infiltration experiments with varying source strength q.

USE OF CARBON STABLE ISOTOPE FOR THE DECHLORINATION OF TRICHLOROETHYLENE ON GRANULAR-GRAPHITE PACKED ELECTRODES (PRESENTATION)

EPA Science Inventory

Trichloroethylene (TCE) is widely used as a solvent in metal processing and electronic manufacturing industries, but waste and spilled TCE often results in blocks of non-aqueous liquid in vadose and saturated zones which become continuous contamination sources for groundwater. El...

Parameterization and Modeling of Coupled Heat and Mass Transport in the Vadose Zone

NASA Astrophysics Data System (ADS)

Mohanty, B.; Yang, Z.

2016-12-01

The coupled heat and mass transport in the vadose zone is essentially a multiphysics issue. Addressing this issue appropriately has remarkable impacts on soil physical, chemical and biological processes. To data, most coupled heat and water transport modeling has focused on the interactions between liquid water, water vapor and heat transport in homogeneous and layered soils. Comparatively little work has been done on structured soils where preferential infiltration and evaporation flow occurs. Moreover, the traditional coupled heat and water model usually neglects the nonwetting phase air flow, which was found to be significant in the state-of-the-art modeling framework for coupled heat and water transport investigation. However, the parameterizations for the nonwetting phase air permeability largely remain elusive so far. In order to address the above mentioned limitations, this study aims to develop and validate a predictive multiphysics modeling framework for coupled soil heat and water transport in the heterogeneous shallow subsurface. To this end, the following research work is specifically conducted: (a) propose an improved parameterization to better predict the nonwetting phase relative permeability; (b) determine the dynamics, characteristics and processes of simultaneous soil moisture and heat movement in homogeneous and layered soils; and (c) develop a nonisothermal dual permeability model for heterogeneous structured soils. The results of our studies showed that: (a) the proposed modified nonwetting phase relative permeability models are much more accurate, which can be adopted for better parameterization in the subsequent nonisothermal two phase flow models; (b) the isothermal liquid film flow, nonwetting phase gas flow and liquid-vapor phase change non-equilibrium effects are significant in the arid and semiarid environments (Riverside, California and Audubon, Arizona); and (c) the developed nonisothermal dual permeability model is capable of

Fluid inclusions in vadose cement with consistent vapor to liquid ratios, Pleistocene Miami Limestone, southeastern Florida

USGS Publications Warehouse

Barker, C.E.; Halley, R.B.

1988-01-01

Vadose cements in the Late Pleistocene Miami Limestone contain regions with two-phase aqueous fluid inclusions that have consistent vapor to liquid (V-L) ratios. When heated, these seemingly primary inclusions homogenize to a liquid phase in a range between 75??C and 130??C (mean = 100??C) and have final melting temperatures between -0.3?? and 0.0??C. The original distribution of Th was broadened during measurements because of fluid inclusion reequilibration. The narrow range of Th in these fluid inclusions suggest unusually consistent V-L ratios. They occur with small, obscure, single phase liquid-filled inclusions, which infer a low temperature origin (less than 60??C), and contradict the higher temperature origin implied by the two phase inclusions. The diagenetic environment producing these seemingly primary fluid inclusions can be inferred from the origin of the host calcite enclosing them. The ??18O composition of these cements (-4 to-5.5%., PDB) and the fresh water in the fluid inclusions are consistent with precipitation from low-temperature meteoric water. The carbon-isotope composition of the vadose cements that contain only rare two-phase fluid inclusions are comparable to the host rock matrix (??13C between 0 and +4%., PDB). Cements that contain common two-phase fluid-inclusions have a distinctly lighter carbon isotopic composition of -3 to -5%.. The carbon isotope composition of cements that contain common two-phase inclusions are about 6%. lighter than those of other vadose cements; models of early meteoric diagenesis indicate that this is the result of precipitation from water that has been influenced by soil gas CO2. Our hypothesis is that the primary fluid inclusions, those with consistent V-L ratios and the single-phase liquid inclusions, form at near-surface temperature (25??C) and pressure when consistent proportions of soil gas and meteoric water percolating through the vadose zone are trapped within elongate vacuoles. This study corroborates

Intermittent flux from a sand filter for household wastewater and integrated solute transfer to the vadose zone.

PubMed

Nasri, Behzad; Fouché, Olivier

2018-02-24

Depending on the actual number of soil-based on-site wastewater treatment system (OWTS) in an area, on-site sanitation may be a significant source of pollutants and a threat to groundwater. Even in the case of a system functioning correctly, here, a sand filter substituted for the in-situ soil, as the treated effluent may reach to the water table, it is necessary evaluating in situ how much the sand and underneath soil respectively contribute to pollutant removal. On the plot of a household in a small rural community, the functioning of a real scale OWTS was monitored for 1.5 years. This system, composed of a septic tank connected to a 5 × 5 m 2 and 0.7-m thick aerobic sand filter was equipped with soil hydrodynamic probes (water content and matrix potential) during construction. By using the instantaneous profile method of water content, the intermittent infiltrated flux was determined across the sand-pack according to position and time. Treated water infiltrates into underneath soil acting as post-treatment. Quality of interstitial liquid from the sand and the soil was analysed each month on a 12-h pumping sample obtained through porous plates. Results of water fluxes and concentrations provide an estimate of the annual flux to the vadose zone and groundwater of metals, nutrients and some organic micro-pollutants (parabens and triclosan) through the OWTS and subsoil.

ANALYSIS OF A GAS-PHASE PARTITIONING TRACER TEST CONDUCTED IN AN UNSATURATED FRACTURED-CLAY FORMATION

EPA Science Inventory

The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured-clay system that is the confin...

Understanding the rapidity of subsurface storm flow response from a fracture-oriented shallow vadose through a new perspective

NASA Astrophysics Data System (ADS)

Zhao, Peng; Zhao, Pei; Liang, Chuan; Li, Tianyang; Zhou, Baojia

2017-01-01

Velocity and celerity in hydrologic systems are controlled by different mechanisms. Efforts were made through joint sample collection and the use of hydrographs and tracers to understand the rapidity of the subsurface flow response to rainstorms on hourly time scales. Three deep subsurface flows during four natural rainstorm events were monitored. The results show that (1) deeper discharge was observed early in responding rainfall events and yielded a high hydrograph amplitude; (2) a ratio index, k, reflecting the dynamic change of the rainfall perturbation intensity in subsurface flow, might reveal inner causal relationships between the flow index and the tracer signal index. Most values of k were larger than 1 at the perturbation stage but approximated 1 at the no-perturbation stage; and (3) for statistical analysis of tracer signals in subsurface flows, the total standard deviation was 17.2, 11.9, 7.4 and 3.5 at perturbation stages and 4.4, 2.5, 1.1, and 0.95 at the non-perturbation stage for observed events. These events were 3-7 times higher in the former rather than the later, reflecting that the variation of tracer signals primarily occurred under rainfall perturbation. Thus, we affirmed that the dynamic features of rainfall have a key effect on rapid processes because, besides the gravity, mechanical waves originating from dynamic rainfall features are another driving factor for conversion between different types of rainfall mechanical energy. A conceptual model for pressure wave propagation was proposed, in which virtual subsurface flow processes in a heterogeneous vadose zone under rainfall are analogous to the water hammer phenomenon in complex conduit systems. Such an analogy can allow pressure in a shallow vadose to increase and decrease and directly influence the velocity and celerity of the flow reflecting a mechanism for rapid subsurface hydrologic response processes in the shallow vadose zone.

GEOPHYSICS AND SITE CHARACTERIZATION AT THE HANFORD SITE THE SUCCESSFUL USE OF ELECTRICAL RESISTIVITY TO POSITION BOREHOLES TO DEFINE DEEP VADOSE ZONE CONTAMINATION - 11509

DOE Office of Scientific and Technical Information (OSTI.GOV)

GANDER MJ; LEARY KD; LEVITT MT

2011-01-14

Historic boreholes confirmed the presence of nitrate and radionuclide contaminants at various intervals throughout a more than 60 m (200 ft) thick vadose zone, and a 2010 electrical resistivity survey mapped the known contamination and indicated areas of similar contaminants, both laterally and at depth; therefore, electrical resistivity mapping can be used to more accurately locate characterization boreholes. At the Hanford Nuclear Reservation in eastern Washington, production of uranium and plutonium resulted in the planned release of large quantities of contaminated wastewater to unlined excavations (cribs). From 1952 until 1960, the 216-U-8 Crib received approximately 379,000,000 L (100,000,000 gal) ofmore » wastewater containing 25,500 kg (56,218 lb) uranium; 1,029,000 kg (1,013 tons) of nitrate; 2.7 Ci of technetium-99; and other fission products including strontium-90 and cesium-137. The 216-U-8 Crib reportedly holds the largest inventory of waste uranium of any crib on the Hanford Site. Electrical resistivity is a geophysical technique capable of identifying contrasting physical properties; specifically, electrically conductive material, relative to resistive native soil, can be mapped in the subsurface. At the 216-U-8 Crib, high nitrate concentrations (from the release of nitric acid [HNO{sub 3}] and associated uranium and other fission products) were detected in 1994 and 2004 boreholes at various depths, such as at the base of the Crib at 9 m (30 ft) below ground surface (bgs) and sporadically to depths in excess of 60 m (200 ft) bgs. These contaminant concentrations were directly correlative with the presence of observed low electrical resistivity responses delineated during the summer 2010 geophysical survey. Based on this correlation and the recently completed mapping of the electrically conductive material, additional boreholes are planned for early 2011 to identify nitrate and radionuclide contamination: (a) throughout the entire vertical length of

Water and vapor transfer in vadose zone of Gobi desert and riparian in the hyper arid environment of Ejina, China

NASA Astrophysics Data System (ADS)

Du, C.; Yu, J.; Sun, F.; Liu, X.

2015-12-01

To reveal how water and vapor transfer in vadose zone affect evapotranspiration in Gobi desert and riparian in hyper arid region is important for understanding eco-hydrological process. Field studies and numerical simulations were imported to evaluate the water and vapor movement processes under non isothermal and lower water content conditions. The soil profiles (12 layers) in Gobi desert and riparian sites of Ejina were installed with sensors to monitor soil moisture and temperature for 1 year. The meteorological conditions and water table were measured by micro weather stations and mini-Divers respectively in the two sites. Soil properties, including particles composition, moisture, bulk density, water retention curve, and saturated hydraulic conductivity of two site soil profiles, was measured. The observations showed that soil temperatures for the two sites displayed large diurnal and seasonal fluctuations. Temperature gradients with depth resulted in a downward in summer and upward in winter and became driving force for thermal vapor movement. Soil moistures in Gobi desert site were very low and varied slowly with time. While the soil moistures in riparian site were complicated due to root distribution but water potentials remained uniform with time. The hydrus-1D was employed to simulate evapotranspiration processes. The simulation results showed the significant difference of evaporation rate in the Gobi desert and riparian sites.

Characterization of 4H <000-1> Silicon Carbide Films Grown by Solvent-Laser Heated Floating Zone

NASA Technical Reports Server (NTRS)

Woodworth, Andrew, A; Sayir, Ali; Neudeck, Philip, G; Raghothamachar, Balaji; Dudley, Michael

2012-01-01

Commercially available bulk silicon carbide (SiC) has a high number (>2000/sq cm) of screw dislocations (SD) that have been linked to degradation of high-field power device electrical performance properties. Researchers at the NASA Glenn Research Center have proposed a method to mass-produce significantly higher quality bulk SiC. In order for this bulk growth method to become reality, growth of long single crystal SiC fibers must first be achieved. Therefore, a new growth method, Solvent-Laser Heated Floating Zone (Solvent-LHFZ), has been implemented. While some of the initial Solvent-LHFZ results have recently been reported, this paper focuses on further characterization of grown crystals and their growth fronts. To this end, secondary ion mass spectroscopy (SIMS) depth profiles, cross section analysis by focused ion beam (FIB) milling and mechanical polishing, and orientation and structural characterization by x-ray transmission Laue diffraction patterns and x-ray topography were used. Results paint a picture of a chaotic growth front, with Fe incorporation dependant on C concentration.

Enhanced biogeochemical cycling and subsequent reduction of hydraulic conductivity associated with soil-layer interfaces in the vadose zone

PubMed Central

Hansen, David J.; McGuire, Jennifer T.; Mohanty, Binayak P.

2013-01-01

Biogeochemical dynamics in the vadose zone are poorly understood due to the transient nature of chemical and hydrologic conditions, but are nonetheless critical to understanding chemical fate and transport. This study explored the effects of a soil layer on linked geochemical, hydrological, and microbiological processes. Three laboratory soil columns were constructed: a homogenized medium-grained sand, a homogenized organic-rich loam, and a sand-over-loam layered column. Upward and downward infiltration of water was evaluated during experiments to simulate rising water table and rainfall events respectively. In-situ collocated probes measured soil water content, matric potential, and Eh while water samples collected from the same locations were analyzed for Br−, Cl−, NO3−, SO42−, NH4+, Fe2+, and total sulfide. Compared to homogenous columns, the presence of a soil layer altered the biogeochemistry and water flow of the system considerably. Enhanced biogeochemical cycling was observed in the layered column over the texturally homogeneous soil columns. Enumerations of iron and sulfate reducing bacteria showed 1-2 orders of magnitude greater community numbers in the layered column. Mineral and soil aggregate composites were most abundant near the soil-layer interface; the presence of which, likely contributed to an observed order-of-magnitude decrease in hydraulic conductivity. These findings show that quantifying coupled hydrologic-biogeochemical processes occurring at small-scale soil interfaces is critical to accurately describing and predicting chemical changes at the larger system scale. Findings also provide justification for considering soil layering in contaminant fate and transport models because of its potential to increase biodegradation and/or slow the rate of transport of contaminants. PMID:22031578

Growth of single crystalline delafossite LaCuO2 by the travelling-solvent floating zone method

NASA Astrophysics Data System (ADS)

Mohan, A.; Büchner, B.; Wurmehl, S.; Hess, C.

2014-09-01

Single crystals of LaCuO2 have been grown for the first time using the travelling-solvent floating zone method. The crystal was grown in an Ar-atmosphere by reduction of La2Cu2O5, which was used as the feed rod composition for the growth. The grown crystal has been characterized with regard to phase purity and single crystallinity using powder X-ray diffraction, energy dispersive X-ray analysis, Laue diffraction and scanning electron microscopy.

Use of Large-Scale Multi-Configuration EMI Measurements to Characterize Subsurface Structures of the Vadose Zone.

NASA Astrophysics Data System (ADS)

Huisman, J. A.; Brogi, C.; Pätzold, S.; Weihermueller, L.; von Hebel, C.; Van Der Kruk, J.; Vereecken, H.

2017-12-01

Subsurface structures of the vadose zone can play a key role in crop yield potential, especially during water stress periods. Geophysical techniques like electromagnetic induction EMI can provide information about dominant shallow subsurface features. However, previous studies with EMI have typically not reached beyond the field scale. We used high-resolution large-scale multi-configuration EMI measurements to characterize patterns of soil structural organization (layering and texture) and their impact on crop productivity at the km2 scale. We collected EMI data on an agricultural area of 1 km2 (102 ha) near Selhausen (NRW, Germany). The area consists of 51 agricultural fields cropped in rotation. Therefore, measurements were collected between April and December 2016, preferably within few days after the harvest. EMI data were automatically filtered, temperature corrected, and interpolated onto a common grid of 1 m resolution. Inspecting the ECa maps, we identified three main sub-areas with different subsurface heterogeneity. We also identified small-scale geomorphological structures as well as anthropogenic activities such as soil management and buried drainage networks. To identify areas with similar subsurface structures, we applied image classification techniques. We fused ECa maps obtained with different coil distances in a multiband image and applied supervised and unsupervised classification methodologies. Both showed good results in reconstructing observed patterns in plant productivity and the subsurface structures associated with them. However, the supervised methodology proved more efficient in classifying the whole study area. In a second step, we selected hundred locations within the study area and obtained a soil profile description with type, depth, and thickness of the soil horizons. Using this ground truth data it was possible to assign a typical soil profile to each of the main classes obtained from the classification. The proposed methodology was

A model for microbially induced precipitation of vadose-zone calcites in fractures at LOS Alamos, New Mexico, USA

NASA Astrophysics Data System (ADS)

Newman, Brent D.; Campbell, Andrew R.; Norman, David I.; Ringelberg, David B.

1997-05-01

Fractures are unique environments that can concentrate the flow of water, nutrients, and contaminants. As such, fractures play an important role in controlling the flux of various substances into and through the vadose zone. Calcite fracture fillings are present in the near surface in the Bandelier Tuff Formation at Los Alamos, New Mexico, and provide a record of the geochemical and hydrologic processes that have occurred in fractures. The objective of this study was to examine calcite fracture fills in order to improve understanding of processes within fractures, and in particular those that lead to precipitation of calcite. Samples of calcite fillings were collected from vertical and horizontal fractures exposed in a shallow waste-burial pit. Scanning electron microscopy show morphologies which suggest that plants, fungi, and bacteria were important in the precipitation process. Quadrupole mass spectrometric analyses of fluid inclusion gases show predominantly methane (17-99%) and little to no oxygen (0-8%), suggesting the development of anaerobic conditions in the fractures. Ester-linked phospholipid biomarkers are evidence for a diverse microbial community in the fractures, and the presence of di-ether lipids indicate that the methane was generated by anaerobic bacteria. The calcite fillings apparently resulted from multiple biological and chemical processes in which plant roots in the fractures were converted to calcite. Roots grew into the fractures, eventually died, and were decomposed by bacteria and fungi. Anaerobic gases were generated from encapsulated organic material within the calcite via microbial decomposition, or were generated by microbes simultaneously with calcite precipitation. It is likely that the biological controls on calcite formation that occurred in the Los Alamos fractures also occurs in soils, and may explain the occurrence of other types of pedogenic calcites.

Transport of Carbon Tetrachloride in a Fractured Vadose Zone due to Atmospheric Pressure Fluctuations, Diffusion, and Vapor Density

NASA Astrophysics Data System (ADS)

McCray, J. E.; Downs, W.; Falta, R. W.; Housley, T.

2005-12-01

DNAPL sources of carbon tetrachloride (CT) vapors are of interest at the Radioactive Waste Management Complex (RWMC) at the Idaho National Engineering and Environmental Laboratory (INEEL). The site is underlain by thick fractured basalt that includes sedimentary interbeds, each are a few meters thick. Daily atmospheric pressure fluctuations serve as driving forces for CT vapor transport in the subsurface. Other important transport processes for vapor movement include gas-phase diffusion and density-driven transport. The objective of this research is to investigate the influence and relative importance of these processes on gaseous transport of CT. Gas pressure and vapor concentration measurements were conducted at various depths in two wells. A numerical multiphase flow model (TOUGH2), calibrated to field pressure data, is used to conduct sensitivity analyses to elucidate the importance of the different transport mechanisms. Results show that the basalt is highly permeable to vertical air flow. The pressure dampening occurs mainly in the sedimentary interbeds. Model-calibrated permeability values for the interbeds are similar to those obtained in a study by the U.S. Geological Survey for shallow sediments, and an order of magnitude higher than column-scale values obtained by previous studies conducted by INEEL scientists. The transport simulations indicate that considering the effect of barometric pressure changes is critical to simulating transport of pollutants in the vadose zone above the DNAPL source. Predicted concentrations can be orders of magnitude smaller than actual concentrations if the effect is not considered. Below the DNAPL vapor source, accounting for density and diffusion alone would yield acceptable results provided that a 20% error in concentrations are acceptable, and that simulating concentrations trends (and not actual concentrations) is the primary goal.

Evaluating BTEX concentration in soil using a simple one-dimensional vado zone model: application to a new fuel station in Valencia (Spain)

NASA Astrophysics Data System (ADS)

Rodrigo-Ilarri, Javier; Rodrigo-Clavero, María-Elena

2017-04-01

Specific studies of the impact of fuel spills on the vadose zone are currently required when trying to obtain the environmental permits for new fuel stations. The development of One-Dimensional mathematical models of fate and transport of BTEX on the vadose zone can therefore be used to understand the behavior of the pollutants under different scenarios. VLEACH - a simple One-Dimensional Finite Different Vadose Zone Leaching Model - uses an numerical approximation of the Millington Equation, a theoretical based model for gaseous diffusion in porous media. This equation has been widely used in the fields of soil physics and hydrology to calculate the gaseous or vapor diffusion in porous media. The model describes the movement of organic contaminants within and between three different phases: (1) as a solute dissolved in water, (2) as a gas in the vapor phase, and (3) as an absorbed compound in the soil phase. Initially, the equilibrium distribution of contaminant mass between liquid, gas and sorbed phases is calculated. Transport processes are then simulated. Liquid advective transport is calculated based on values defined by the user for infiltration and soil water content. The contaminant in the vapor phase migrates into or out of adjacent cells based on the calculated concentration gradients that exist between adjacent cells. After the mass is exchanged between the cells, the total mass in each cell is recalculated and re-equilibrated between the different phases. At the end of the simulation, (1) an overall area-weighted groundwater impact for the entire modeled area and (2) the concentration profile of BTEX on the vadose zone are calculated. This work shows the results obtained when applying VLEACH to analyze the contamination scenario caused by a BTEX spill coming from a set of future underground storage tanks located on a new fuel station in Aldaia (Valencia region - Spain).

In Situ Bioremediation of Perchlorate in Vadose Zone Source Areas

DTIC Science & Technology

2011-01-01

agricultural bags (e.g., ITRC, 2008; Evans et al., 2008). Phytoremediation has also been tested for soil treatment (ITRC, 2008). However, these...within the saturated zone (through in situ bioremediation or groundwater extraction and ex-situ treatment), phytoremediation , which is unlikely to

Use of once-through treat gas to remove the heat of reaction in solvent hydrogenation processes

DOEpatents

Nizamoff, Alan J.

1980-01-01

In a coal liquefaction process wherein feed coal is contacted with molecular hydrogen and a hydrogen-donor solvent in a liquefaction zone to form coal liquids and vapors and coal liquids in the solvent boiling range are thereafter hydrogenated to produce recycle solvent and liquid products, the improvement which comprises separating the effluent from the liquefaction zone into a hot vapor stream and a liquid stream; cooling the entire hot vapor stream sufficiently to condense vaporized liquid hydrocarbons; separating condensed liquid hydrocarbons from the cooled vapor; fractionating the liquid stream to produce coal liquids in the solvent boiling range; dividing the cooled vapor into at least two streams; passing the cooling vapors from one of the streams, the coal liquids in the solvent boiling range, and makeup hydrogen to a solvent hydrogenation zone, catalytically hydrogenating the coal liquids in the solvent boiling range and quenching the hydrogenation zone with cooled vapors from the other cooled vapor stream.

Stochastic inversion of time-lapse geophysical data to characterize the vadose zone at the Arrenaes field site (Denmark)

NASA Astrophysics Data System (ADS)

Marie, S.; Irving, J. D.; Looms, M. C.; Nielsen, L.; Holliger, K.

2011-12-01

Geophysical methods such as ground-penetrating radar (GPR) can provide valuable information on the hydrological properties of the vadose zone. In particular, there is evidence to suggest that the stochastic inversion of such data may allow for significant reductions in uncertainty regarding subsurface van-Genuchten-Mualem (VGM) parameters, which characterize unsaturated hydrodynamic behaviour as defined by the combination of the water retention and hydraulic conductivity functions. A significant challenge associated with the use of geophysical methods in a hydrological context is that they generally exhibit an indirect and/or weak sensitivity to the hydraulic parameters of interest. A novel and increasingly popular means of addressing this issue involves the acquisition of geophysical data in a time-lapse fashion while changes occur in the hydrological condition of the probed subsurface region. Another significant challenge when attempting to use geophysical data for the estimation of subsurface hydrological properties is the inherent non-linearity and non-uniqueness of the corresponding inverse problems. Stochastic inversion approaches have the advantage of providing a comprehensive exploration of the model space, which makes them ideally suited for addressing such issues. In this work, we present the stochastic inversion of time-lapse zero-offset-profile (ZOP) crosshole GPR traveltime data, collected during a forced infiltration experiment at the Arreneas field site in Denmark, in order to estimate subsurface VGM parameters and their corresponding uncertainties. We do this using a Bayesian Markov-chain-Monte-Carlo (MCMC) inversion approach. We find that the Bayesian-MCMC methodology indeed allows for a substantial refinement in the inferred posterior parameter distributions of the VGM parameters as compared to the corresponding priors. To further understand the potential impact on capturing the underlying hydrological behaviour, we also explore how the posterior

Utilizing High-Performance Computing to Investigate Parameter Sensitivity of an Inversion Model for Vadose Zone Flow and Transport

NASA Astrophysics Data System (ADS)

Fang, Z.; Ward, A. L.; Fang, Y.; Yabusaki, S.

2011-12-01

High-resolution geologic models have proven effective in improving the accuracy of subsurface flow and transport predictions. However, many of the parameters in subsurface flow and transport models cannot be determined directly at the scale of interest and must be estimated through inverse modeling. A major challenge, particularly in vadose zone flow and transport, is the inversion of the highly-nonlinear, high-dimensional problem as current methods are not readily scalable for large-scale, multi-process models. In this paper we describe the implementation of a fully automated approach for addressing complex parameter optimization and sensitivity issues on massively parallel multi- and many-core systems. The approach is based on the integration of PNNL's extreme scale Subsurface Transport Over Multiple Phases (eSTOMP) simulator, which uses the Global Array toolkit, with the Beowulf-Cluster inspired parallel nonlinear parameter estimation software, BeoPEST in the MPI mode. In the eSTOMP/BeoPEST implementation, a pre-processor generates all of the PEST input files based on the eSTOMP input file. Simulation results for comparison with observations are extracted automatically at each time step eliminating the need for post-process data extractions. The inversion framework was tested with three different experimental data sets: one-dimensional water flow at Hanford Grass Site; irrigation and infiltration experiment at the Andelfingen Site; and a three-dimensional injection experiment at Hanford's Sisson and Lu Site. Good agreements are achieved in all three applications between observations and simulations in both parameter estimates and water dynamics reproduction. Results show that eSTOMP/BeoPEST approach is highly scalable and can be run efficiently with hundreds or thousands of processors. BeoPEST is fault tolerant and new nodes can be dynamically added and removed. A major advantage of this approach is the ability to use high-resolution geologic models to preserve

The DNAPL Remediation Challenge: Is There a Case for Source Depletion?

DTIC Science & Technology

2003-12-01

fermentation products acting as electron donors to promote reductive dechlorination of chlorinated solvents (e.g., see discussion on Sages and Bachman...has been primarily used to remove organic contamination in the vadose zone (see e.g., Stegemeier and Vinegar , 2001). Signifi cant removals of...Stegemeier, G.L., and H.J. Vinegar . 2001. Thermal conduction heating for in-situ thermal desorption of soils. In: Hazardous and Radioactive Waste Treatment

CO2 leakage monitoring and analysis to understand the variation of CO2 concentration in vadose zone by natural effects

NASA Astrophysics Data System (ADS)

Joun, Won-Tak; Ha, Seung-Wook; Kim, Hyun Jung; Ju, YeoJin; Lee, Sung-Sun; Lee, Kang-Kun

2017-04-01

Controlled ex-situ experiments and continuous CO2 monitoring in the field are significant implications for detecting and monitoring potential leakage from CO2 sequestration reservoir. However, it is difficult to understand the observed parameters because the natural disturbance will fluctuate the signal of detections in given local system. To identify the original source leaking from sequestration reservoir and to distinguish the camouflaged signal of CO2 concentration, the artificial leakage test was conducted in shallow groundwater environment and long-term monitoring have been performed. The monitoring system included several parameters such as pH, temperature, groundwater level, CO2 gas concentration, wind speed and direction, atmospheric pressure, borehole pressure, and rainfall event etc. Especially in this study, focused on understanding a relationship among the CO2 concentration, wind speed, rainfall and pressure difference. The results represent that changes of CO2 concentration in vadose zone could be influenced by physical parameters and this reason is helpful in identifying the camouflaged signal of CO2 concentrations. The 1-D column laboratory experiment also was conducted to understand the sparking-peak as shown in observed data plot. The results showed a similar peak plot and could consider two assumptions why the sparking-peak was shown. First, the trapped CO2 gas was escaped when the water table was changed. Second, the pressure equivalence between CO2 gas and water was broken when the water table was changed. These field data analysis and laboratory experiment need to advance due to comprehensively quantify local long-term dynamics of the artificial CO2 leaking aquifer. Acknowledgement Financial support was provided by the "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003)

Influence of a strong sample solvent on analyte dispersion in chromatographic columns.

PubMed

Mishra, Manoranjan; Rana, Chinar; De Wit, A; Martin, Michel

2013-07-05

In chromatographic columns, when the eluting strength of the sample solvent is larger than that of the carrier liquid, a deformation of the analyte zone occurs because its frontal part moves at a relatively high velocity due to a low retention factor in the sample solvent while the rear part of the analyte zone is more retained in the carrier liquid and hence moves at a lower velocity. The influence of this solvent strength effect on the separation of analytes is studied here theoretically using a mass balance model describing the spatio-temporal evolution of the eluent, the sample solvent and the analyte. The viscosity of the sample solvent and carrier fluid is supposed to be the same (i.e. no viscous fingering effects are taken into account). A linear isotherm adsorption with a retention factor depending upon the local concentration of the liquid phase is considered. The governing equations are numerically solved by using a Fourier spectral method and parametric studies are performed to analyze the effect of various governing parameters on the dispersion and skewness of the analyte zone. The distortion of this zone is found to depend strongly on the difference in eluting strength between the mobile phase and the sample solvent as well as on the sample volume. Copyright © 2013 Elsevier B.V. All rights reserved.

Self-adjusted flux for the traveling solvent floating zone growth of YBaCuFeO5 crystal

NASA Astrophysics Data System (ADS)

Lai, Yen-Chung; Shu, Guo-Jiun; Chen, Wei-Tin; Du, Chao-Hung; Chou, Fang-Cheng

2015-03-01

A modified traveling solvent floating zone (TSFZ) technique was used to successfully grow a large size and high quality single crystal of multiferroic material YBaCuFeO5. This modified TSFZ growth uses a stoichiometric feed rod and pure copper oxide as the initial flux without prior knowledge of the complex phase diagram involving four elements, and the optimal flux for the growth of incongruently melt crystal is self-adjusted after a prolonged stable pulling. The wetting of the feed rod edge that often perturbs the molten zone stability was avoided by adding 2 wt% B2O3. The optimal flux concentration for the YBaCuFeO5 growth can be extracted to be near YBaCuFeO5:CuO=13:87 in molar ratio. The crystal quality was confirmed by the satisfactory refinement of crystal structure of space group P4mm and the two consecutive anisotropic antiferromagnetic phase transitions near 455 K and 170 K.

Sorption and mineralization of S-metolachlor and its ionic metabolites in soils and vadose zone solids: consequences on groundwater quality in an alluvial aquifer (Ain Plain, France).

PubMed

Baran, Nicole; Gourcy, Laurence

2013-11-01

This study characterizes the transfer of S-metolachlor (SMOC) and its metabolites, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA) to the alluvial aquifer. Sorption and mineralization of SMOC and its two ionic metabolites were characterized for cultivated soils and solids from the vadose (unsaturated) zone in the Ain Plain (France). Under sterile soil conditions, the absence of mineralization confirms the importance of biotic processes in SMOC degradation. There is some adsorption and mineralization of the parent molecule and its metabolites in the unsaturated zone, though less than in soils. For soils, the MESA adsorption constant is statistically higher than that of MOXA and the sorption constants of the two metabolites are significantly lower than that of SMOC. After 246 days, for soils, maximums of 26% of the SMOC, 30% of the MESA and 38% of the MOXA were mineralized. This partly explains the presence of these metabolites in the groundwater at concentrations generally higher than those of the parent molecule for MESA, although there is no statistical difference in the mineralization of the 3 molecules. The laboratory results make it possible to explain the field observations made during 27 months of groundwater quality monitoring (monthly sampling frequency). The evolution of both metabolite concentrations in the groundwater is directly related to recharge dynamics; there is a positive correlation between concentrations and the groundwater level. The observed lag of several months between the signals of the parent molecule and those of the metabolites is probably due to greater sorption of the parent molecule than of its metabolites and/or to degradation kinetics. © 2013.

The role of rock moisture on regulating hydrologic and solute fluxes in the critical zone

NASA Astrophysics Data System (ADS)

Rempe, D. M.; Druhan, J. L.; Hahm, W. J.; Wang, J.; Murphy, C.; Cargill, S.; Dietrich, W. E.; Tune, A. K.

2017-12-01

In environments where the vadose zone extends below the soil layer into underlying weathered bedrock, the water held in the weathering -generated pores can be an important source of moisture to vegetation. The heterogeneous distribution of pore space in weathered bedrock, furthermore, controls the subsurface water flowpaths that dictate how water is partitioned in the critical zone (CZ) and evolves geochemically. Here, we present the results of direct monitoring of the fluxes of water and solutes through the deep CZ using a novel vadose zone monitoring system (VMS) as well as geophysical logging and sampling in a network of deep wells across a steep hillslope in Northern California. At our study site (Eel River CZO), multi-year monitoring reveals that a significant fraction of incoming rainfall (up to 30%) is seasonally stored in the fractures and matrix of the upper 12 m of weathered bedrock as rock moisture. Intensive geochemical and geophysical observations distributed from the surface to the depth of unweathered bedrock indicate that the seasonal addition and depletion of rock moisture has key implications for hydrologic and geochemical processes. First, rock moisture storage provides an annually consistent water storage reservoir for use by vegetation during the summer, which buffers transpiration fluxes against variability in seasonal precipitation. Second, because the timing and magnitude of groundwater recharge and streamflow are controlled by the annual filling and drainage of the rock moisture, rock moisture regulates the partitioning of hydrologic fluxes. Third, we find that rock moisture dynamics—which influence the myriad geochemical and microbial processes that weather bedrock—strongly correspond with the observed vertical weathering profile. As a result of the coupling between chemical weathering reactions and hydrologic fluxes, the geochemical composition of groundwater and streamflow is influenced by the temporal dynamics of rock moisture. Our

Evaluation of air sparging and vadose zone aeration for remediation of iron and manganese-impacted groundwater at a closed municipal landfill.

PubMed

Pleasant, Saraya; O'Donnell, Amanda; Powell, Jon; Jain, Pradeep; Townsend, Timothy

2014-07-01

High concentrations of iron (Fe(II)) and manganese (Mn(II)) reductively dissolved from soil minerals have been detected in groundwater monitoring wells near many municipal solid waste landfills. Air sparging and vadose zone aeration (VZA) were evaluated as remedial approaches at a closed, unlined municipal solid waste landfill in Florida, USA. The goal of aeration was to oxidize Fe and Mn to their respective immobile forms. VZA and shallow air sparging using a partially submerged well screen were employed with limited success (Phase 1); decreases in dissolved iron were observed in three of nine monitoring wells during shallow air sparging and in two of 17 wells at VZA locations. During Phase 2, where deeper air sparging was employed, dissolved iron levels decreased in a significantly greater number of monitoring wells surrounding injection points, however no radial pattern was observed. Additionally, in wells affected positively by air sparging (mean total iron (FeTOT) <4.2mg/L, after commencement of air sparging), rising manganese concentrations were observed, indicating that the redox potential of the groundwater moved from an iron-reducing to a manganese-reducing environment. The mean FeTOT concentration observed in affected monitoring wells throughout the study was 1.40 mg/L compared to a background of 15.38 mg/L, while the mean Mn concentration was 0.60 mg/L compared to a background level of 0.27 mg/L. Reference wells located beyond the influence of air sparging areas showed little variation in FeTOT and Mn, indicating the observed effects were the result of air injection activities at study locations and not a natural phenomenon. Air sparging was found effective in intercepting plumes of dissolved Fe surrounding municipal landfills, but the effect on dissolved Mn was contrary to the desired outcome of decreased Mn groundwater concentrations. Copyright © 2014 Elsevier B.V. All rights reserved.

You Don't Need Richards'... A New General 1-D Vadose Zone Solution Method that is Reliable

NASA Astrophysics Data System (ADS)

Ogden, F. L.; Lai, W.; Zhu, J.; Steinke, R. C.; Talbot, C. A.

2015-12-01

Hydrologic modelers and mathematicians have strived to improve 1-D Richards' equation (RE) solution reliability for predicting vadose zone fluxes. Despite advances in computing power and the numerical solution of partial differential equations since Richards first published the RE in 1931, the solution remains unreliable. That is to say that there is no guarantee that for a particular set of soil constitutive relations, moisture profile conditions, or forcing input that a numerical RE solver will converge to an answer. This risk of non-convergence renders prohibitive the use of RE solvers in hydrological models that need perhaps millions of infiltration solutions. In lieu of using unreliable numerical RE solutions, researchers have developed a wide array of approximate solutions that more-or-less mimic the behavior of the RE, with some notable deficiencies such as parameter insensitivity or divergence over time. The improved Talbot-Ogden (T-O) finite water-content scheme was shown by Ogden et al. (2015) to be an extremely good approximation of the 1-D RE solution, with a difference in cumulative infiltration of only 0.2 percent over an 8 month simulation comparing the improved T-O scheme with a RE numerical solver. The reason is that the newly-derived fundamental flow equation that underpins the improved T-O method is equivalent to the RE minus a term that is equal to the diffusive flux divided by the slope of the wetting front. Because the diffusive flux has zero mean, this term is not important in calculating the mean flux. The wetting front slope is near infinite (sharp) in coarser soils that produce more significant hydrological interactions between surface and ground waters, which also makes this missing term 1) disappear in the limit, and, 2) create stability challenges for the numerical solution of RE. The improved T-O method is a replacement for the 1-D RE in soils that can be simulated as homogeneous layers, where the user is willing to neglect the effects

Biodegradation of organic compounds in vadose zone and aquifer sediments.

PubMed Central

Konopka, A; Turco, R

1991-01-01

The microbial processes that occur in the subsurface under a typical Midwest agricultural soil were studied. A 26-m bore was installed in November of 1988 at a site of the Purdue University Agronomy Research Center. Aseptic collections of soil materials were made at 17 different depths. Physical analysis indicated that the site contained up to 14 different strata. The site materials were primarily glacial tills with a high carbonate content. The N, P, and organic C contents of sediments tended to decrease with depth. Ambient water content was generally less than the water content, which corresponds to a -0.3-bar equivalent. No pesticides were detected in the samples, and degradation of added 14C-labeled pesticides (atrazine and metolachlor) was not detected in slurry incubations of up to 128 days. The sorption of atrazine and metolachlor was correlated with the clay content of the sediments. Microbial biomass (determined by direct microscopic count, viable count, and phospholipid assay) in the tills was lower than in either the surface materials or the aquifer located at 25 m. The biodegradation of glucose and phenol occurred rapidly and without a lag in samples from the aquifer capillary fringe, saturated zone, and surface soils. In contrast, lag periods and smaller biodegradation rates were found in the till samples. Subsurface sediments are rich in microbial numbers and activity. The most active strata appear to be transmissive layers in the saturated zone. This implies that the availability of water may limit activity in the profile. PMID:1768098

ANNUAL REPORT FOR ENVIRONMENTAL MANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACE METALS IN GROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 AND OTHER DIVALENT METALS AND RADIONUCLIDES AT ARID WESTERN DOE SITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Robert W.; Fujita, Yoshiko; Ferris, F. Grant

2003-06-15

Radionuclide and metal contaminants such as 90Sr are present beneath U.S. Department of Energy (DOE) lands in both the groundwater (e.g., 100-N area at Hanford, WA) and vadose zone (e.g., Idaho Nuclear Technology and Engineering Center at the Idaho National Engineering and Environmental Laboratory). In situ containment and stabilization of these contaminants is a cost-effective treatment strategy. However, implementing in situ containment and stabilization approaches requires definition of the mechanisms that control contaminant sequestration. We are investigating the in situ immobilization of radionuclides or contaminant metals (e.g., 90Sr) by their facilitated co-precipitation with calcium carbonate in groundwater and vadose zonemore » systems. Our facilitated approach, shown schematically in Figure 1, relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity. Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface urea hydrolyzing microorganisms. Because the precipitation process tends to be irreversible and many western aquifers are saturated with respect to calcite, the coprecipitated metals and radionuclides will be effectively removed from the aqueous phase over the long-term. Another advantage of the ureolysis approach is that the ammonium ions produced by the reaction can exchange with radionuclides sorbed to subsurface minerals, thereby enhancing the availability of the radionuclides for re-capture in a more stable solid phase (co-precipitation rather than adsorption).« less

Experimental quantification of solute transport through the vadose zone under dynamic boundary conditions with dye tracers and optical methods.

NASA Astrophysics Data System (ADS)

Cremer, Clemens; Neuweiler, Insa

2017-04-01

transport through the material interface which differs between the stationary (unilateral) and dynamic cases (bilateral). This qualitative observation is confirmed by breakthrough curves for dynamic experiments which generally show the trend of faster initial breakthrough and increased tailing when compared to stationary infiltration results. Literature Cremer, C.J.M., I. Neuweiler, M. Bechtold, J. Vanderborght (2016): Solute Transport in Heterogeneous Soil with Time-Dependent Boundary Conditions, Vadose Zone Journal 15 (6) DOI: 10.2136/vzj2015.11.0144

A simulation model for projecting changes in salinity concentrations and species dominance in the coastal margin habitats of the Everglades

USGS Publications Warehouse

Teh, S.Y.; DeAngelis, D.L.; Sternberg, L.D.S.L.; Miralles-Wilhelm, F. R.; Smith, T.J.; Koh, H. L.

2008-01-01

Sharp boundaries typically separate the salinity tolerant mangroves from the salinity intolerant hardwood hammock species, which occupy the similar geographical areas of southern Florida. Evidence of strong feedback between tree community-type and the salinity of the unsaturated (vadose) zone of the soil suggests that a severe disturbance that significantly tilts the salinity in the vadose zone might cause a shift from one vegetation type to the other. In this study, a model based upon the feedback dynamics between vegetation and salinity of the vadose zone of the soil was used to take account of storm surge events to investigate the mechanisms that by which this large-scale disturbance could affect the spatial pattern of hardwood hammocks and mangroves. Model simulation results indicated that a heavy storm surge that completely saturated the vadose zone at 30 ppt for 1 day could lead to a regime shift in which there is domination by mangroves of areas previously dominated by hardwood hammocks. Lighter storm surges that saturated the vadose zone at less than 7 ppt did not cause vegetation shifts. Investigations of model sensitivity analysis indicated that the thickness of the vadose zone, coupled with precipitation, influenced the residence time of high salinity in the vadose zone and therefore determined the rate of mangrove domination. The model was developed for a southern Florida coastal ecosystem, but its applicability may be much broader. ?? 2008 Elsevier B.V. All rights reserved.

Quasi 3D modeling of water flow in vadose zone and groundwater

USDA-ARS?s Scientific Manuscript database

The complexity of subsurface flow systems calls for a variety of concepts leading to the multiplicity of simplified flow models. One habitual simplification is based on the assumption that lateral flow and transport in unsaturated zone are not significant unless the capillary fringe is involved. In ...

Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Stronthium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Robert W.; Fujita, Yoshiko

2007-11-07

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers’ exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadosemore » zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the

Characterization of Vadose Zone Sediment: RCRA Borehole 299-E33-338 Located Near the B-BX-BY Waste Management Area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindenmeier, Clark W.; Serne, R. Jeffrey; Bjornstad, Bruce N.

2003-09-11

This report summarizes data collected from samples in borehole 299-E33-338 (C3391). Borehole 299-E33-338 was drilled for two purposes. One purpose was for installation of a RCRA ground-water monitoring well and the other was to characterize the in situ soils and background porewater chemistry near WMA B-BX-BY that have been largely uncontaminated by tank farm and crib and trench discharge operations. This borehole was drilled just outside the southeast fence line of the B tank farm. The borehole was drilled between July 23 and August 8, 2001 to a total depth of 80.05 m (275.75 ft) bgs using the cable-tool methodmore » (Horton 2002). The water table was contacted at 77.5 m (254.2 ft) bgs and the top of basalt at 82.6 m (271 ft) bgs. Samples to the top of basalt were collected via a drive barrel/splitspoon, before switching to a hard tool to drill 5 feet into the basalt. Nearly continuous core was obtained down to a depth of ~78.6 m (258 ft) bgs. Two hundred and two 2-ft long by 4-in diameter cores were retrieved, which accounts for ~75% the total length of the borehole. Each 2-ft splitspoon contained two 1-ft lexan-lined core segments. The lithology of this borehole was summarized onto a field geologist's log by a CH2M HILL Hanford Group, Inc. geologist (L. D. Walker); subsequently visual inspection of the cores was performed in the laboratory by K. A. Lindsey (Kennedy/Jenks), K. D. Reynolds (Duratek), and B. N. Bjornstad (Pacific Northwest National Laboratory), who also collected 24 samples for paleomagnetic analysis. Subsamples were taken from all 102 cores for moisture content (Table B.1). In addition, 21 core subsamples were collected from a depth of geological interest for mineralogical and geochemical analysis. Data from these samples allow for comparison of uncontaminated versus contaminated soils to better understand the contributions of tank wastes and other wastewaters on the vadose zone in and around WMA B-BX-BY.« less

Susceptibility to enhanced chemical migration from depression-focused preferential flow, High Plains aquifer

USGS Publications Warehouse

Gurdak, Jason J.; Walvoord, Michelle Ann; McMahon, Peter B.

2008-01-01

Aquifer susceptibility to contamination is controlled in part by the inherent hydrogeologic properties of the vadose zone, which includes preferential-flow pathways. The purpose of this study was to investigate the importance of seasonal ponding near leaky irrigation wells as a mechanism for depression-focused preferential flow and enhanced chemical migration through the vadose zone of the High Plains aquifer. Such a mechanism may help explain the widespread presence of agrichemicals in recently recharged groundwater despite estimates of advective chemical transit times through the vadose zone from diffuse recharge that exceed the historical period of agriculture. Using a combination of field observations, vadose zone flow and transport simulations, and probabilistic neural network modeling, we demonstrated that vadose zone transit times near irrigation wells range from 7 to 50 yr, which are one to two orders of magnitude faster than previous estimates based on diffuse recharge. These findings support the concept of fast and slow transport zones and help to explain the previous discordant findings of long vadose zone transit times and the presence of agrichemicals at the water table. Using predictions of aquifer susceptibility from probabilistic neural network models, we delineated approximately 20% of the areal extent of the aquifer to have conditions that may promote advective chemical transit times to the water table of <50 yr if seasonal ponding and depression-focused flow exist. This aquifer-susceptibility map may help managers prioritize areas for groundwater monitoring or implementation of best management practices.

Spatial and temporal variability of nitrate and nitrous oxide concentrations in the unsaturated zone at a corn field in the US Midwest

NASA Astrophysics Data System (ADS)

Gopalakrishnan, G.; Negri, C.

2011-12-01

There has been a significant increase in reactive nitrogen in the environment as a result of human activity. Reactive nitrogen of anthropogenic origin now equals that derived from natural terrestrial nitrogen fixation and is expected to exceed it by the end of the decade. Nitrogen is applied to crops as fertilizer and impacts the environment through water quality impairments (mostly as nitrate) and as greenhouse gas emissions (as nitrous oxide). Research on environmental impacts resulting from nitrogen application in the form of fertilizers has focused disproportionately on the degradation of water quality from agricultural non-point sources. The impacts of this degradation are registered both locally, with runoff and percolation of agrochemicals into local surface water and groundwater, and on a larger scale, such as the increase in the anoxic zone in the Gulf of Mexico attributed to nitrate from the Mississippi River. Impacts to the global climate from increased production of nitrous oxide as a result of increased fertilization are equally significant. Nitrous oxide is a greenhouse gas with a warming potential that is approximately 300 times greater than carbon dioxide. Direct emissions of nitrous oxide from the soil have been expressed as 1% of the applied nitrogen. Indirect emissions due to runoff, leaching and volatilization of the nitrogen from the field have been expressed as 0.75% of the applied nitrogen. Many studies have focused on processes governing nitrogen fluxes in the soil, surface water and groundwater systems. However, research on the biogeochemical processes regulating nitrogen fluxes in the unsaturated zone and consequent impacts on nitrate and nitrous oxide concentrations in groundwater are lacking. Our study explores the spatial and temporal variability of nitrate and nitrous oxide concentrations in the vadose zone at a 15 acre corn field in the US Midwest and links it to the concentrations found in the groundwater at the field site. Results

Vadose zone isobaric well

DOEpatents

Hubbell, Joel M.; Sisson, James B.

2001-01-01

A deep tensiometer is configured with an outer guide tube having a vented interval along a perforate section at its lower end, which is isolated from atmospheric pressure at or above grade. A transducer having a monitoring port and a reference port is located within a coaxial inner guide tube. The reference port of the transducer is open to the vented interval of the outer guide tube, which has the same gas pressure as in the sediment surrounding the tensiometer. The reference side of the pressure transducer is thus isolated from the effects of atmospheric pressure changes and relative to pressure changes in the material surrounding the tensiometer measurement location and so it is automatically compensated for such pressure changes.

Plants as bio-indicators of subsurface conditions: impact of groundwater level on BTEX concentrations in trees.

PubMed

Wilson, Jordan; Bartz, Rachel; Limmer, Matt; Burken, Joel

2013-01-01

Numerous studies have demonstrated trees' ability to extract and translocate moderately hydrophobic contaminants, and sampling trees for compounds such as BTEX can help delineate plumes in the field. However, when BTEX is detected in the groundwater, detection in nearby trees is not as reliable an indicator of subsurface contamination as other compounds such as chlorinated solvents. Aerobic rhizospheric and bulk soil degradation is a potential explanation for the observed variability of BTEX in trees as compared to groundwater concentrations. The goal of this study was to determine the effect of groundwater level on BTEX concentrations in tree tissue. The central hypothesis was increased vadose zone thickness promotes biodegradation of BTEX leading to lower BTEX concentrations in overlying trees. Storage methods for tree core samples were also investigated as a possible reason for tree cores revealing lower than expected BTEX levels in some sampling efforts. The water level hypothesis was supported in a greenhouse study, where water table level was found to significantly affect tree BTEX concentrations, indicating that the influx of oxygen coupled with the presence of the tree facilitates aerobic biodegradation of BTEX in the vadose zone.

T Tank Farm Interim Surface Barrier Demonstration - Vadose Zone Monitoring FY09 Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Z. F.; Strickland, Christopher E.; Field, Jim G.

2010-01-01

DOE’s Office of River Protection constructed a temporary surface barrier over a portion of the T Tank Farm as part of the T Farm Interim Surface Barrier Demonstration Project. As part of the demonstration effort, vadose zone moisture is being monitored to assess the effectiveness of the barrier at reducing soil moisture. A solar-powered system was installed to continuously monitor soil water conditions at four locations (i.e., instrument Nests A, B, C, and D) beneath the barrier and outside the barrier footprint as well as site meteorological conditions. Nest A is placed in the area outside the barrier footprint andmore » serves as a control, providing subsurface conditions outside the influence of the surface barrier. Nest B provides subsurface measurements to assess surface-barrier edge effects. Nests C and D are used to assess changes in soil-moisture conditions beneath the interim surface barrier. Each instrument nest is composed of a capacitance probe (CP) with multiple sensors, multiple heat-dissipation units (HDUs), and a neutron probe (NP) access tube. The monitoring results in FY09 are summarized below. The solar panels functioned normally and could provide sufficient power to the instruments. The CP in Nest C after September 20, 2009, was not functional. The CP sensors in Nest B after July 13 and the 0.9-m CP sensor in Nest D before June 10 gave noisy data. Other CPs were functional normally. All the HDUs were functional normally but some pressure-head values measured by HDUs were greater than the upper measurement-limit. The higher-than-upper-limit values might be due to the very wet soil condition and/or measurement error but do not imply the malfunction of the sensors. Similar to FY07 and FY08, in FY09, the soil under natural conditions (Nest A) was generally recharged during the winter period (October-March) and discharged during the summer period (April-September). Soil water conditions above about 1.5-m to 2-m depth from all three types of

Process for producing low-sulfur boiler fuel by hydrotreatment of solvent deashed SRC

DOEpatents

Roberts, George W.; Tao, John C.

1985-01-01

In this invention, a process is disclosed characterized by heating a slurry of coal in the presence of a process-derived recycle solvent and passing same to a dissolver zone, separating the resultant gases and liquid/solid products therefrom, vacuum distilling the liquid/solids products, separating the portions of the liquid/solids vacuum distillation effluent into a solid ash, unconverted coal particles and SRC material having a boiling point above 850.degree. F. and subjecting same to a critical solvent deashing step to provide an ash-free SRC product. The lighter liquid products from the vacuum distillation possess a boiling point below 850.degree. F. and are passed through a distillation tower, from which recycled solvent is recovered in addition to light distillate boiling below 400.degree. F. (overhead). The ash-free SRC product in accompanyment with at least a portion of the process derived solvent is passed in combination to a hydrotreating zone containing a hydrogenation catalyst and in the presence of hydrogen is hydroprocessed to produce a desulfurized and denitrogenized low-sulfur, low-ash boiler fuel and a process derived recycle solvent which is recycled to slurry the coal in the beginning of the process before heating.

Persistence of uranium groundwater plumes: contrasting mechanisms at two DOE sites in the groundwater-river interaction zone.

PubMed

Zachara, John M; Long, Philip E; Bargar, John; Davis, James A; Fox, Patricia; Fredrickson, Jim K; Freshley, Mark D; Konopka, Allan E; Liu, Chongxuan; McKinley, James P; Rockhold, Mark L; Williams, Kenneth H; Yabusaki, Steve B

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (zone and a continuous influx of U(VI) from natural, up-gradient sources influence plume persistence. Rate-limited mass transfer and surface complexation also control U(VI) migration velocity in the sub-oxic Rifle groundwater. Flux of U(VI) from the vadose zone at the Rifle site may be locally important, but it is not the dominant process that sustains the plume. A wide range in microbiologic functional diversity exists at both sites. Strains of Geobacter and other metal reducing bacteria are present at low natural abundance that are capable of enzymatic U(VI) reduction in localized zones of accumulated detrital organic carbon or after organic carbon amendment. Major differences between the

Persistence of uranium groundwater plumes: Contrasting mechanisms at two DOE sites in the groundwater-river interaction zone

NASA Astrophysics Data System (ADS)

Zachara, John M.; Long, Philip E.; Bargar, John; Davis, James A.; Fox, Patricia; Fredrickson, Jim K.; Freshley, Mark D.; Konopka, Allan E.; Liu, Chongxuan; McKinley, James P.; Rockhold, Mark L.; Williams, Kenneth H.; Yabusaki, Steve B.

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (< one pore volume). At the Rifle site, slow oxidation of naturally reduced, contaminant U(IV) in the saturated zone and a continuous influx of U(VI) from natural, up-gradient sources influence plume persistence. Rate-limited mass transfer and surface complexation also control U(VI) migration velocity in the sub-oxic Rifle groundwater. Flux of U(VI) from the vadose zone at the Rifle site may be locally important, but it is not the dominant process that sustains the plume. A wide range in microbiologic functional diversity exists at both sites. Strains of Geobacter and other metal reducing bacteria are present at low natural abundance that are capable of enzymatic U(VI) reduction in localized zones of accumulated detrital organic carbon or after organic carbon amendment. Major differences between

Simulation of Flow and Long-Term Plutonium (Pu) Transport in the Vadose Zone at the Savannah River National Laboratory (SRNL)

NASA Astrophysics Data System (ADS)

Demirkanli, I.; Molz, F. J.; Kaplan, D. I.; Fjeld, R. A.; Serkiz, S. M.

2006-05-01

An improved understanding of flow and radionuclide transport in vadose zone sediments is fundamental to all types of future planning involving radioactive materials. One way to obtain such understanding is to perform long-term experimental studies of Pu transport in complex natural systems. With this in mind, a series of field experiments were initiated at the SRNL in the early 1980s. Lysimeters containing sources of different Pu oxidation states were placed in the shallow subsurface and left open to the natural environment for 2 to 11 years. At the end of the experiments, Pu activities were measured along vertical cores obtained from the lysimeters. Pu distributions were anomalous in nature, with transport from oxidized Pu sources being less than expected, and a small fraction of Pu from reduced sources moving more. Laboratory studies with lysimeter sediments suggested that surface-mediated, oxidation/reduction (redox) reactions could be responsible for the anomalous behavior, and this hypothesis is tested by performing both steady-state and transient Pu transport simulations that include retardation along with first-order redox reactions on mineral surfaces. Based on the simulations, we conclude that the surface-mediated, redox hypothesis is consistent with the observed downward Pu activity profiles in the experiments, and such profiles are captured well by a steady-state, net downward, flow model. (Discussion is presented as to why a steady model appears to work in a highly transient flow environment.) The redox model explains how Pu(V/VI) sources release activity that moves downward more slowly than expected based on adsorptive retardation alone, and how Pu(III/IV) sources result in a small fraction of activity that moves downward more rapidly than expected. The calibrated parameter values were robust and relatively well-defined throughout all four sets of simulations. Pu(V/VI) (i.e., oxidized Pu)retardation factors were about 15, and reduced Pu

Improvements to measuring water flux in the vadose zone.

PubMed

Masarik, Kevin C; Norman, John M; Brye, Kristofor R; Baker, John M

2004-01-01

Evaluating the impact of land use practices on ground water quality has been difficult because few techniques are capable of monitoring the quality and quantity of soil water flow below the root zone without disturbing the soil profile and affecting natural flow processes. A recently introduced method, known as equilibrium tension lysimetry, was a major improvement but it was not a true equilibrium since it still required manual intervention to maintain proper lysimeter suction. We addressed this issue by developing an automated equilibrium tension lysimeter (AETL) system that continuously matches lysimeter tension to soil-water matric potential of the surrounding soil. The soil-water matric potential of the bulk soil is measured with a heat-dissipation sensor, and a small DC pump is used to apply suction to a lysimeter. The improved automated approach reported here was tested in the field for a 12-mo period. Powered by a small 12-V rechargeable battery, the AETLs were able to continuously match lysimeter suction to soil-water matric potential for 2-wk periods with minimal human attention, along with the added benefit of collecting continuous soil-water matric potential data. We also demonstrated, in the laboratory, methods for continuous measurement of water depth in the AETL, a capability that quantifies drainage on a 10-min interval, making it a true water-flux meter. Equilibrium tension lysimeters have already been demonstrated to be a reliable method of measuring drainage flux, and the further improvements have created a more effective device for studying water drainage and chemical leaching through the soil matrix.

Tracer transport in soils and shallow groundwater: model abstraction with modern tools

USDA-ARS?s Scientific Manuscript database

Vadose zone controls contaminant transport from the surface to groundwater, and modeling transport in vadose zone has become a burgeoning field. Exceedingly complex models of subsurface contaminant transport are often inefficient. Model abstraction is the methodology for reducing the complexity of a...

In Situ Thermal Treatment of Chlorinated Solvents: Fundamentals and Field Applications

EPA Pesticide Factsheets

This report contains information about the use of in situ thermal treatment technologies to treat chlorinated solvents in source zones containing free-phase contamination or high concentrations of contaminants.

DEMONSTRATION BULLETIN: IN-SITU VACUUM EXRACTION: TERRA VAC, INC.

EPA Science Inventory

This in-situ vacuum extraction technology is a process for the removal and venting of volatile organic compounds (VOCs) from the vadose or unsaturated zone of soils. Often, these compounds can be removed from the vadose zone before they have a chance to contaminate groundwater. ...

Uncertainty assessment and implications for data acquisition in support of integrated hydrologic models

NASA Astrophysics Data System (ADS)

Brunner, Philip; Doherty, J.; Simmons, Craig T.

2012-07-01

The data set used for calibration of regional numerical models which simulate groundwater flow and vadose zone processes is often dominated by head observations. It is to be expected therefore, that parameters describing vadose zone processes are poorly constrained. A number of studies on small spatial scales explored how additional data types used in calibration constrain vadose zone parameters or reduce predictive uncertainty. However, available studies focused on subsets of observation types and did not jointly account for different measurement accuracies or different hydrologic conditions. In this study, parameter identifiability and predictive uncertainty are quantified in simulation of a 1-D vadose zone soil system driven by infiltration, evaporation and transpiration. The worth of different types of observation data (employed individually, in combination, and with different measurement accuracies) is evaluated by using a linear methodology and a nonlinear Pareto-based methodology under different hydrological conditions. Our main conclusions are (1) Linear analysis provides valuable information on comparative parameter and predictive uncertainty reduction accrued through acquisition of different data types. Its use can be supplemented by nonlinear methods. (2) Measurements of water table elevation can support future water table predictions, even if such measurements inform the individual parameters of vadose zone models to only a small degree. (3) The benefits of including ET and soil moisture observations in the calibration data set are heavily dependent on depth to groundwater. (4) Measurements of groundwater levels, measurements of vadose ET or soil moisture poorly constrain regional groundwater system forcing functions.

Technology summary of the in situ bioremediation demonstration (methane biostimulation) via horizontal wells at the Savannah River Site Integrated Demonstration Project

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hazen, T.C.; Looney, B.B.; Fliermans, C.B.

1994-06-01

The US Department of Energy, Office of Technology Development, has been sponsoring full-scale environmental restoration technology demonstrations for the past 4 years. The Savannah River Site Integrated Demonstration focuses on ``Clean-up of Soils ad Groundwater Contaminated with Chlorinated VOCs.`` Several laboratories including our own had demonstrated the ability of methanotrophic bacteria to completely degrade or mineralize chlorinated solvents, and these bacteria were naturally found in soil and aquifer material. Thus the test consisted of injection of methane mixed with air into the contaminated aquifer via a horizontal well and extraction from the vadose zone via a parallel horizontal well.

Technetium, Iodine, and Chromium Adsorption/Desorption Kd Values for Vadose Zone Pore Water, ILAW Glass, and Cast Stone Leachates Contacting an IDF Sand Sequence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Last, George V.; Snyder, Michelle M.V.; Um, Wooyong

Performance and risk assessments of immobilized low-activity waste (ILAW) at the Integrated Disposal Facility (IDF) have shown that risks to groundwater are quite sensitive to adsorption-desorption interactions occurring in the near- and far-field environment. These interactions between the underlying sediments and the contaminants present in the leachates that descend from the buried glass, secondary waste grouts, and potentially Cast Stone low-activity waste packages have been represented in these assessments using the contaminant distribution coefficient (Kd) construct. Some contaminants (99Tc, 129I, and Cr) present in significant quantities in these wastes have low Kd values and tend to drive risk to publicmore » health and the environment. Relatively small changes in the Kd value can cause relatively large changes in the retardation factor. Thus, even relatively small uncertainty in the Kd value can result in a relatively large uncertainty in the risk determined through performance assessment modeling. The purpose of this study is to further reduce the uncertainty in Kd values for 99Tc, iodine (iodide and iodate), and Cr (chromate; CrO42-) by conducting systematic adsorption-desorption experiments using actual sand-dominated Hanford formation sediments from beneath the IDF and solutions that closely mimic Hanford vadose zone pore water and leachates from Cast Stone and ILAW glass waste forms. Twenty-four batch and 21 flow-through column experiments were conducted, yielding 261 Kd measurements for these key contaminants, and contributing to our understanding for predicting transport from wastes disposed to the IDF. While the batch Kd methodology is not well-suited for measuring Kd values for non-sorbing species (as noted by the U.S. Environmental Protection Agency), the batch Kd results presented here are not wholly inconsistent with the column Kd results, and could be used for sensitivity purposes. Results from the column experiments are consistent with the

Paleomagnetism of Basaltic Lava Flows in Coreholes ICPP 213, ICPP-214, ICPP-215, and USGS 128 Near the Vadose Zone Research Park, Idaho Nuclear Technology and Engineering Center, Idaho National Engineering and Environmental Laboratory, Idaho

USGS Publications Warehouse

Champion, Duane E.; Herman, Theodore C.

2003-01-01

A paleomagnetic study was conducted on basalt from 41 lava flows represented in about 2,300 ft of core from coreholes ICPP-213, ICPP-214, ICPP-215, and USGS 128. These wells are in the area of the Idaho Nuclear Technology and Engineering Center (INTEC) Vadose Zone Research Park within the Idaho National Engineering and Environmental Laboratory (INEEL). Paleomagnetic measurements were made on 508 samples from the four coreholes, which are compared to each other, and to surface outcrop paleomagnetic data. In general, subhorizontal lines of correlation exist between sediment layers and between basalt layers in the area of the new percolation ponds. Some of the basalt flows and flow sequences are strongly correlative at different depth intervals and represent important stratigraphic unifying elements. Some units pinch out, or thicken or thin even over short separation distances of about 1,500 ft. A more distant correlation of more than 1 mile to corehole USGS 128 is possible for several of the basalt flows, but at greater depth. This is probably due to the broad subsidence of the eastern Snake River Plain centered along its topographic axis located to the south of INEEL. This study shows this most clearly in the oldest portions of the cored sections that have differentially subsided the greatest amount.

Origin of increased sulfate in groundwater at the ETF disposal site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thornton, E.C.

1997-09-01

Treated effluent being discharged to the vadose zone from the C-018H Effluent Treatment Facility (ETF) at the Hanford Site has infiltrated vertically to the unconfined aquifer, as indicated by increasing tritium activity levels in the groundwater. Well 699-48-77A, in particular, exhibits increased levels of tritium and also sulfate in the groundwater. The origin of increased sulfate levels in the groundwater is attributed to the dissolution of gypsum as the effluent flows through the vadose zone. This is supported by the observation that sulfate was found to be present in soils collected from the vadose zone at an average value ofmore » about 10.6 ppm. The maximum observed sulfate concentration of 190 mg/L from well 699-48-77A was observed on August 6, 1996, and is less than the maximum value of 879 mg/L that potentially could be achieved if water in the vadose zone was to attain saturation with respect to gypsum and calcite. It is suggested that infiltration rates were high enough that the effluent did not completely equilibrate with gypsum in the vadose zone, and thus, sulfate levels remained below gypsum saturation levels. Sulfate levels appear to be dropping, which may be attributed to the completion of the dissolution of the bulk of gypsum present along the vadose zone flow path traversed by the effluent. Geochemical modeling was undertaken to evaluate the influence of effluent chemistry on sulfate concentration levels in the presence of excess calcite and gypsum. In general, the effect is fairly minor for dilute solutions, but becomes more significant for concentrated solutions.« less

The Vapor-phase Multi-stage CMD Test for Characterizing Contaminant Mass Discharge Associated with VOC Sources in the Vadose Zone: Application to Three Sites in Different Lifecycle Stages of SVE Operations

PubMed Central

Brusseau, M.L.; Mainhagu, J.; Morrison, C.; Carroll, K.C.

2015-01-01

Vapor-phase multi-stage contaminant mass discharge (CMD) tests were conducted at three field sites to measure mass discharge associated with contaminant sources located in the vadose zone. The three sites represent the three primary stages along the soil vapor extraction (SVE) operations lifecycle- pre/initial-SVE, mid-lifecycle, and near-closure. A CMD of 32 g/d was obtained for a site at which soil vapor SVE has been in operation for approximately 6 years, and for which mass removal is currently in the asymptotic stage. The contaminant removal behavior exhibited for the vapor extractions conducted at this site suggests that there is unlikely to be a significant mass of non-vapor-phase contaminant (e.g., DNAPL, sorbed phase) remaining in the advective domains, and that most remaining mass is likely located in poorly accessible domains. Given the conditions for this site, this remaining mass is hypothesized to be associated with the low-permeability (and higher water saturation) region in the vicinity of the saturated zone and capillary fringe. A CMD of 25 g/d was obtained for a site wherein SVE has been in operation for several years but concentrations and mass-removal rates are still relatively high. A CMD of 270 g/d was obtained for a site for which there were no prior SVE operations. The behavior exhibited for the vapor extractions conducted at this site suggest that non-vapor-phase contaminant mass (e.g., DNAPL) may be present in the advective domains. Hence, the asymptotic conditions observed for this site most likely derive from a combination of rate-limited mass transfer from DNAPL (and sorbed) phases present in the advective domain as well as mass residing in lower-permeability (“non-advective”) regions. The CMD values obtained from the tests were used in conjunction with a recently developed vapor-discharge tool to evaluate the impact of the measured CMDs on groundwater quality. PMID:26047819

The vapor-phase multi-stage CMD test for characterizing contaminant mass discharge associated with VOC sources in the vadose zone: Application to three sites in different lifecycle stages of SVE operations.

PubMed

Brusseau, M L; Mainhagu, J; Morrison, C; Carroll, K C

2015-08-01

Vapor-phase multi-stage contaminant mass discharge (CMD) tests were conducted at three field sites to measure mass discharge associated with contaminant sources located in the vadose zone. The three sites represent the three primary stages of the soil vapor extraction (SVE) operations lifecycle-pre/initial-SVE, mid-lifecycle, and near-closure. A CMD of 32g/d was obtained for a site at which soil vapor SVE has been in operation for approximately 6years, and for which mass removal is currently in the asymptotic stage. The contaminant removal behavior exhibited for the vapor extractions conducted at this site suggests that there is unlikely to be a significant mass of non-vapor-phase contaminant (e.g., DNAPL, sorbed phase) remaining in the advective domains, and that most remaining mass is likely located in poorly accessible domains. Given the conditions for this site, this remaining mass is hypothesized to be associated with the low-permeability (and higher water saturation) region in the vicinity of the saturated zone and capillary fringe. A CMD of 25g/d was obtained for a site wherein SVE has been in operation for several years but concentrations and mass-removal rates are still relatively high. A CMD of 270g/d was obtained for a site for which there were no prior SVE operations. The behavior exhibited for the vapor extractions conducted at this site suggest that non-vapor-phase contaminant mass (e.g., DNAPL) may be present in the advective domains. Hence, the asymptotic conditions observed for this site most likely derive from a combination of rate-limited mass transfer from DNAPL (and sorbed) phases present in the advective domain as well as mass residing in lower-permeability ("non-advective") regions. The CMD values obtained from the tests were used in conjunction with a recently developed vapor-discharge tool to evaluate the impact of the measured CMDs on groundwater quality. Copyright © 2015 Elsevier B.V. All rights reserved.

A novel 9 × 9 map-based solvent selection strategy for targeted counter-current chromatography isolation of natural products.

PubMed

Liang, Junling; Meng, Jie; Wu, Dingfang; Guo, Mengzhe; Wu, Shihua

2015-06-26

Counter-current chromatography (CCC) is an efficient liquid-liquid chromatography technique for separation and purification of complex mixtures like natural products extracts and synthetic chemicals. However, CCC is still a challenging process requiring some special technical knowledge especially in the selection of appropriated solvent systems. In this work, we introduced a new 9 × 9 map-based solvent selection strategy for CCC isolation of targets, which permit more than 60 hexane-ethyl acetate-methanol-water (HEMWat) solvent systems as the start candidates for the selection of solvent systems. Among these solvent systems, there are clear linear correlations between partition coefficient (K) and the system numbers. Thus, an appropriate CCC solvent system (i.e., sweet spot for K = 1) may be hit by measurement of k values of the target only in two random solvent systems. Besides this, surprisingly, we found that through two sweet spots, we could get a line ("Sweet line") where there are infinite sweet solvent systems being suitable for CCC separation. In these sweet solvent systems, the target has the same partition coefficient (K) but different solubilities. Thus, the better sweet solvent system with higher sample solubility can be obtained for high capacity CCC preparation. Furthermore, we found that there is a zone ("Sweet zone") where all solvent systems have their own sweet partition coefficients values for the target in range of 0.4 < K< 2.5 or extended range of 0.25 < K < 16. All results were validated by using 14 pure GUESSmix mimic natural products as standards and further confirmed by isolation of several targets including honokiol and magnolol from the extracts of Magnolia officinalis Rehd. Et Wils and tanshinone IIA from Salvia miltiorrhiza Bunge. In practice, it is much easier to get a suitable solvent system only by making a simple screening two to four HEMWat two-phase solvent systems to obtain the sweet line or sweet zone without special knowledge

Borehole environmental tracers for evaluating net infiltration and recharge through desert bedrock

USGS Publications Warehouse

Heilweil, V.M.; Solomon, D.K.; Gardner, P.M.

2006-01-01

Permeable bedrock aquifers in arid regions are being increasingly developed as water supplies, yet little is generally known about recharge processes and spatial and temporal variability. Environmental tracers from boreholes were used in this study to investigate net infiltration and recharge to the fractured Navajo Sandstone aquifer. Vadose zone tracer profiles at the Sand Hollow study site in southwestern Utah look similar to those of desert soils at other sites, indicating the predominance of matrix flow. However, recharge rates are generally higher in the Navajo Sandstone than in unconsolidated soils in similar climates because the sandstone matrix allows water movement but not root penetration. Water enters the vadose zone either as direct infiltration of precipitation through exposed sandstone and sandy soils or as focused infiltration of runoff. Net infiltration and recharge exhibit extreme spatial variability. High-recharge borehole sites generally have large amounts of vadose zone tritium, low chloride concentrations, and small vadose zone oxygen-18 evaporative shifts. Annual net-infiltration and recharge rates at different locations range from about 1 to 60 mm as determined using vadose zone tritium, 0 to 15 mm using vadose zone chloride, and 3 to 60 mm using groundwater chloride. Environmental tracers indicate a cyclical net-infiltration and recharge pattern, with higher rates earlier in the Holocene and lower rates during the late Holocene, and a return to higher rates during recent decades associated with anomalously high precipitation during the latter part of the 20th century. The slightly enriched stable isotopic composition of modern groundwater indicates this recent increase in precipitation may be caused by a stronger summer monsoon or winter southern Pacific El Nin??o storm track. ?? Soil Science Society of America.

Miscellaneous chemical basin expedited site characterization report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riha, B.D.; Pemberton, B.E.; Rossabi, J.

1996-12-01

A total of twenty nine cone penetrometer test (CPT) pushes in three weeks were conducted for vadose zone characterization of the Miscellaneous Chemical Basin (MCB) waste unit at the Savannah River Site. The shallow, unlined basin received liquid chemical wastes over an 18 year period beginning in 1956. This characterization was initiated to determine the vertical and lateral extent of contamination in the vadose zone and to install vadose zone wells for remediation by barometric pumping or active vapor extraction to help prevent further contamination of groundwater. The CPT locations within the waste site were selected based on results frommore » previous shallow soil gas surveys, groundwater contamination data, and the suspected basin center. Geophysical data and soil gas samples were collected at twenty five locations and twenty five vadose zone wells were installed. The wells were screened to target the clay zones and areas of higher soil gas concentrations. The well construction diagrams are provided in Appendix B. Baro-Ball{trademark} valves for enhanced barometric pumping were installed on each well upon completion to immediately begin the remediation treatability study at the site.« less

Infiltration and recharge at Sand Hollow, an upland bedrock basin in southwestern Utah: Chapter I in Ground-water recharge in the arid and semiarid southwestern United States (Professional Paper 1703)

USGS Publications Warehouse

Heilweil, Victor M.; Solomon, D. Kip; Gardner, Philip M.; Stonestrom, David A.; Constantz, Jim; Ferré, Ty P.A.; Leake, Stanley A.

2007-01-01

Permeable bedrock aquifers in arid regions of the southwestern United States are being used increasingly as a source of water for rapidly growing populations, yet in many areas little is known about recharge processes and amounts available for sustainable development. Environmental tracers were used in this study to investigate infiltration and recharge to the Navajo Sandstone at Sand Hollow in the eastern Mojave Desert of southwestern Utah. Average annual precipitation is about 210 millimeters per year. Tracers included bromide, chloride, deuterium, oxygen-18, and tritium. The basin-wide average recharge rate, based on ground-water chloride mass balance, is about 8 millimeters per year, or 4 percent of precipitation. However, infiltration and recharge are highly variable spatially within Sand Hollow. Recharge primarily occurs both as focused infiltration of runoff from areas of outcropping bedrock and as direct infiltration beneath coarse surficial soils. Locations with higher rates generally have lower vadose-zone and ground-water chloride concentrations, smaller vadose-zone oxygen-18 evaporative shifts, and higher ground-water tritium concentrations. Infiltration rates estimated from vadose-zone tritium concentrations at borehole sites within Sand Hollow range from 1 to more than 57 millimeters per year; rates calculated from average vadose-zone chloride concentrations between land surface and the bottom of the chloride bulge range from 0 to 9 millimeters per year; rates calculated from average vadose-zone chloride concentrations below the chloride bulge range from 0.5 to 15 millimeters per year; and rates calculated from ground-water chloride concentrations range from 3 to 60 millimeters per year. A two-end-member deuterium-mixing model indicates that about 85 percent of ground-water recharge in Sand Hollow occurs in the 50 percent of the basin covered by coarser soils and bedrock. Vadose-zone chloride concentrations at individual boreholes represent as much as

Dynamics of Nutrients Transport in Onsite Wastewater Treatment Systems

NASA Astrophysics Data System (ADS)

Toor, G.; De, M.

2013-05-01

Domestic wastewater is abundant in nutrients¬ that originate from various activities in the households. In developed countries, wastewater is largely managed by (1) centralized treatment where wastewater from large population is collected, treated, and discharged and (2) onsite treatment where wastewater is collected from an individual house, treated, and dispersed onsite; this system is commonly known as septic system or onsite wastewater treatment system (OWTS) and consist of a septic tank (collects wastewater) and drain-field (disperses wastewater in soil). In areas with porous sandy soils, the transport of nutrients from drain-field to shallow groundwater is accelerated. To overcome this limitation, elevated disposal fields (commonly called mounds) on top of the natural soil are constructed to provide unsaturated conditions for wastewater treatment. Our objective was to study the dynamics of nitrogen (N) and phosphorus (P) transport in the vadose zone and groundwater in traditional and advanced OWTS. Soil water samples were collected from the vadose zone by using suction cup lysimeters and groundwater samples were collected by using piezometers. Collected samples (wastewater, soil-water, groundwater) were analyzed for various water quality parameters. The pH (4.39-4.78) and EC (0.28-0.34 dS/m) of groundwater was much lower than both wastewater and soil-water. In contrast to >50 mg/L of ammonium-N in wastewater, concentrations in all lysimeters (0.02-0.81 mg/L) and piezometers (0.01-0.82 mg/L) were <1 mg/L; suggesting that >99% disappeared (primarily nitrified) in the vadose zone (<1.05-m soil profile depth). In the vadose zone of advanced system, heterotrophic and autrotrophic denitrification reduced nitrate-N concentrations to <0.12 mg/L, compared with >20 mg/L in the vadose zones of traditional systems (drip dispersal and gravel trench). Concentrations of chloride showed a distinct pattern of nitrate-N breakthrough in vadose zone and groundwater; the

Impact of material heterogeneity on solute transport behavior in the unsaturated zone of the Calcaire de Beauce aquifer (France)

NASA Astrophysics Data System (ADS)

Viel, Emelie; Coquet, Yves

2016-04-01

Since a few decades, the Calcaire de Beauce aquifer is contaminated with nitrate. The nitrate dynamics in the aquifer and in the surface soil are quite well understood, but its transport through the vadose zone remains largely unknown. When models fail to simulate nitrate concentrations in wells, preferential flow or physical non-equilibrium transport in soil and in the vadose zone is usually put forward to explain this failure. To study transport processes in the vadose zone of the Calcaire de Beauce aquifer, undisturbed cores (30 cm length and 20 cm diameter) have been taken below the deepest soil horizon. At the field scale, the vadose zone is composed of powdery limestone spatially very heterogeneous, and including a variable amount of coarse elements. Two columns were selected: column "6" is made of very fine homogeneous limestone whereas column "8" is very heterogeneous with a large proportion of coarse elements. Elution experiments have been performed on both columns. A tracer (Br- or DFBA) in a solution of 5 mM CaCl2 was spread as a pulse on the top of the column with a rainfall simulator. Input flow rate was kept constant for steady state cases, or suddenly closed for flux interruption cases. Outflow was collected as a function of time for tracer concentration measurement. The collected fractions were analyzed by HPLC (High-performance liquid chromatography) with a UV detector. Three types of experiments took place: • For steady state experiments, three rainfall rates, respectively 4, 8, and 16 mm/h, have been used to study the occurrence of immobile water in the columns. The tracer was injected during 120 min followed by CaCl2 tracer-free solution at same flow rate. • For flux-interruption experiments, only the 4 and 8 mm/h rainfall rates were used. The tracer was injected during 120 min, input and output fluxes were then stopped and restarted seven days later with the same flow rate. • For drainage experiments, only the 4 and 8 mm/h rainfall rates

Climate variability controls on unsaturated water and chemical movement, High Plains aquifer, USA

USGS Publications Warehouse

Gurdak, J.J.; Hanson, R.T.; McMahon, P.B.; Bruce, B.W.; McCray, J.E.; Thyne, G.D.; Reedy, R.C.

2007-01-01

Responses in the vadose zone and groundwater to interannual, interdecadal, and multidecadal climate variability have important implications for groundwater resource sustainability, yet they are poorly documented and not well understood in most aquifers of the USA. This investigation systematically examines the role of interannual to multidecadal climate variability on groundwater levels, deep infiltration (3-23 m) events, and downward displacement (>1 m) of chloride and nitrate reservoirs in thick (15-50 m) vadose zones across the regionally extensive High Plains aquifer. Such vadose zone responses are unexpected across much of the aquifer given a priori that unsaturated total-potential profiles indicate upward water movement from the water table toward the root zone, mean annual potential evapotranspiration exceeds mean annual precipitation, and millennia-scale evapoconcentration results in substantial vadose zone chloride and nitrate reservoirs. Using singular spectrum analysis (SSA) to reconstruct precipitation and groundwater level time-series components, variability was identified in all time series as partially coincident with known climate cycles, such as the Pacific Decadal Oscillation (PDO) (10-25 yr) and the El Nin??o/Southern Oscillation (ENSO) (2-6 yr). Using these lag-correlated hydrologic time series, a new method is demonstrated to estimate climate-varying unsaturated water flux. The results suggest the importance of interannual to interdecadal climate variability on water-flux estimation in thick vadose zones and provide better understanding of the climate-induced transients responsible for the observed deep infiltration and chemical-mobilization events. Based on these results, we discuss implications for climate-related sustainability of the High Plains aquifer. ?? Soil Science Society of America.

Spatio-temporal Root Zone Soil Moisture Estimation for Indo - Gangetic Basin from Satellite Derived (AMSR-2 and SMOS) Surface Soil Moisture

NASA Astrophysics Data System (ADS)

Sure, A.; Dikshit, O.

2017-12-01

Root zone soil moisture (RZSM) is an important element in hydrology and agriculture. The estimation of RZSM provides insight in selecting the appropriate crops for specific soil conditions (soil type, bulk density, etc.). RZSM governs various vadose zone phenomena and subsequently affects the groundwater processes. With various satellite sensors dedicated to estimating surface soil moisture at different spatial and temporal resolutions, estimation of soil moisture at root zone level for Indo - Gangetic basin which inherits complex heterogeneous environment, is quite challenging. This study aims at estimating RZSM and understand its variation at the level of Indo - Gangetic basin with changing land use/land cover, topography, crop cycles, soil properties, temperature and precipitation patterns using two satellite derived soil moisture datasets operating at distinct frequencies with different principles of acquisition. Two surface soil moisture datasets are derived from AMSR-2 (6.9 GHz - `C' Band) and SMOS (1.4 GHz - `L' band) passive microwave sensors with coarse spatial resolution. The Soil Water Index (SWI), accounting for soil moisture from the surface, is derived by considering a theoretical two-layered water balance model and contributes in ascertaining soil moisture at the vadose zone. This index is evaluated against the widely used modelled soil moisture dataset of GLDAS - NOAH, version 2.1. This research enhances the domain of utilising the modelled soil moisture dataset, wherever the ground dataset is unavailable. The coupling between the surface soil moisture and RZSM is analysed for two years (2015-16), by defining a parameter T, the characteristic time length. The study demonstrates that deriving an optimal value of T for estimating SWI at a certain location is a function of various factors such as land, meteorological, and agricultural characteristics.

The Relative Importance of the Vadose Zone in Multimedia Risk Assessment Modeling Applied at a National Scale: An Analysis of Benzene Using 3MRA

NASA Astrophysics Data System (ADS)

Babendreier, J. E.

2002-05-01

, along with the conceptual layout of an accompanying java-based paralleling software toolset. Preliminary work is also reported for a scenario involving Benzene disposal that describes the relative importance of the vadose zone in driving risk levels for ecological receptors and human health. Incorporating landfills, waste piles, aerated tanks, surface impoundments, and land application units, the site-based data used in the analysis included 201 national facilities representing 419 site-WMU combinations.

New biphasic solvent system based on cyclopentyl methyl ether for the purification of a non-polar synthetic peptide by pH-zone refining centrifugal partition chromatography.

PubMed

Amarouche, Nassima; Boudesocque, Leslie; Borie, Nicolas; Giraud, Matthieu; Forni, Luciano; Butte, Alessandro; Edwards, Florence; Renault, Jean-Hugues

2014-06-01

A new type 1 ternary biphasic system composed of cyclopentyl methyl ether, dimethylformamide and water was developed, characterized and successfully used for the purification of a lipophilic, protected peptide by pH-zone refining centrifugal partition chromatography. The protected peptide is an 8-mer, key intermediate in bivalirudin (Angiomax®) synthesis and shows a very low solubility in the solvents usually used in liquid chromatography. All ionic groups, except the N-terminal end of the peptide, are protected by a benzyl group. The purification of this peptide was achieved with a purity of about 99.04% and a recovery of 94% using the new ternary biphasic system cyclopentyl methyl ether/dimethylformamide/water (49:40:11, v/v) in the descending pH-zone refining mode with triethylamine (28 mM) as the retainer and methanesulfonic acid (18 mM) as the eluter. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

UZIG USGS research: Advances through interdisciplinary interaction

USGS Publications Warehouse

Nimmo, J.R.; Andraski, Brian J.; Rafael, M.-C.

2009-01-01

BBecause vadose zone research relates to diverse disciplines, applications, and modes of research, collaboration across traditional operational and topical divisions is especially likely to yield major advances in understanding. The Unsaturated Zone Interest Group (UZIG) is an informal organization sponsored by the USGS to encourage and support interdisciplinary collaboration in vadose or unsaturated zone hydrologic research across organizational boundaries. It includes both USGS and non-USGS scientists. Formed in 1987, the UZIG operates to promote communication, especially through periodic meetings with presentations, discussions, and field trips. The 10th meeting of the UZIG at Los Alamos, NM, in August 2007 was jointly sponsored by the USGS and Los Alamos National Laboratory. Presentations at this meeting served as the initial basis for selecting papers for this special section of Vadose Zone Journal, the purpose of which is to present noteworthy cutting-edge unsaturated zone research promoted by, facilitated by, or presented in connection with the UZIG.

Percolation characteristics of solvent invasion in rough fractures under miscible conditions

NASA Astrophysics Data System (ADS)

Korfanta, M.; Babadagli, T.; Develi, K.

2017-10-01

Surface roughness and flow rate effects on the solvent transport under miscible conditions in a single fracture are studied. Surface replicas of seven different rocks (marble, granite, and limestone) are used to represent different surface roughness characteristics each described by different mathematical models including three fractal dimensions. Distribution of dyed solvent is investigated at various flow rate conditions to clarify the effect of roughness on convective and diffusive mixing. After a qualitative analysis using comparative images of different rocks, the area covered by solvent with respect to time is determined to conduct a semi-quantitative analysis. In this exercise, two distinct zones are identified, namely the straight lines obtained for convective (early times) and diffusive (late times) flow. The bending point between these two lines is used to point the transition between the two zones. Finally, the slopes of the straight lines and the bending points are correlated to five different roughness parameters and the rate (Peclet number). It is observed that both surface roughness and flow rate have significant effect on solvent spatial distribution. The largest area covered is obtained at moderate flow rates and hence not only the average surface roughness characteristic is important, but coessentially total fracture surface area needs to be considered when evaluating fluid distribution. It is also noted that the rate effect is critically different for the fracture samples of large grain size (marbles and granite) compared to smaller grain sizes (limestones). Variogram fractal dimension exhibits the strongest correlation with the maximum area covered by solvent, and display increasing trend at the moderate flow rates. Equations with variogram surface fractal dimension in combination with any other surface fractal parameter coupled with Peclet number can be used to predict maximum area covered by solvent in a single fracture, which in turn can be

Single crystal growth of spin-ladder compound La8Cu7O19 by the travelling-solvent floating zone method

NASA Astrophysics Data System (ADS)

Mohan, A.; Singh, S.; Partzsch, S.; Zwiebler, M.; Geck, J.; Wurmehl, S.; Büchner, B.; Hess, C.

2016-08-01

Large single crystals of La8Cu7O19 have been grown using the travelling-solvent floating zone method. A rather high oxygen pressure of 9 bar in the growth chamber and a slow growth speed of 0.5 mm/h were among the most important parameters in stabilizing the growth of this incongruently melting compound. Interestingly, a novel growth scenario has been witnessed. The crystal structure of the grown La8Cu7O19 crystal has been analyzed using single crystal diffractometry to extract important structural parameters of this compound. We find that La8Cu7O19 crystallizes in a monoclinic structure with space group C 2 / c and has the lattice parameters a ≈ 13.83 Å, b ≈ 3.75 Å, c ≈ 34.59 Å, and β ≈ 99.33 °, in good agreement with the data obtained on polycrystalline samples in the literature. The magnetization shows a highly anisotropic behavior, and an anomaly at T ≈103 K.

Hanford Site 100-N Area In Situ Bioremediation of UPR-100-N-17, Deep Petroleum Unplanned Release - 13245

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saueressig, Daniel G.

2013-07-01

In 1965 and 1966, approximately 303 m{sup 3} of Number 2 diesel fuel leaked from a pipeline used to support reactor operations at the Hanford Site's N Reactor. N Reactor was Hanford's longest operating reactor and served as the world's first dual purpose reactor for military and power production needs. The Interim Action Record of Decision for the 100-N Area identified in situ bioremediation as the preferred alternative to remediate the deep vadose zone contaminated by this release. A pilot project supplied oxygen into the vadose zone to stimulate microbial activity in the soil. The project monitored respiration rates asmore » an indicator of active biodegradation. Based on pilot study results, a full-scale system is being constructed and installed to remediate the vadose zone contamination. (authors)« less

Estimation of Hydraulic Properties Influencing Recharge and Contaminant Transport through Complex Vadose Zones by Analyzing Perched Water Data from the 1994 Large-Scale Infiltration Test at the Idaho National Laboratory

NASA Astrophysics Data System (ADS)

Creasey, K. M.; Nimmo, J. R.

2014-12-01

Layers of strong geologic contrast within the vadose zone can control recharge and contaminant transport to underlying aquifers. Above the eastern Snake River Plain Aquifer, multiple sedimentary interbeds are interspersed between fractured basalt. These interbeds have a variety of thicknesses and hydraulic properties, and can impede water flow, which allows perched water to collect on the interbeds. The Large-Scale Infiltration Test (LSIT) of 1994 at the Idaho National Laboratory (INL) maintained a circular pond, 200 meters in diameter, at a constant head for 20 days. Monitoring wells were arranged in circles of different radii around and within the pond, and perched water levels on a major sedimentary interbed, 55 meters below ground surface, were measured over time. Data showed that water formed a mound on the interbed before seeping through the interbed. Such behavior is consistent with a hypothesis of rapid flow through the fractured basalt being impeded by the sedimentary interbed. In 2014, the USGS, in cooperation with the U.S. Department of Energy, used a modified version of a Hantush (1967) equation to model the time-dependent perched water table heights from the LSIT as a function of radial distance from the pond center. The modeled volume change between time-steps and the known inflows to the pond were used in a mass balance to estimate the time-varying volume of water seeping through the interbed. This volume of water, the height of perched water, and the interbed thickness were used in Darcy's Law to estimate the effective saturated hydraulic conductivity of the impeding interbed. Results indicate a slightly higher effective conductivity than laboratory measurements of small core samples taken from the interbed, reflecting the presence of fractures or other heterogeneities that facilitate field-scale flow through the interbed. Applied to other locations, this method can improve estimates of recharge and contaminant transport to underlying aquifers.

Continuous countercurrent membrane column for the separation of solute/solvent and solvent/solvent systems

DOEpatents

Nerad, Bruce A.; Krantz, William B.

1988-01-01

A reverse osmosis membrane process or hybrid membrane - complementary separator process for producing enriched product or waste streams from concentrated and dilute feed streams for both solvent/solvent and solute/solvent systems is described.

Geothermal evolution of an intruded dike in the rift zone of Kilauea volcano, Hawaii from VLF and self-potential measurements

NASA Astrophysics Data System (ADS)

Davis, Paul M.

2015-09-01

Self-potential (SP) and VLF measurements were made in 1973, 1975, 1995, 1997 and 2012 across a basaltic dike that intruded into the Koae fault zone of Kilauea volcano, Hawaii in May 1973. The SP anomaly remained strong throughout. In 2012 it was at about 60% of the strength it had in 1973. In contrast, the VLF anomaly, though diminished, was still observable in 1995/1997, but by 2012 it had disappeared. A hydrothermal dike model, with parameters calibrated by modeling the solidification of Kilauea Iki lava lake, is used to calculate temperatures and conductivity variation. Following Jaeger's (1957) method, we find that the time in years for a dike of width W (m) to solidify is 0.0075W2. Thus, a 1 m dike solidifies within the first few days, and after 39 years is only tens of degrees above ambient. Given the orders of magnitude difference between the conductivities of wet and dry basalt, we infer, that after solidification, the VLF anomalies were caused by induction in a localized veil of wet, hot basalt enveloping the dike, that was generated initially by condensation of steam, and subsequently by condensation of evaporated water as temperatures reduced. The conductivity anomaly persisted until the mid-nineties. By 2012, temperatures and condensation were too small for a VLF signal. The persistent SP anomaly is attributed to localized fluid disruption, with evaporation mainly at the water table and in the vadose zone. Streaming potentials are associated with evaporative circulation in the vadose zone. Next to the dike a positive potential is generated by upward flow of moisture-laden air, with a smaller negative potential on its flanks from downward infiltrating rainwater. The analysis indicates that the combination of SP and VLF measurements can characterize the evolving geothermal regime of intrusions above the water table.

An Isotopic view of water and nitrogen transport through the ...

EPA Pesticide Factsheets

Groundwater nitrate contamination affects thousands of households in Oregon’s southern Willamette Valley and many more across the Pacific Northwest. The southern Willamette Valley Groundwater Management Area (SWV GWMA) was established in 2004 due to nitrate levels in the groundwater exceeding the human health standard of 10 mg nitrate-N L-1. Much of the nitrogen inputs to the GWMA comes from agricultural nitrogen use, and thus efforts to reduce N inputs to groundwater are focused upon improving N management. However, the effectiveness of these improvements on groundwater quality is unclear because of the complexity of nutrient transport through the vadose zone and long groundwater residence times. Our objective was to focus on vadose zone transport and understand the dynamics and timing of N and water movement below the rooting zone in relation to N management and water inputs. Stable isotopes are a powerful tool for tracking water movement, and understanding nitrogen transformations within the vadose zone. In partnership with local farmers, and state agencies, we established lysimeters and groundwater wells in multiple agricultural fields in the GWMA, and have monitored nitrate, nitrate isotopes, and water isotopes weekly for multiple years. Our results indicate that vadose zone transport is highly complex, and the residence time of water collected in lysimeters was much longer than expected. While input precipitation water isotopes were highly variab

An Isotopic view of water and nitrogen transport through the ...

EPA Pesticide Factsheets

Background/Question/MethodsGroundwater nitrate contamination affects thousands of households in Oregon's southern Willamette Valley and many more across the Pacific Northwest. The southern Willamette Valley Groundwater Management Area (SWV GWMA) was established in 2004 due to nitrate levels in the groundwater exceeding the human health standard of 10 mg nitrate-N L-1. Much of the nitrogen inputs to the GWMA comes from agricultural nitrogen use, and thus efforts to reduce N inputs to groundwater are focused upon improving N management. However, the effectiveness of these improvements on groundwater quality is unclear because of the complexity of nutrient transport through the vadose zone and long groundwater residence times. Our objective was to focus on vadose zone transport and understand the dynamics and timing of N and water movement below the rooting zone in relation to N management and water inputs. Stable isotopes are a powerful tool for tracking water movement, and understanding nitrogen transformations within the vadose zone. In partnership with local farmers, and state agencies, we established lysimeters and groundwater wells in multiple agricultural fields in the GWMA, and have monitored nitrate, nitrate isotopes, and water isotopes weekly for multiple years Results/ConclusionsOur results indicate that vadose zone transport is highly complex, and the residence time of water collected in lysimeters was much longer than expected. While input precipitatio

Vadose Zone as a Potential Carbon Source: a Look at Seasonal Spikes in Hyporheic Zone pCO2

NASA Astrophysics Data System (ADS)

Brandes, J.

2016-12-01

Connections between soils, terrestrial streams and the atmosphere are not yet thoroughly understood as contributing factors to the global carbon budget. We collected data from an undisturbed soil column adjacent to a small stream in a forested watershed in the H. J. Andrews Experimental Forest in the Western Cascades of Oregon in the United States. Our data includes: CO2 (ppm); temperature (oC); depth below water table (m); and soil moisture (cm3/cm3) and spans approximately one year. We are analyzing the data using the gradient method and have observed distinct seasonal patterns which may support previous research describing temporal processes. We can expect to see changing soil moisture characteristics which may promote either vertical CO2 diffusion out of the surface or vertical/lateral advection into subsurface flow. We hypothesize that there is flushing of soil CO2 into the hyporheic zone during precipitation events following soil CO2 buildup.

Part 1: Vadose-zone column studies of toluene (enhanced bioremediation) in a shallow unconfined aquifer

USGS Publications Warehouse

Tindall, J.A.; Friedel, M.J.; Szmajter, R.J.; Cuffin, S.M.

2005-01-01

The objectives of the laboratory study described in this paper were (1) to determine the effectiveness of four nutrient solutions and a control in stimulating the microbial degradation of toluene in the unsaturated zone as an alternative to bioremediation methodologies such as air sparging, in situ vitrification, or others (Part I), and (2) to compare the effectiveness of the addition of the most effective nutrient solution from Part I (modified Hoagland type, nitrate-rich) and hydrogen peroxide (H2O2) on microbial degradation of toluene for repeated, simulated spills in the unsaturated zone (Part II). For Part 1, fifteen columns (30-cm diameter by 150-cm height), packed with air-dried, 0.25-mm, medium-fine sand, were prepared to simulate shallow unconfined aquifer conditions. Toluene (10 mL) was added to the surface of each column, and soil solution and soil gas samples were collected from the columns every third day for 21 days. On day 21, a second application of toluene (10 mL) was made, and the experiment was run for another 21 days. Solution 4 was the most effective for microbial degradation in Part I. For Part II, three columns were designated nutrient-rich 3-day toluene columns and received toluene injections every 3 days; three columns were designated as nutrient-rich 7-day columns and received toluene injections every 7 days; and two columns were used as controls to which no nutrient was added. As measured by CO2 respiration, the initial benefits for aerobic organisms from the O2 enhancement were sustained by the bacteria for only a short period of time (about 8 days). Degradation benefits from the nutrient solution were sustained throughout the experiment. The O2 and nutrient-enhanced columns degraded significantly more toluene than the control columns when simulating repeated spills onto the unsaturated zone, and demonstrated a potentially effective in situ bioremediation technology when used immediately or within days after a spill. The combined usage

Solvent wash solution

DOEpatents

Neace, J.C.

1984-03-13

A process is claimed for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 vol % of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Solvent wash solution

DOEpatents

Neace, James C.

1986-01-01

Process for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 volume percent of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Transport of Nitrogen and Phosphorus from Onsite Wastewater Treatment Systems to Shallow Groundwater

NASA Astrophysics Data System (ADS)

Toor, G.

2014-12-01

The knowledge about the nutrients transport from the vadose zone of onsite wastewater treatment systems (commonly called septic systems) is crucial to protect groundwater quality as 25% of US population uses septic systems to discharge household wastewater. For example, our preliminary data showed that about 47% of applied water was recovered at 60-cm below drainfield of septic systems. This implies that contaminants present in wastewater, if not attenuated in the vadose zone, can be transported to shallow groundwater. This presentation will focus on the biophysical and hydrologic controls on the transport of nitrogen (N) and phosphorus (P) from the vadose of two conventional (drip dispersal, gravel trench) and an advanced (with aerobic and anaerobic medias) system. These systems were constructed using two rows of drip pipe (37 emitters/mound) placed 0.3 m apart in the center of 6 m x 0.6 m drainfield. Each system received 120 L of wastewater per day. During 20-month period (May 2012 to December 2013), soil-water samples were collected from the vadose zone using suction cup lysimeters installed at 0.30, 0.60, and 1.05 m depth and groundwater samples were collected from piezometers installed at 3-3.30 m depth below the drainfield. A complimentary 1-year study using smaller drainfields (0.5 m long, 0.9 m wide, 0.9 m high) was conducted to obtain better insights in the vadose zone. A variety of instruments (multi-probe sensors, suction cup lysimeters, piezometers, tensiometers) were installed in the vadose zones. Results showed that nitrification controlled N evolution in drainfield and subsequent transport of N plumes (>10 mg/L) into groundwater. Most of the wastewater applied soluble inorganic P (>10 mg/L) was quickly attenuated in the drainfield due to fixation (sorption, precipitation) in the vadose zone (<0.10 mg/L), which was further reduced to <0.05 mg/L in groundwater. The hydrologic controls (primarily rainfall during June-September) facilitated transport of

Factors Effecting the Fate and Transport of CL-20 in the Vadose Zone and Groundwater: Final Report 2002 - 2004 SERDP Project CP-1255

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; Riley, Robert G.; Devary, Brooks J.

2005-06-01

This SERDP-funded project was initiated to investigate the fate of CL-20 in the subsurface environment, with a focus on identification and quantification of geochemical and microbial reactions of CL-20. CL-20 can be released to the surface and subsurface terrestrial environment by: a) manufacturing processes, b) munition storage, and c) use with low order detonation or unexploded ordnance. The risk of far-field subsurface migration was assessed through labora-tory experiments with a variety of sediments and subsurface materials to quantify processes that control CL-20 sorption-limited migration and degradation. Results of this study show that CL-20 will exhibit differing behavior in the subsurfacemore » terrestrial environment: 1. CL-20 on the sediment surface will photodegrade and interact with plants/animals (described in other SERDP projects CU 1254, 1256). CL-20 will exhibit greater sorption in humid sediments to organic matter. Transport will be solubility limited (i.e., low CL-20 aqueous solubility). 2. CL-20 infiltration into soils (<2 m) from spills will be subject to sorption to soil organic matter (if present), and low to high biodegradation rates (weeks to years) depending on the microbial population (greater in humid environment). 3. CL-20 in the vadose zone (>2 m) will be, in most cases, subject to low sorption and low degradation rates, so would persist in the subsurface environment and be at risk for deep migration. Low water content in arid regions will result in a decrease in both sorption and the degradation rate. Measured degradation rates in unsaturated sediments of years would result in significant subsurface migration distances. 4. CL-20 in groundwater will be subject to some sorption but likely very slow degradation rates. CL-20 sorption will be greater than RDX. Most CL-20 degradation will be abiotic (ferrous iron and other transition metals), because most deep subsurface systems have extremely low natural microbial populations

Transuranic Contamination in Sediment and Groundwater at the U.S. DOE Hanford Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cantrell, Kirk J.

2009-08-20

A review of transuranic radionuclide contamination in sediments and groundwater at the DOE’s Hanford Site was conducted. The review focused primarily on plutonium-239/240 and americium-241; however, other transuranic nuclides were discussed as well, including neptunium-237, plutonium-238, and plutonium-241. The scope of the review included liquid process wastes intentionally disposed to constructed waste disposal facilities such as trenches and cribs, burial grounds, and unplanned releases to the ground surface. The review did not include liquid wastes disposed to tanks or solid wastes disposed to burial grounds. It is estimated that over 11,800 Ci of plutonium-239, 28,700 Ci of americium-241, and 55more » Ci of neptunium-237 have been disposed as liquid waste to the near surface environment at the Hanford Site. Despite the very large quantities of transuranic contaminants disposed to the vadose zone at Hanford, only minuscule amounts have entered the groundwater. Currently, no wells onsite exceed the DOE derived concentration guide for plutonium-239/240 (30 pCi/L) or any other transuranic contaminant in filtered samples. The DOE derived concentration guide was exceeded by a small fraction in unfiltered samples from one well (299-E28-23) in recent years (35.4 and 40.4 pCi/L in FY 2006). The primary reason that disposal of these large quantities of transuranic radionuclides directly to the vadose zone at the Hanford Site has not resulted in widespread groundwater contamination is that under the typical oxidizing and neutral to slightly alkaline pH conditions of the Hanford vadose zone, transuranic radionuclides (plutonium and americium in particular) have a very low solubility and high affinity for surface adsorption to mineral surfaces common within the Hanford vadose zone. Other important factors are the fact that the vadose zone is typically very thick (hundreds of feet) and the net infiltration rate is very low due to the desert climate. In some cases where

Enhanced Amendment Delivery to Subsurface Using Shear Thinning Fluid and Aqueous Foam for Metal, Radionuclide, and NAPL Remediation

NASA Astrophysics Data System (ADS)

Zhong, L.; Szecsody, J.; Li, X.; Oostrom, M.; Truex, M.

2010-12-01

In many contamination sites, removal of contaminants by any active remediation efforts is not practical due to the high cost and technological limitations. Alternatively, in situ remediation is expected to be the most important remediation strategy. Delivery of reactive amendment to the contamination zone is essential for the reactions between the contaminants and remedial amendments to proceed in situ. It is a challenge to effectively deliver remedial amendment to the subsurface contamination source areas in both aquifer and vadose zone. In aquifer, heterogeneity induces fluid bypassing the low-permeability zones, resulting in certain contaminated areas inaccessible to the remedial amendment delivered by water injection, thus inhibiting the success of remedial operations. In vadose zone in situ remediation, conventional solution injection and infiltration for amendment delivery have difficulties to achieve successful lateral spreading and uniform distribution of the reactive media. These approaches also tend to displace highly mobile metal and radionuclide contaminants such as hexavalent chromium [Cr(VI)] and technetium (Tc-99), causing spreading of contaminations. Shear thinning fluid and aqueous foam can be applied to enhance the amendment delivery and improve in situ subsurface remediation efficiency under aquifer and vadose zone conditions, respectively. Column and 2-D flow cell experiments were conducted to demonstrate the enhanced delivery and improved remediation achieved by the application of shear thinning fluid and foam injection at the laboratory scale. Solutions of biopolymer xanthan gum were used as the shear thinning delivering fluids. Surfactant sodium lauryl ether sulfate (STEOL CS-330) was the foaming agent. The shear thinning fluid delivery (STFD) considerably improved the sweeping efficiency over a heterogeneous system and enhanced the non-aqueous liquid phase (NAPL) removal. The delivery of amendment into low-perm zones (LPZs) by STFD also

Reproducible research in vadose zone sciences

USDA-ARS?s Scientific Manuscript database

A significant portion of present-day soil and Earth science research is computational, involving complex data analysis pipelines, advanced mathematical and statistical models, and sophisticated computer codes. Opportunities for scientific progress are greatly diminished if reproducing and building o...

Thixotropic gel for vadose zone remediation

DOEpatents

Riha, Brian D.

2012-07-03

A thixotropic gel suitable for use in subsurface bioremediation is provided along with a process of using the gel. The thixotropic gel provides a non-migrating injectable substrate that can provide below ground barrier properties. In addition, the gel components provide for a favorable environment in which certain contaminants are preferentially sequestered in the gel and subsequently remediated by either indigenous or introduced microorganisms.

Thixotropic gel for vadose zone remediation

DOEpatents

Rhia, Brian D [Augusta, GA

2011-03-01

A thixotropic gel suitable for use in subsurface bioremediation is provided along with a process of using the gel. The thixotropic gel provides a non-migrating injectable substrate that can provide below ground barrier properties. In addition, the gel components provide for a favorable environment in which certain contaminants are preferentially sequestered in the gel and subsequently remediated by either indigenous or introduced microorganisms.

Thixotropic gel for vadose zone remediation

DOEpatents

Riha, Brian D.; Looney, Brian B.

2015-10-27

A thixotropic gel suitable for use in subsurface bioremediation is provided along with a process of using the gel. The thixotropic gel provides a non-migrating injectable substrate that can provide below ground barrier properties. In addition, the gel components provide for a favorable environment in which certain contaminants are preferentially sequestered in the gel and subsequently remediated by either indigenous or introduced microorganisms.

Vadose zone flow convergence test suite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Butcher, B. T.

Performance Assessment (PA) simulations for engineered disposal systems at the Savannah River Site involve highly contrasting materials and moisture conditions at and near saturation. These conditions cause severe convergence difficulties that typically result in unacceptable convergence or long simulation times or excessive analyst effort. Adequate convergence is usually achieved in a trial-anderror manner by applying under-relaxation to the Saturation or Pressure variable, in a series of everdecreasing RELAxation values. SRNL would like a more efficient scheme implemented inside PORFLOW to achieve flow convergence in a more reliable and efficient manner. To this end, a suite of test problems that illustratemore » these convergence problems is provided to facilitate diagnosis and development of an improved convergence strategy. The attached files are being transmitted to you describing the test problem and proposed resolution.« less

Laboratory and numerical experiments on water and energy fluxes during freezing and thawing in the unsaturated zone

NASA Astrophysics Data System (ADS)

Holländer, Hartmut; Montasir Islam, Md.; Šimunek, Jirka

2017-04-01

Frozen soil has a major effect in many hydrologic processes, and its effects are difficult to predict. A prime example is flood forecasting during spring snowmelt within the Canadian Prairies. One key driver for the extent of flooding is the antecedent soil moisture and the possibility for water to infiltrate into frozen soils. Therefore, these situations are crucial for accurate flood prediction during every spring. The main objective of this study was to evaluate the water flow and heat transport within HYDRUS-1D version 4.16 and with Hansson's model, which is a detailed freezing/thawing module (Hansson et al., 2004), to predict the impact of frozen and partly frozen soil on infiltration. We developed a standardized data set of water flow and heat transport into (partial) frozen soil by laboratory experiments using fine sand. Temperature, soil moisture, and percolated water were observed at different freezing conditions as well as at thawing conditions. Significant variation in soil moisture was found between the top and the bottom of the soil column at the starting of the thawing period. However, with increasing temperature, the lower depth of the soil column showed higher moisture as the soil became enriched with moisture due to the release of heat by soil particles during the thawing cycle. We applied vadose zone modeling using the results from the laboratory experiments. The simulated water content by HYDRUS-1D 4.16 showed large errors compared to the observed data showing by negative Nash-Sutcliffe Efficiency. Hansson's model was not able to predict soil water fluxes due to its unstable behavior (Šimunek et al., 2016). The soil temperature profile simulated using HYDRUS-1D 4.16 was not able to predict the release of latent heat during the phase change of water that was visible in Hansson's model. Hansson's model includes the energy gain/loss due to the phase change in the amount of latent energy stored in the modified heat transport equation. However, in

Effect of Selected Modeling Assumptions on Subsurface Radionuclide Transport Projections for the Potential Environmental Management Disposal Facility at Oak Ridge, Tennessee

DOE Office of Scientific and Technical Information (OSTI.GOV)

Painter, Scott L.

2016-06-28

The Department of Energy’s Office of Environmental Management recently revised a Remedial Investigation/ Feasibility Study (RI/FS) that included an analysis of subsurface radionuclide transport at a potential new Environmental Management Disposal Facility (EMDF) in East Bear Creek Valley near Oak Ridge, Tennessee. The effect of three simplifying assumptions used in the RI/FS analyses are investigated using the same subsurface pathway conceptualization but with more flexible modeling tools. Neglect of vadose zone dispersion was found to be conservative or non-conservative, depending on the retarded travel time and the half-life. For a given equilibrium distribution coefficient, a relatively narrow range of half-lifemore » was identified for which neglect of vadose zone transport is non-conservative and radionuclide discharge into surface water is non-negligible. However, there are two additional conservative simplifications in the reference case that compensate for the non-conservative effect of neglecting vadose zone dispersion: the use of a steady infiltration rate and vadose zone velocity, and the way equilibrium sorption is used to represent transport in the fractured material of the saturated aquifer. With more realistic representations of all three processes, the RI/FS reference case was found to either provide a reasonably good approximation to the peak concentration or was significantly conservative (pessimistic) for all parameter combinations considered.« less

Non-steady state partitioning of dry cleaning surfactants between tetrachloroethylene (PCE) and water in porous media.

PubMed

Hoggan, James L; Bae, Keonbeom; Kibbey, Tohren C G

2007-08-15

Trapped organic solvents, in both the vadose zone and below the water table, are frequent sources of environmental contamination. A common source of organic solvent contamination is spills, leaks, and improper solvent disposal associated with dry cleaning processes. Dry cleaning solvents, such as tetrachloroethylene (PCE), are typically enhanced with the addition of surfactants to improve cleaning performance. The objective of this work was to examine the partitioning behavior of surfactants from PCE in contact with water. The relative rates of surfactants partitioning and PCE dissolution are important for modeling the behavior of waste PCE in the subsurface, in that they influence the interfacial tension of the PCE, and how (or if) interfacial tension changes over time in the subsurface. The work described here uses a flow-through system to examine simultaneous partitioning and PCE dissolution in a porous medium. Results indicate that both nonylphenol ethoxylate nonionic surfactants and a sulfosuccinate anionic surfactant partition out of residual PCE much more rapidly than the PCE dissolves, suggesting that in many cases interfacial tension changes caused by partitioning may influence infiltration and distribution of PCE in the subsurface. Non-steady-state partitioning is found to be well-described by a linear driving force model incorporating measured surfactant partition coefficients.

Potential Habitats for Exotic Life Within the Life Supporting Zone

NASA Astrophysics Data System (ADS)

Leitner, Johannes J.; Firneis, Maria G.; Hitzenberger, Regina

2010-05-01

Questions like "Are we alone in the universe?", "How unique is Earth as a planet?" or "How unique is water-based life in the universe?" still are nowhere near of being answered. In recent years, discussions on these topics are more and more influenced by questions whether water is really the only possible solvent, or which conditions are necessary for life to evolve in planetary habitats. A change in our present geocentric mindset on the existence of life is required, in order to address these new questions [see also 1]. In May 2009 a new research platform at the University of Vienna was initiated in order to contribute to the solution of these questions. One task is to find essential biomarkers relevant to the problem of the detection of exotic life. In this context exotic life means: life, which is not necessarily based on a double bond between carbon and oxygen (C=O) and not on water as the only possible solvent. At present little is known about metabolistic systems, which are not based on C=O or on metabolisms which are operative in alternative solvents and a high effort of future laboratory work is necessary to open this window for looking for exotic life. To address the whole spectrum of life the concept of a general life supporting zone is introduced in order to extend the classical habitable zone (which is based on liquid water on a planetary surface, [2]). The life supporting zone of a planetary system is composed of different single "habitable zones" for the liquid phases of specific solvents and composites between water and other solvents. Besides exoplanetary systems which seem to be the most promising place for exotic life in our present understanding, some potential places could also exist within our Solar System and habitats like the subsurface of Enceladus, liquid ethane/methane lakes on Titan or habitable niches in the Venus atmosphere will also be taken into account. A preliminary list of appropriate solvents and their abundances in the Solar

Modeling Water Flux at the Base of the Rooting Zone for Soils with Varying Glacial Parent Materials

NASA Astrophysics Data System (ADS)

Naylor, S.; Ellett, K. M.; Ficklin, D. L.; Olyphant, G. A.

2013-12-01

Soils of varying glacial parent materials in the Great Lakes Region (USA) are characterized by thin unsaturated zones and widespread use of agricultural pesticides and nutrients that affect shallow groundwater. To better our understanding of the fate and transport of contaminants, improved models of water fluxes through the vadose zones of various hydrogeologic settings are warranted. Furthermore, calibrated unsaturated zone models can be coupled with watershed models, providing a means for predicting the impact of varying climate scenarios on agriculture in the region. To address these issues, a network of monitoring sites was developed in Indiana that provides continuous measurements of precipitation, potential evapotranspiration (PET), soil volumetric water content (VWC), and soil matric potential to parameterize and calibrate models. Flux at the base of the root zone is simulated using two models of varying complexity: 1) the HYDRUS model, which numerically solves the Richards equation, and 2) the soil-water-balance (SWB) model, which assumes vertical flow under a unit gradient with infiltration and evapotranspiration treated as separate, sequential processes. Soil hydraulic parameters are determined based on laboratory data, a pedo-transfer function (ROSETTA), field measurements (Guelph permeameter), and parameter optimization. Groundwater elevation data are available at three of six sites to establish the base of the unsaturated zone model domain. Initial modeling focused on the groundwater recharge season (Nov-Feb) when PET is limited and much of the annual vertical flux occurs. HYDRUS results indicate that base of root zone fluxes at a site underlain by glacial ice-contact parent materials are 48% of recharge season precipitation (VWC RMSE=8.2%), while SWB results indicate that fluxes are 43% (VWC RMSE=3.7%). Due in part to variations in surface boundary conditions, more variable fluxes were obtained for a site underlain by alluvium with the SWB model (68

Environmental factors controlling transient and seasonal changes of trace gases within shallow vadose zone

NASA Astrophysics Data System (ADS)

Pla, Concepcion; Galiana-Merino, Juan Jose; Cuezva, Soledad; Fernandez-Cortes, Angel; Garcia-Anton, Elena; Cuevas, Jaime; Cañaveras, Juan Carlos; Sanchez-Moral, Sergio; Benavente, David

2014-05-01

Shallow vadose environments below soil, mainly caves, show significant seasonal and even daily variations in gas composition of ground air, which involves the exchange of large amounts of gases, e.g. greenhouse gases (GHGs) as CO2 or CH4, with the lower troposphere. To understand better the role of caves as a sink or depot of GHGs, geochemical tracing of air (atmosphere, soil and ground air) was performed at Rull cave (southeast Spain) by monitoring CH4, CO2 and the stable carbon isotopic delta13C[CO2] using cavity ring-down spectroscopy (CRDS). A comprehensive microclimatic monitoring of exterior and cave atmosphere was simultaneously conducted to GHGs-tracking, including factors as temperature, barometric pressure, relative humidity and concentration of CO2 and 222Rn. The analysis of the measured data allows understanding outgassing and isolation processes taking place in the karst cavity. Annual patterns of gases behaviour can be distinguished, depending on the prevailing relationship between outer atmosphere, indoor atmosphere and soil system. Cave air temperature fluctuates around 15.7 ºC and relative humidity remains higher than 96% the whole annual cycle. The mean concentration of 222Rn is 1584 Bq m-3 while CO2 remains 1921 ppm. When external temperature is higher of indoor temperature (April-October), the highest levels of both trace gases are reached, while levels drop to its lowest values in the coldest months. Preliminary results obtained show an annual variation in concentration of CO2 inside the cave between 3300 ppm and 900 ppm, whereas corresponding isotopic signal delta13CO2 varies between -24‰ and -21‰. The results have been studied by Keeling model that approximates the isotopic signal of the source contribution in a resulting air mix. The values registered inside the cave were represented joined to results for exterior air (average values round 410 ppm of CO2 and -9 ‰ for delta13C). Value obtained is -27‰ pointing to a high influence of

Travelling-solvent floating-zone growth of the dilutely Co-doped spin-ladder compound Sr14(Cu, Co)24O41

NASA Astrophysics Data System (ADS)

Bag, Rabindranath; Karmakar, Koushik; Singh, Surjeet

2017-01-01

We present here crystal growth of dilutely Co-doped spin-ladder compounds Sr14(Cu 1-x, Cox)24O41 (x = 0, 0.01, 0.03, 0.05, 0.1) using the Travelling Solvent Floating Zone (TSFZ) technique associated with an image furnace. We carried out detailed microstructure and compositional analysis. The microstructure of the frozen-in FZ revealed two bands: a lower band consisting of well-aligned single-crystalline stripes of the phase Sr14(Cu, Co)24O41 embedded in the eutectic mixture of composition SrO 18% and (Cu, Co)O 82%; and an upper band consisting of a criss-crossed pattern of these stripes. These analyses were also employed to determine the distribution coefficient of the dopants in Sr14Cu24O41. The distribution coefficient turned out to be close to 1, different from Sr2CuO3 reported previously where Co tend to accumulate in the molten zone. Direct access to the composition of the frozen-in zone eliminated any previous ambiguities associated with the composition of the peritectic point of Sr14Cu24O41; and also the eutectic point in the binary SrO-CuO phase diagram. The lattice parameters show an anisotropic variation upon Co-doping with parameters a and b increasing, c decreasing; and with an overall decrease of the unit cell volume. Magnetic susceptibility measurements were carried out on the pristine and the Co-doped crystals along the principal crystallographic axes. The spin susceptibility of the x = 0.01 crystal exhibits a strong anisotropy, which is in stark contrast with the isotropic behaviour of the pristine crystal. This anisotropy seems to arise from the intradimer exchange interaction as inferred from the anisotropy of the dimer contribution to the susceptibility of the Co-doped crystal. The Curie-tail in the magnetic susceptibility of Sr14(Cu 1-x, Cox)24O41 (x = 0, 0.01, 0.03, 0.05, 0.1) crystals (field applied parallel to the ladder) was found to scale with Co-doping - the scaling is employed to confirm a homogeneous distribution of Co in a x = 0

Carbon dioxide, ground air and carbon cycling in Gibraltar karst

NASA Astrophysics Data System (ADS)

Mattey, D. P.; Atkinson, T. C.; Barker, J. A.; Fisher, R.; Latin, J.-P.; Durrell, R.; Ainsworth, M.

2016-07-01

We put forward a general conceptual model of CO2 behaviour in the vadose zone of karst aquifers, based on physical principles of air flow through porous media and caves, combined with a geochemical interpretation of cave monitoring data. This 'Gibraltar model' links fluxes of water, air and carbon through the soil with the porosity of the vadose zone, the circulation of ground air and the ventilation of caves. Gibraltar hosts many natural caves whose locations span the full length and vertical range of the Rock. We report results of an 8-year monitoring study of carbon in soil organic matter and bedrock carbonate, dissolved inorganic carbon in vadose waters, and gaseous CO2 in soil, cave and ground air. Results show that the regime of cave air CO2 results from the interaction of cave ventilation with a reservoir of CO2-enriched ground air held within the smaller voids of the bedrock. The pCO2 of ground air, and of vadose waters that have been in close contact with it, are determined by multiple factors that include recharge patterns, vegetation productivity and root respiration, and conversion of organic matter to CO2 within the soil, the epikarst and the whole vadose zone. Mathematical modelling and field observations show that ground air is subject to a density-driven circulation that reverses seasonally, as the difference between surface and underground temperatures reverses in sign. The Gibraltar model suggests that cave air pCO2 is not directly related to CO2 generated in the soil or the epikarstic zone, as is often assumed. Ground air CO2 formed by the decay of organic matter (OM) washed down into the deeper unsaturated zone is an important additional source of pCO2. In Gibraltar the addition of OM-derived CO2 is the dominant control on the pCO2 of ground air and the Ca-hardness of waters within the deep vadose zone. The seasonal regime of CO2 in cave air depends on the position of a cave in relation to the density-driven ground air circulation pattern which

Optimization of buffer injection for the effective bioremediation of chlorinated solvents in aquifers

NASA Astrophysics Data System (ADS)

Brovelli, A.; Robinson, C.; Barry, A.; Kouznetsova, I.; Gerhard, J.

2008-12-01

Various techniques have been proposed to enhance biologically-mediated reductive dechlorination of chlorinated solvents in the subsurface, including the addition of fermentable organic substrate for the generation of H2 as an electron donor. One rate-limiting factor for enhanced dechlorination is the pore fluid pH. Organic acids and H+ ions accumulate in dechlorination zones, generating unfavorable conditions for microbial activity (pH < 6.5). The pH variation is a nonlinear function of the amount of reduced chlorinated solvents, and is affected by the organic material fermented, the chemical composition of the pore fluid and the soil's buffering capacity. Consequently, in some cases enhanced remediation schemes rely on buffer injection (e.g., bicarbonate) to alleviate this problem, particularly in the presence of solvent nonaqueous phase liquid (NAPL) source zones. However, the amount of buffer required - particularly in complex, evolving biogeochemical environments - is not well understood. To investigate this question, this work builds upon a geochemical numerical model (Robinson et al., Science of the Total Environment, submitted), which computes the amount of additional buffer required to maintain the pH at a level suitable for bacterial activity for batch systems. The batch model was coupled to a groundwater flow/solute transport/chemical reaction simulator to permit buffer optimization computations within the context of flowing systems exhibiting heterogeneous hydraulic, physical and chemical properties. A suite of simulations was conducted in which buffer optimization was examined within the bounds of the minimum concentration necessary to sustain a pH favorable to microbial activity and the maximum concentration to avoid excessively high pH values (also not suitable to bacterial activity) and mineral precipitation (e.g., calcite, which may lead to pore-clogging). These simulations include an examination of the sensitivity of this buffer concentration range

Hydrogen donor solvent coal liquefaction process

DOEpatents

Plumlee, Karl W.

1978-01-01

An indigenous hydrocarbon product stream boiling within a range of from about C.sub.1 -700.degree. F., preferably C.sub.1 -400.degree. F., is treated to produce an upgraded hydrocarbon fuel component and a component which can be recycled, with a suitable donor solvent, to a coal liquefaction zone to catalyze the reaction. In accordance therewith, a liquid hydrocarbon fraction with a high end boiling point range up to about 700.degree. F., preferably up to about 400.degree. F., is separated from a coal liquefaction zone effluent, the separated fraction is contacted with an alkaline medium to provide a hydrocarbon phase and an aqueous extract phase, the aqueous phase is neutralized, and contacted with a peroxygen compound to convert indigenous components of the aqueous phase of said hydrocarbon fraction into catalytic components, such that the aqueous stream is suitable for recycle to the coal liquefaction zone. Naturally occurring phenols and alkyl substituted phenols, found in the aqueous phase, are converted, by the addition of hydroxyl constituents to phenols, to dihydroxy benzenes which, as disclosed in copending Application Ser. Nos. 686,813 now U.S. Pat. No. 4,049,536; 686,814 now U.S. Pat. No. 4,049,537; 686,827 now U.S. Pat. No. 4,051,012 and 686,828, K. W. Plumlee et al, filed May 17, 1976, are suitable hydrogen transfer catalysts.

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

Water chemistry at Snowshoe Mountain, Colorado: mixed processes in a common bedrock

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.

2001-01-01

At Snowshoe Mountain the primary bedrock is quite homogeneous, but weathering processes vary as waters moves through the soils, vadose zone and phreatic zone of the subsurface. In the thin soil, physical degradation of tuff facilitates preferential dissolution of potassium ion from glass within the rock matrix, while other silicate minerals remain unaltered. In the vadose zone, in the upper few meters of fractured bedrock, dilute water infiltrates during spring snowmelt and summer storms, leading to preferential dissolution of augite exposed on fracture surfaces. Deeper yet, in the phreatic zone of the fractured bedrock, Pleistocene calcite fracture fillings dissolve, and dioctahedral and trioctahedral clays form as penetrative weathering alters feldspar and pyroxene. Alkalinity is generated and silica concentrations are buffered by mineral alteration reactions.

Compound-specific isotope analysis (CSIA) for assessing pesticide dynamics in soil and vadose zone

NASA Astrophysics Data System (ADS)

Torrentó, Clara; Bakkour, Rani; Melsbach, Aileen; Ponsin, Violaine; Lihl, Christina; Prasuhn, Volker; Hofstetter, Thomas B.; Elsner, Martin; Hunkeler, Daniel

2017-04-01

A lysimeter facility was used to study long-term pesticide fate and transport through two different soils. The present investigation focuses on some commonly and worldwide used herbicides for weed control on corn (atrazine, acetochlor and metolachlor) and sugar beet (chloridazon), together with their main degradation products. Since some degradation products are found more frequently and at higher concentrations that their parent compounds, there is growing environmental concern. The fate of these metabolites is, however, not well-understood. Twelve weighing lysimeters filled with two typical arable soils in Switzerland (a well-drained sandy loam cambisol developed from a stony alluvium-"gravel soil"- and a poorly-drained loam cambisol developed from moraine deposits -"moraine soil"-) were cropped with corn in the first and third seasons, and sugar beet in the second one. Three types of experiments were performed: (1) herbicides application at the surface simulating the common application scenario, (2) herbicides injection at a depth of 40 cm for simulating high preferential transport through the topsoil and assessing the dynamics below the root zone, and (3) metabolites (2,6-dichlorobenzamide, desphenylchloridazon and desethylatrazine) application at the surface to simulate rapid generation of transformation products from the parent compounds. Leachate was collected and the concentration of the applied substances and main degradation products was determined. Since assessing transport and fate of micropollutants in the environment is extremely difficult because transformation processes are slow and may not become evident from analysis of concentrations, multi-element (C, N, Cl) compound-specific isotope analysis (CSIA) is also being used. With both surface application and depth injection, compound breakthrough by preferential as well as matrix flow was observed. A few days after their application, significant infiltration of the herbicides took place by

Used Solvent Testing and Reclamation. Volume 2. Vapor Degreasing and Precision Cleaning Solvents

DTIC Science & Technology

1988-12-01

of 5 to 500 ppm in halogenated solvents using Karl - Fischer reagent. Arbitrary criteria to identify a spent solvent have evolved in various industries... methods of managing waste solvent. Some DOD installations are reclaiming used solvents rather than discarding them. Reclamation is feasible because the...most E E CT E reliable methods for testing solvent quality. Further testing isnecessary for chlorinated solvents to determine the inhibitor con- FEB 24

Solvent/Non-Solvent Sintering To Make Microsphere Scaffolds

NASA Technical Reports Server (NTRS)

Laurencin, Cato T.; Brown, Justin L.; Nair, Lakshmi

2011-01-01

A solvent/non-solvent sintering technique has been devised for joining polymeric microspheres to make porous matrices for use as drug-delivery devices or scaffolds that could be seeded with cells for growing tissues. Unlike traditional sintering at elevated temperature and pressure, this technique is practiced at room temperature and pressure and, therefore, does not cause thermal degradation of any drug, protein, or other biochemical with which the microspheres might be loaded to impart properties desired in a specific application. Also, properties of scaffolds made by this technique are more reproducible than are properties of comparable scaffolds made by traditional sintering. The technique involves the use of two miscible organic liquids: one that is and one that is not a solvent for the affected polymer. The polymeric microspheres are placed in a mold having the size and shape of the desired scaffold, then the solvent/non-solvent mixture is poured into the mold to fill the void volume between the microspheres, then the liquid mixture is allowed to evaporate. Some of the properties of the resulting scaffold can be tailored through choice of the proportions of the liquids and the diameter of the microspheres.

Solvent exposure and related work practices amongst apprentice spray painters in automotive body repair workshops.

PubMed

Winder, C; Turner, P J

1992-08-01

As part of a multidisciplinary study into the health effects of solvents, workplace assessments and airborne solvent vapour monitoring was conducted in 46 spray painting workshops in the Sydney metropolitan area. Breathing-zone samples were taken from 50 apprentices and 14 experienced spray painters. An interview schedule was developed to obtain information about the use of acrylic or two-pack paint systems, the use of engineering controls, the use of personal protective equipment and the availability of material safety data sheets. Contaminants typical of the chemical products used in this industry were encountered (aromatic hydrocarbons, C5-C7 aliphatic hydrocarbons, ketones, esters). The results of airborne solvent monitoring indicate a total solvent exposure in the range 1-99% of a combined Worksafe Australia exposure standard, with a mean of 19%. Solvent exposure was highest when spraying acrylic paint in the open workshop and lowest when spraying two pack paint in a spray booth. Much the same personal protective equipment was available in all workshops, but wide variation in its use was observed. Material safety data sheets were not observed in any of the workshops.

Exploring strategies to remove contaminants from subsurface plumes: iron-bearing materials and calcite

NASA Astrophysics Data System (ADS)

Lawter, A.; Qafoku, N. P.; Garcia, W.; Lee, B.; Freedman, V. L.

2017-12-01

At the Hanford site in eastern Washington, depending on the particular waste site, radionuclide (Tc99/I129) laden liquid waste was not of a sufficient volume to carry the contamination through the vadose zone to the groundwater. Contaminants are therefore retained in the vadose zone, which represents a continuous source of these contaminants to groundwater through flux created by precipitation recharge. Deployment of treatment technologies in the vadose zone that will intercept flow from vadose zone recharge and sequester contaminants is needed for future groundwater protection. In this study, first we tested zero valent iron (ZVI) and sulfur modified iron (SMI) to determine the feasibility of using these materials to intercept Tc migrating from the vadose zone into the groundwater. Secondly, this study focused on testing the ZVI and SMI in conjunction with several potential amendments needed for capture of additional contaminants present (e.g., IO3) to immobilize contaminants both individually and combined. Previous testing has shown removal of IO3 by incorporation into calcite; these experiments test the effect of ZVI/SMI on the efficiency of the removal of IO3 by calcite and vice versa. Preliminary results have shown strong removal of high Tc concentrations (i.e., 22 ppm or 44 ppm) at solid to solution ratios of 1 g to 100 mL, but when the solid and the Tc concentration was scaled down to more field relevant conditions (i.e., 0.42 ppm), the Tc removal was slower and the amount of Tc removed (per gram of Fe solid) was decreased. In some tests, results indicated that there is no interference from IO3 on Tc removal, but presence of ZVI/SMI has a negative impact on the removal of IO3 by calcite incorporation, likely due to the fast reduction of iodate to iodide by the ZVI/SMI (iodide is usually not incorporated into calcite).

Mechanisms of recharge in a fractured porous rock aquifer in a semi-arid region

NASA Astrophysics Data System (ADS)

Manna, Ferdinando; Walton, Kenneth M.; Cherry, John A.; Parker, Beth L.

2017-12-01

Eleven porewater profiles in rock core from an upland exposed sandstone vadose zone in southern California, with thickness varying between 10 and 62 m, were analyzed for chloride (Cl) concentration to examine recharge mechanisms, estimate travel times in the vadose zone, assess spatial and temporal variability of recharge, and determine effects of land use changes on recharge. As a function of their location and the local terrain, the profiles were classified into four groups reflecting the range of site characteristics. Century- to millennium-average recharge varied from 4 to 23 mm y-1, corresponding to <1-5% of the average annual precipitation (451 mm over the 1878-2016 period). Based on the different average Cl concentrations in the vadose zone and in groundwater, the contribution of diffuse flow (estimated at 80%) and preferential flow (20%) to the total recharge was quantified. This model of dual porosity recharge was tested by simulating transient Cl transport along a physically based narrow column using a discrete fracture-matrix numerical model. Using a new approach based on partitioning both water and Cl between matrix and fracture flow, porewater was dated and vertical displacement rates estimated to range in the sandstone matrix from 3 to 19 cm y-1. Moreover, the temporal variability of recharge was estimated and, along each profile, past recharge rates calculated based on the sequence of Cl concentrations in the vadose zone. Recharge rates increased at specific times coincident with historical changes in land use. The consistency between the timing of land use modifications and changes in Cl concentration and the match between observed and simulated Cl concentration values in the vadose zone provide confidence in porewater age estimates, travel times, recharge estimates, and reconstruction of recharge histories. This study represents an advancement of the application of the chloride mass balance method to simultaneously determine recharge mechanisms and

Process for solvent refining of coal using a denitrogenated and dephenolated solvent

DOEpatents

Garg, Diwakar; Givens, Edwin N.; Schweighardt, Frank K.

1984-01-01

A process is disclosed for the solvent refining of non-anthracitic coal at elevated temperatures and pressure in a hydrogen atmosphere using a hydrocarbon solvent which before being recycled in the solvent refining process is subjected to chemical treatment to extract substantially all nitrogenous and phenolic constituents from the solvent so as to improve the conversion of coal and the production of oil in the solvent refining process. The solvent refining process can be either thermal or catalytic. The extraction of nitrogenous compounds can be performed by acid contact such as hydrogen chloride or fluoride treatment, while phenolic extraction can be performed by caustic contact or contact with a mixture of silica and alumina.

Dendrochemistry of multiple releases of chlorinated solvents at a former industrial site

USGS Publications Warehouse

Balouet, Jean Christophe; Burken, Joel G.; Karg, Frank; Vroblesky, Don; Smith, Kevin T.; Grudd, Hakan; Rindby, Anders; Beaujard, Francois; Chalot, Michel

2012-01-01

Trees can take up and assimilate contaminants from the soil, subsurface, and groundwater. Contaminants in the transpiration stream can become bound or incorporated into the annual rings formed in trees of the temperate zones. The chemical analysis of precisely dated tree rings, called dendrochemistry, can be used to interpret past plant interactions with contaminants. This investigation demonstrates that dendrochemistry can be used to generate historical scenarios of past contamination of groundwater by chlorinated solvents at a site in Verl, Germany. Increment cores from trees at the Verl site were collected and analyzed by energy-dispersive X-ray fluorescence (EDXRF) line scanning. The EDXRF profiles showed four to six time periods where tree rings had anomalously high concentrations of chlorine (Cl) as an indicator of potential contamination by chlorinated solvents.

Solvent-Ion Interactions in Salt Water: A Simple Experiment.

ERIC Educational Resources Information Center

Willey, Joan D.

1984-01-01

Describes a procedurally quick, simple, and inexpensive experiment which illustrates the magnitude and some effects of solvent-ion interactions in aqueous solutions. Theoretical information, procedures, and examples of temperature, volume and hydration number calculations are provided. (JN)

Self-potential investigations of a gravel bar in a restored river corridor

USGS Publications Warehouse

Linde, N.; Doetsch, J.; Jougnot, D.; Genoni, O.; Durst, Y.; Minsley, B.J.; Vogt, T.; Pasquale, N.; Luster, J.

2011-01-01

Self-potentials (SP) are sensitive to water fluxes and concentration gradients in both saturated and unsaturated geological media, but quantitative interpretations of SP field data may often be hindered by the superposition of different source contributions and time-varying electrode potentials. Self-potential mapping and close to two months of SP monitoring on a gravel bar were performed to investigate the origins of SP signals at a restored river section of the Thur River in northeastern Switzerland. The SP mapping and subsequent inversion of the data indicate that the SP sources are mainly located in the upper few meters in regions of soil cover rather than bare gravel. Wavelet analyses of the time-series indicate a strong, but non-linear influence of water table and water content variations, as well as rainfall intensity on the recorded SP signals. Modeling of the SP response with respect to an increase in the water table elevation and precipitation indicate that the distribution of soil properties in the vadose zone has a very strong influence. We conclude that the observed SP responses on the gravel bar are more complicated than previously proposed semi-empiric relationships between SP signals and hydraulic head or the thickness of the vadose zone. We suggest that future SP monitoring in restored river corridors should either focus on quantifying vadose zone processes by installing vertical profiles of closely spaced SP electrodes or by installing the electrodes within the river to avoid signals arising from vadose zone processes and time-varying electrochemical conditions in the vicinity of the electrodes. ?? 2011 Author(s).

An analytical solution for predicting the transient seepage from a subsurface drainage system

NASA Astrophysics Data System (ADS)

Xin, Pei; Dan, Han-Cheng; Zhou, Tingzhang; Lu, Chunhui; Kong, Jun; Li, Ling

2016-05-01

Subsurface drainage systems have been widely used to deal with soil salinization and waterlogging problems around the world. In this paper, a mathematical model was introduced to quantify the transient behavior of the groundwater table and the seepage from a subsurface drainage system. Based on the assumption of a hydrostatic pressure distribution, the model considered the pore-water flow in both the phreatic and vadose soil zones. An approximate analytical solution for the model was derived to quantify the drainage of soils which were initially water-saturated. The analytical solution was validated against laboratory experiments and a 2-D Richards equation-based model, and found to predict well the transient water seepage from the subsurface drainage system. A saturated flow-based model was also tested and found to over-predict the time required for drainage and the total water seepage by nearly one order of magnitude, in comparison with the experimental results and the present analytical solution. During drainage, a vadose zone with a significant water storage capacity developed above the phreatic surface. A considerable amount of water still remained in the vadose zone at the steady state with the water table situated at the drain bottom. Sensitivity analyses demonstrated that effects of the vadose zone were intensified with an increased thickness of capillary fringe, capillary rise and/or burying depth of drains, in terms of the required drainage time and total water seepage. The analytical solution provides guidance for assessing the capillary effects on the effectiveness and efficiency of subsurface drainage systems for combating soil salinization and waterlogging problems.

Self-potential investigations of a gravel bar in a restored river corridor

USGS Publications Warehouse

Linde, N.; Doetsch, J.; Jougnot, D.; Genoni, O.; Durst, Y.; Minsley, Burke J.; Vogt, T.; Pasquale, N.; Luster, J.

2011-01-01

 Self-potentials (SP) are sensitive to water fluxes and concentration gradients in both saturated and unsaturated geological media, but quantitative interpretations of SP field data may often be hindered by the superposition of different source contributions and time-varying electrode potentials. Self-potential mapping and close to two months of SP monitoring on a gravel bar were performed to investigate the origins of SP signals at a restored river section of the Thur River in northeastern Switzerland. The SP mapping and subsequent inversion of the data indicate that the SP sources are mainly located in the upper few meters in regions of soil cover rather than bare gravel. Wavelet analyses of the time-series indicate a strong, but non-linear influence of water table and water content variations, as well as rainfall intensity on the recorded SP signals. Modeling of the SP response with respect to an increase in the water table elevation and precipitation indicate that the distribution of soil properties in the vadose zone has a very strong influence. We conclude that the observed SP responses on the gravel bar are more complicated than previously proposed semi-empiric relationships between SP signals and hydraulic head or the thickness of the vadose zone. We suggest that future SP monitoring in restored river corridors should either focus on quantifying vadose zone processes by installing vertical profiles of closely spaced SP electrodes or by installing the electrodes within the river to avoid signals arising from vadose zone processes and time-varying electrochemical conditions in the vicinity of the electrodes.

Activated Persulfate Treatment of 1,4-Dioxane in the Presence of Chlorinated Solvent Co-contaminants

NASA Astrophysics Data System (ADS)

Boving, T. T.; Eberle, D. E. H.; Ball, R.

2014-12-01

1,4-dioxane is an emerging groundwater contaminant and a likely human carcinogen. Due to its history as a stabilizer in chlorinated solvents, 1,4-dioxane is often found as a co-contaminant at solvent releases sites such as landfills, solvent recycling facilities, vapor decreasing operations, and fire-training areas. Historically, 1,4-dioxane was not routinely analyzed for at solvent release sites. The lack of analyses and the limitations of the analyses that were performed (i.e. high reporting limits) means that the scale of 1,4-dioxane subsurface contamination is still emerging. With the number of known 1,4-dioxane sites increasing, the need for cost effective 1,4-dioxane remediation technologies is rising as well. Remediation strategies that are capable of treating both 1,4-dioxane as well as chlorinated co-contaminants are of particular importance, especially when treating mixed-waste source zones. In the present study, we examined the fate of 1,4-dioxane during the targeted remediation of aqueous phase volatile organic compounds (VOC) using an activated persulfate based ISCO method (OxyZone®). Bench scale laboratory experiments are used to evaluate the treatability of 1,4-dioxane both as a single compound and in the presence of trichloroethene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA). Possible dependencies on oxidant concentration and reaction kinetics were studied. Preliminary results are promising and show that OxyZone® is persistent and long lived, with oxidation of 1,4-dioxane continuing more than 12 days after initial dosage, even at dilute oxidant concentrations. The oxidative destruction of 1,4-dioxane, TCE and 1,1,1-TCA in single compound batch systems followed pseudo first order reaction kinetics. The rate of oxidation for each contaminant increased linearly with increasing persulfate concentration over the range of oxidant concentrations tested. The rate of oxidative destruction, from most easily degraded to least was: TCE > 1,4-Dioxane > 1

Deep Vadose Zone Flow and Transport Behavior at T-Tunnel Complex, Rainier Mesa, Nevada National Security Site

NASA Astrophysics Data System (ADS)

Parashar, R.; Reeves, D. M.

2010-12-01

Rainier Mesa, a tuffaceous plateau on the Nevada National Security Site, has been the location of numerous subsurface nuclear tests conducted in a series of tunnel complexes located approximately 450 m below the top of the mesa and 500 m above the regional groundwater flow system. The tunnels were constructed near the middle of an 800 m Tertiary sequence of faulted, low-permeability welded and non-welded bedded, vitric, and zeolitized tuff units. Water levels from wells in the vicinity of the T-tunnel complex indicate the presence of a perched saturation zone located approximately 100 m above the T-tunnel complex. This upper zone of saturation extends downward through most of the Tertiary sequence. The groundwater table is located at an elevation of 1300 m within a thrust sheet of Paleozoic carbonates, corresponding to the lower carbonate aquifer hydrostratigraphic unit (LCA3). The LCA3 is considered to be hydraulically connected to the Death Valley regional flow system. The objective of this project is to simulate complex downward patterns of fluid flow and radionuclide transport from the T-tunnel complex through the matrix and fault networks of the Tertiary tuff units to the water table. We developed an improved fracture characterization and mapping methodology consisting of displacement-length scaling relationships, simulation of realistic fault networks based on site-specific data, and the development of novel fracture network upscaling techniques that preserves fracture network flow and transport properties on coarse continuum grid. Development of upscaling method for fracture continua is based on the concepts of discrete fracture network modeling approach which performs better at honoring network connectivity and anisotropy of sparse networks in comparison to other established methods such as a tensor approach. Extensive flow simulations in the dual-continuum framework demonstrate that the characteristics of fault networks strongly influences the saturation

Effect of saline waste solution infiltration rates on uranium retention and spatial distribution in Hanford sediments.

PubMed

Wan, Jiamin; Tokunaga, Tetsu K; Kim, Yongman; Wang, Zheming; Lanzirotti, Antonio; Saiz, Eduardo; Serne, R Jeffrey

2008-03-15

The accidental overfilling of waste liquid from tank BX-102 at the Hanford Site in 1951 put about 10 t of U(VI) into the vadose zone. In order to understand the dominant geochemical reactions and transport processes that occurred during the initial infiltration and to help understand current spatial distribution, we simulated the waste liquid spilling event in laboratory sediment columns using synthesized metal waste solution. We found that, as the plume propagated through sediments, pH decreased greatly (as much as 4 units) at the moving plume front. Infiltration flow rates strongly affect U behavior. Slower flow rates resulted in higher sediment-associated U concentrations, and higher flow rates (> or =5 cm/day) permitted practically unretarded U transport. Therefore, given the very high Ksat of most of Hanford formation, the low permeability zones within the sediment could have been most important in retaining high concentrations of U during initial release into the vadose zone. Massive amount of colloids, including U-colloids, formed at the plume fronts. Total U concentrations (aqueous and colloid) within plume fronts exceeded the source concentration by up to 5-fold. Uranium colloid formation and accumulation at the neutralized plume front could be one mechanism responsible for highly heterogeneous U distribution observed in the contaminated Hanford vadose zone.

Using Airborne Geophysics to Improve the Management of Produced Water from Coal Bed Natural Gas Extraction in the Powder River Basin

NASA Astrophysics Data System (ADS)

Sams, J.; Lipinski, B.; Hammack, R.; Veloski, G.; Ackman, T.; Harbert, B.

2005-05-01

The Powder River Basin (PRB) of Wyoming and Montana has seen a boom in drilling for coalbed natural gas (CBNG), the natural gas contained in coal seams. Large quantities of water are coproduced during the extraction process. The water is currently managed by land application (irrigation), returned to shallow groundwater aquifers via infiltration basins, directly discharged to ephemeral or perennial streams, or injected into the deep subsurface via injection wells. At present, there are over 28,000 CBNG wells permitted or drilled in the PRB and it is estimated that another 50,000 to 100,000 new wells will be drilled in the future. Produced water management is a major challenge to the oil and gas industry as well as federal and state regulators. The purpose of this study was to evaluate the use of airborne electromagnetic (AEM) methods for the large-scale mapping of vadose zone properties. The base maps derived from the AEM data show the location of conductive anomalies within the vadose zone. These conductive anomalies have been identified as conditions related to soil properties, geologic features, saturated areas, and seepage zones. In the PRB, the data can be used to identify suitable locations for constructing impoundments in areas that avoid highly conductive soils where infiltrating water may leach salts through the vadose zone and into shallow aquifers. Hydrologic changes within the vadose zone were evaluated by completing an AEM survey in 2003 and 2004 over two coincident spatial areas. The data were analyzed to determine statistical relationships between the data sets, in particular data outliers which may represent areas of significant change between each year. Some outliers plot near areas of CBNG development. Ultimately, it is hoped that the information from these surveys will identify cost effective treatment or disposal options for produced water that address both production and environmental issues.

Estimation of the nucleation kinetics for the anti-solvent crystallisation of paracetamol in methanol/water solutions

NASA Astrophysics Data System (ADS)

Ó'Ciardhá, Clifford T.; Frawley, Patrick J.; Mitchell, Niall A.

2011-08-01

In this work the primary nucleation kinetics have been estimated for the anti-solvent crystallisation of paracetamol in methanol-water solutions from metastable zone widths (MSZW) and induction times at 25 °C. Laser back-scattering via a focused beam reflectance Measurement (FBRM ®) is utilised to detect the onset of nucleation. The theoretical approach of Kubota was employed to estimate the nucleation kinetics, which accounts for the sensitivity of the nucleation detection technique. This approach is expanded in this work to analyse the induction time for an anti-solvent crystallisation process. Solvent composition is known to have a significant impact on the measured induction times and MSZW. The induction time in this paper was measured from 40% to 70% mass water and the MSZW is measured from 40% to 60% mass water. The primary focus of the paper was to gauge the extent of how solvent composition affects nucleation kinetics so that this effect may be incorporated into a population balance model. Furthermore, the effects of solvent composition on the estimated nucleation rates are investigated. The primary nucleation rates were found to decrease with dynamic solvent composition, with the extent of their reduction linked to the gradient of the solubility curve. Finally, both MSZW and induction time methods have been found to produce similar estimates for the nucleation parameters.

Occupational solvent exposure and cognition

PubMed Central

Sabbath, E.L.; Glymour, M.M.; Berr, C.; Singh-Manoux, A.; Zins, M.; Goldberg, M.

2012-01-01

Objective: Chronic occupational solvent exposure is associated with long-term cognitive deficits. Cognitive reserve may protect solvent-exposed workers from cognitive impairment. We tested whether the association between chronic solvent exposure and cognition varied by educational attainment, a proxy for cognitive reserve. Methods: Data were drawn from a prospective cohort of French national gas and electricity (GAZEL) employees (n = 4,134). Lifetime exposure to 4 solvent types (chlorinated solvents, petroleum solvents, benzene, and nonbenzene aromatic solvents) was assessed using a validated job-exposure matrix. Education was dichotomized at less than secondary school or below. Cognitive impairment was defined as scoring below the 25th percentile on the Digit Symbol Substitution Test at mean age 59 (SD 2.8; 88% of participants were retired at testing). Log-binomial regression was used to model risk ratios (RRs) for poor cognition as predicted by solvent exposure, stratified by education and adjusted for sociodemographic and behavioral factors. Results: Solvent exposure rates were higher among less-educated patients. Within this group, there was a dose-response relationship between lifetime exposure to each solvent type and RR for poor cognition (e.g., for high exposure to benzene, RR = 1.24, 95% confidence interval 1.09–1.41), with significant linear trends (p < 0.05) in 3 out of 4 solvent types. Recency of solvent exposure also predicted worse cognition among less-educated patients. Among those with secondary education or higher, there was no significant or near-significant relationship between any quantification of solvent exposure and cognition. Conclusions: Solvent exposure is associated with poor cognition only among less-educated individuals. Higher cognitive reserve in the more-educated group may explain this finding. PMID:22641403

Solvents and sustainable chemistry

PubMed Central

Welton, Tom

2015-01-01

Solvents are widely recognized to be of great environmental concern. The reduction of their use is one of the most important aims of green chemistry. In addition to this, the appropriate selection of solvent for a process can greatly improve the sustainability of a chemical production process. There has also been extensive research into the application of so-called green solvents, such as ionic liquids and supercritical fluids. However, most examples of solvent technologies that give improved sustainability come from the application of well-established solvents. It is also apparent that the successful implementation of environmentally sustainable processes must be accompanied by improvements in commercial performance. PMID:26730217

NEPTUNIUM SOLVENT EXTRACTION PROCESS

DOEpatents

Dawson, L.R.; Fields, P.R.

1959-10-01

The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

Quantifying the Influence of Near-Surface Water-Energy Budgets on Soil Thermal Properties Using a Network of Coupled Meteorological and Vadose Zone Instrument Arrays in Indiana, USA

NASA Astrophysics Data System (ADS)

Naylor, S.; Gustin, A. R.; Ellett, K. M.

2012-12-01

Weather stations that collect reliable, sustained meteorological data sets are becoming more widely distributed because of advances in both instrumentation and data server technology. However, sites collecting soil moisture and soil temperature data remain sparse with even fewer locations where complete meteorological data are collected in conjunction with soil data. Thanks to the advent of sensors that collect continuous in-situ thermal properties data for soils, we have gone a step further and incorporated thermal properties measurements as part of hydrologic instrument arrays in central and northern Indiana. The coupled approach provides insights into the variability of soil thermal conductivity and diffusivity attributable to geologic and climatological controls for various hydrogeologic settings. These data are collected to facilitate the optimization of ground-source heat pumps (GSHPs) in the glaciated Midwest by establishing publicly available data that can be used to parameterize system design models. A network of six monitoring sites was developed in Indiana. Sensors that determine thermal conductivity and diffusivity using radial differential temperature measurements around a heating wire were installed at 1.2 meters below ground surface— a typical depth for horizontal GSHP systems. Each site also includes standard meteorological sensors for calculating reference evapotranspiration following the methods by the Food and Agriculture Organization (FAO) of the United Nations. Vadose zone instrumentation includes time domain reflectometry soil-moisture and temperature sensors installed at 0.3-meter depth intervals down to a 1.8-meter depth, in addition to matric potential sensors at 0.15, 0.3, 0.6, and 1.2 meters. Cores collected at 0.3-meter intervals were analyzed in a laboratory for grain size distribution, bulk density, thermal conductivity, and thermal diffusivity. Our work includes developing methods for calibrating thermal properties sensors based on

Solvent cleaning system and method for removing contaminants from solvent used in resin recycling

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2009-01-06

A two step solvent and carbon dioxide based system that produces essentially contaminant-free synthetic resin material and which further includes a solvent cleaning system for periodically removing the contaminants from the solvent so that the solvent can be reused and the contaminants can be collected and safely discarded in an environmentally safe manner.

Natural Attenuation in Streambed Sediment Receiving Chlorinated Solvents from Underlying Fracture Networks

DOE PAGES

Şimşir, Burcu; Yan, Jun; Im, Jeongdae; ...

2017-03-22

Contaminant discharge from fractured bedrock formations remains a remediation challenge. Here, we applied an integrated approach to assess the natural attenuation potential of sediment that forms the transition zone between upwelling groundwater from a chlorinated solvent-contaminated fractured bedrock aquifer and the receiving surface water. In situ measurements demonstrated that reductive dechlorination in the sediment attenuated chlorinated compounds before reaching the water column. Microcosms established with creek sediment or in situ incubated Bio-Sep beads degraded C 1-C 3 chlorinated solvents to less-chlorinated or innocuous products. Quantitative PCR and 16S rRNA gene amplicon sequencing revealed the abundance and spatial distribution of knownmore » dechlorinator biomarker genes within the creek sediment and demonstrated that multiple dechlorinator populations degrading chlorinatedC 1-C 3 alkanes and alkenes co-inhabit the sediment. Phylogenetic classification of bacterial and archaeal sequences indicated a relatively uniform distribution over spatial (300 m horizontally) scale, but Dehalococcoides and Dehalobacter were more abundant in deeper sediment, where 5.7 ± 0.4 × 10 5 and 5.4 ± 0.9 × 10 6 16S rRNA gene copies per g of sediment, respectively, were measured. The microbiological and hydrogeological characterization demonstrated that microbial processes at the fractured bedrock-sediment interface were crucial for preventing contaminants reaching the water column, emphasizing the relevance of this critical zone environment for contaminant attenuation.« less

Natural Attenuation in Streambed Sediment Receiving Chlorinated Solvents from Underlying Fracture Networks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Şimşir, Burcu; Yan, Jun; Im, Jeongdae

Contaminant discharge from fractured bedrock formations remains a remediation challenge. Here, we applied an integrated approach to assess the natural attenuation potential of sediment that forms the transition zone between upwelling groundwater from a chlorinated solvent-contaminated fractured bedrock aquifer and the receiving surface water. In situ measurements demonstrated that reductive dechlorination in the sediment attenuated chlorinated compounds before reaching the water column. Microcosms established with creek sediment or in situ incubated Bio-Sep beads degraded C 1-C 3 chlorinated solvents to less-chlorinated or innocuous products. Quantitative PCR and 16S rRNA gene amplicon sequencing revealed the abundance and spatial distribution of knownmore » dechlorinator biomarker genes within the creek sediment and demonstrated that multiple dechlorinator populations degrading chlorinatedC 1-C 3 alkanes and alkenes co-inhabit the sediment. Phylogenetic classification of bacterial and archaeal sequences indicated a relatively uniform distribution over spatial (300 m horizontally) scale, but Dehalococcoides and Dehalobacter were more abundant in deeper sediment, where 5.7 ± 0.4 × 10 5 and 5.4 ± 0.9 × 10 6 16S rRNA gene copies per g of sediment, respectively, were measured. The microbiological and hydrogeological characterization demonstrated that microbial processes at the fractured bedrock-sediment interface were crucial for preventing contaminants reaching the water column, emphasizing the relevance of this critical zone environment for contaminant attenuation.« less

An analytical model for solute transport in an infiltration tracer test in soil with a shallow groundwater table

NASA Astrophysics Data System (ADS)

Liang, Ching-Ping; Hsu, Shao-Yiu; Chen, Jui-Sheng

2016-09-01

It is recommended that an in-situ infiltration tracer test is considered for simultaneously determining the longitudinal and transverse dispersion coefficients in soil. Analytical solutions have been derived for two-dimensional advective-dispersive transport in a radial geometry in the literature which can be used for interpreting the result of such a tracer test. However, these solutions were developed for a transport domain with an unbounded-radial extent and an infinite thickness of vadose zone which might not be realistically manifested in the actual solute transport during a field infiltration tracer test. Especially, the assumption of infinite thickness of vadose zone should be invalid for infiltration tracer tests conducted in soil with a shallow groundwater table. This paper describes an analytical model for interpreting the results of an infiltration tracer test based on improving the transport domain with a bounded-radial extent and a finite thickness of vadose zone. The analytical model is obtained with the successive application of appropriate integral transforms and their corresponding inverse transforms. A comparison of the newly derived analytical solution against the previous analytical solutions in which two distinct sets of radial extent and thickness of vadose zone are considered is conducted to determine the influence of the radial and exit boundary conditions on the solute transport. The results shows that both the radial and exit boundary conditions substantially affect the trailing segment of the breakthrough curves for a soil medium with large dispersion coefficients. Previous solutions derived for a transport domain with an unbounded-radial and an infinite thickness of vadose zone boundary conditions give lower concentration predictions compared with the proposed solution at late times. Moreover, the differences between two solutions are amplified when the observation positions are near the groundwater table. In addition, we compare our

In situ remediation of DNAPL compounds in low permeability media fate/transport, in situ control technologies, and risk reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-08-01

In this project, in situ remediation technologies are being tested and evaluated for both source control and mass removal of dense, non-aqueous phase liquid (DNAPL) compounds in low permeability media (LPM). This effort is focused on chlorinated solvents (e.g., trichloroethylene and perchloroethylene) in the vadose and saturated zones of low permeability, massive deposits, and stratified deposits with inter-bedded clay lenses. The project includes technology evaluation and screening analyses and field-scale testing at both clean and contaminated sites in the US and Canada. Throughout this project, activities have been directed at understanding the processes that influence DNPAL compound migration and treatmentmore » in LPM and to assessing the operation and performance of the remediation technologies developed and tested. Selected papers are indexed separately for inclusion in the Energy Science and Technology Database.« less

Porous fiber formation in polymer-solvent system undergoing solvent evaporation

NASA Astrophysics Data System (ADS)

Dayal, Pratyush; Kyu, Thein

2006-08-01

Temporal evolution of the fiber morphology during dry spinning has been investigated in the framework of Cahn-Hilliard equation [J. Chem. Phys. 28, 258 (1958)] pertaining to the concentration order parameter or volume fraction given by the Flory-Huggins free energy of mixing [P. J. Flory, Principles of Polymer Chemistry (Cornell University Press, Ithaca, NY, 1953), p. 672] in conjunction with the solvent evaporation rate. To guide the solvent evaporation induced phase separation, equilibrium phase diagram of the starting polymer solution was established on the basis of the Flory-Huggins free energy of mixing. The quasi-steady-state approximation has been adopted to account for the nonconserved nature of the concentration field caused by the solvent loss. The process of solvent evaporation across the fiber skin-air interface was treated in accordance with the classical Fick's law [R. B. Bird et al., Transport Phenomena (J. Wiley, New York, 1960), p. 780]. The simulated morphologies include gradient type, hollow fiber type, bicontinuous type, and host-guest type. The development of these diverse fiber morphologies is explicable in terms of the phase diagram of the polymer solution in a manner dependent on the competition between the phase separation dynamics and rate of solvent evaporation.

Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: comparison between hard-sphere solvent and water.

PubMed

Oshima, Hiraku; Kinoshita, Masahiro

2015-04-14

In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent models and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient

Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: Comparison between hard-sphere solvent and water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oshima, Hiraku; Kinoshita, Masahiro, E-mail: kinoshit@iae.kyoto-u.ac.jp

In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent modelsmore » and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the

MODELS FOR LEACHING OF PESTICIDES IN SOILS AND GROUNDWATER

EPA Science Inventory

Models are developed which describe leaching of pesticides in the root zone and the intermediate vadose zone, and flushing of residual solute mass in the aquifer. Pollutants' loss pathways in the soil, such as volatilization, crop uptake, and biochemical decay, are emphasized, a...

Regional variability of nitrate fluxes in the unsaturated zone and groundwater, Wisconsin, USA

USGS Publications Warehouse

Green, Christopher T.; Liao, Lixia; Nolan, Bernard T.; Juckem, Paul F.; Shope, Christopher L.; Tesoriero, Anthony J.; Jurgens, Bryant

2018-01-01

Process-based modeling of regional NO3− fluxes to groundwater is critical for understanding and managing water quality, but the complexity of NO3− reactive transport processes make implementation a challenge. This study introduces a regional vertical flux method (VFM) for efficient estimation of reactive transport of NO3− in the vadose zone and groundwater. The regional VFM was applied to 443 well samples in central-eastern Wisconsin. Chemical measurements included O2, NO3−, N2 from denitrification, and atmospheric tracers of groundwater age including carbon-14, chlorofluorocarbons, tritium, and tritiogenic helium. VFM results were consistent with observed chemistry, and calibrated parameters were in-line with estimates from previous studies. Results indicated that (1) unsaturated zone travel times were a substantial portion of the transit time to wells and streams (2) since 1945 fractions of applied N leached to groundwater have increased for manure-N, possibly due to increased injection of liquid manure, and decreased for fertilizer-N, and (3) under current practices and conditions, approximately 60% of the shallow aquifer will eventually be affected by downward migration of NO3−, with denitrification protecting the remaining 40%. Recharge variability strongly affected the unsaturated zone lag times and the eventual depth of the NO3− front. Principal components regression demonstrated that VFM parameters and predictions were significantly correlated with hydrogeochemical landscape features. The diverse and sometimes conflicting aspects of N management (e.g. limiting N volatilization versus limiting N losses to groundwater) warrant continued development of large-scale holistic strategies to manage water quality and quantity.

Regional Variability of Nitrate Fluxes in the Unsaturated Zone and Groundwater, Wisconsin, USA

NASA Astrophysics Data System (ADS)

Green, Christopher T.; Liao, Lixia; Nolan, Bernard T.; Juckem, Paul F.; Shope, Christopher L.; Tesoriero, Anthony J.; Jurgens, Bryant C.

2018-01-01

Process-based modeling of regional NO3- fluxes to groundwater is critical for understanding and managing water quality, but the complexity of NO3- reactive transport processes makes implementation a challenge. This study introduces a regional vertical flux method (VFM) for efficient estimation of reactive transport of NO3- in the vadose zone and groundwater. The regional VFM was applied to 443 well samples in central-eastern Wisconsin. Chemical measurements included O2, NO3-, N2 from denitrification, and atmospheric tracers of groundwater age including carbon-14, chlorofluorocarbons, tritium, and tritiogenic helium. VFM results were consistent with observed chemistry, and calibrated parameters were in-line with estimates from previous studies. Results indicated that (1) unsaturated zone travel times were a substantial portion of the transit time to wells and streams, (2) since 1945 fractions of applied N leached to groundwater have increased for manure-N, possibly due to increased injection of liquid manure, and decreased for fertilizer-N, and (3) under current practices and conditions, approximately 60% of the shallow aquifer will eventually be affected by downward migration of NO3-, with denitrification protecting the remaining 40%. Recharge variability strongly affected the unsaturated zone lag times and the eventual depth of the NO3- front. Principal components regression demonstrated that VFM parameters and predictions were significantly correlated with hydrogeochemical landscape features. The diverse and sometimes conflicting aspects of N management (e.g., limiting N volatilization versus limiting N losses to groundwater) warrant continued development of large-scale holistic strategies to manage water quality and quantity.

Enhanced Remedial Amendment Delivery to Subsurface Using Shear Thinning Fluid and Aqueous Foam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Lirong; Szecsody, James E.; Oostrom, Martinus

2011-04-23

A major issue with in situ subsurface remediation is the ability to achieve an even spatial distribution of remedial amendments to the contamination zones in an aquifer or vadose zone. Delivery of amendment to the aquifer using shear thinning fluid and to the vadose zone using aqueous foam has the potential to enhance the amendment distribution into desired locations and improve the remediation. 2-D saturated flow cell experiments were conducted to evaluate the enhanced sweeping, contaminant removal, and amendment persistence achieved by shear thinning fluid delivery. Bio-polymer xanthan gum solution was used as the shear thinning fluid. Unsaturated 1-D columnmore » and 2-D flow cell experiments were conducted to evaluate the mitigation of contaminant mobilization, amendment uniform distribution enhancement, and lateral delivery improvement by foam delivery. Surfactant sodium lauryl ether sulfate was used as the foaming agent. It was demonstrated that the shear thinning fluid injection enhanced the fluid sweeping over a heterogeneous system and increased the delivery of remedial amendment into low-permeability zones. The persistence of the amendment distributed into the low-perm zones by the shear thinning fluid was prolonged compared to that of amendment distributed by water injection. Foam delivery of amendment was shown to mitigate the mobilization of highly mobile contaminant from sediments under vadose zone conditions. Foam delivery also achieved more uniform amendment distribution in a heterogeneous unsaturated system, and demonstrated remarkable increasing in lateral distribution of the injected liquid compared to direct liquid injection.« less

Solvent replacement for green processing.

PubMed Central

Sherman, J; Chin, B; Huibers, P D; Garcia-Valls, R; Hatton, T A

1998-01-01

The implementation of the Montreal Protocol, the Clean Air Act, and the Pollution Prevention Act of 1990 has resulted in increased awareness of organic solvent use in chemical processing. The advances made in the search to find "green" replacements for traditional solvents are reviewed, with reference to solvent alternatives for cleaning, coatings, and chemical reaction and separation processes. The development of solvent databases and computational methods that aid in the selection and/or design of feasible or optimal environmentally benign solvent alternatives for specific applications is also discussed. Images Figure 2 Figure 3 PMID:9539018

The solvent component of macromolecular crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weichenberger, Christian X.; Afonine, Pavel V.; Kantardjieff, Katherine

2015-04-30

On average, the mother liquor or solvent and its constituents occupy about 50% of a macromolecular crystal. Ordered as well as disordered solvent components need to be accurately accounted for in modelling and refinement, often with considerable complexity. The mother liquor from which a biomolecular crystal is grown will contain water, buffer molecules, native ligands and cofactors, crystallization precipitants and additives, various metal ions, and often small-molecule ligands or inhibitors. On average, about half the volume of a biomolecular crystal consists of this mother liquor, whose components form the disordered bulk solvent. Its scattering contributions can be exploited in initialmore » phasing and must be included in crystal structure refinement as a bulk-solvent model. Concomitantly, distinct electron density originating from ordered solvent components must be correctly identified and represented as part of the atomic crystal structure model. Herein, are reviewed (i) probabilistic bulk-solvent content estimates, (ii) the use of bulk-solvent density modification in phase improvement, (iii) bulk-solvent models and refinement of bulk-solvent contributions and (iv) modelling and validation of ordered solvent constituents. A brief summary is provided of current tools for bulk-solvent analysis and refinement, as well as of modelling, refinement and analysis of ordered solvent components, including small-molecule ligands.« less

Next Generation Solvent Performance in the Modular Caustic Side Solvent Extraction Process - 15495

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Tara E.; Scherman, Carl; Martin, David

Changes to the Modular Caustic Side Solvent Extraction Unit (MCU) flow-sheet were implemented in the facility. Implementation included changing the scrub and strip chemicals and concentrations, modifying the O/A ratios for the strip, scrub, and extraction contactor banks, and blending the current BoBCalixC6 extractant-based solvent in MCU with clean MaxCalix extractant-based solvent. During the successful demonstration period, the MCU process was subject to rigorous oversight to ensure hydraulic stability and chemical/radionuclide analysis of the key process tanks (caustic wash tank, solvent hold tank, strip effluent hold tank, and decontaminated salt solution hold tank) to evaluate solvent carryover to downstream facilitiesmore » and the effectiveness of cesium removal from the liquid salt waste. Results indicated the extraction of cesium was significantly more effective with an average Decontamination Factor (DF) of 1,129 (range was 107 to 1,824) and that stripping was effective. The contactor hydraulic performance was stable and satisfactory, as indicated by contactor vibration, contactor rotational speed, and flow stability; all of which remained at or near target values. Furthermore, the Solvent Hold Tank (SHT) level and specific gravity was as expected, indicating that solvent integrity and organic hydraulic stability were maintained. The coalescer performances were in the range of processing results under the BOBCalixC6 flow sheet, indicating negligible adverse impact of NGS deployment. After the Demonstration period, MCU began processing via routine operations. Results to date reiterate the enhanced cesium extraction and stripping capability of the Next Generation Solvent (NGS) flow sheet. This paper presents process performance results of the NGS Demonstration and continued operations of MCU utilizing the blended BobCalixC6-MaxCalix solvent under the NGS flowsheet.« less

Alternative Green Solvents Project

NASA Technical Reports Server (NTRS)

Maloney, Phillip R.

2012-01-01

Necessary for safe and proper functioning of equipment. Mainly halogenated solvents. Tetrachloride, Trichloroethylene (TCE), CFC-113. No longer used due to regulatory/safety concerns. Precision Cleaning at KSC: Small % of total parts. Used for liquid oxygen (LOX) systems. Dual solvent process. Vertrel MCA (decafluoropentane (DFP) and trons-dichloroethylene) HFE-7100. DFP has long term environmental concerns. Project Goals: a) Identify potential replacements. b) 22 wet chemical processes. c) 3 alternative processes. d) Develop test procedures. e) Contamination and cleaning. f) Analysis. g) Use results to recommend alternative processes. Conclusions: a) No alternative matched Vertrel in this study. b) No clear second place solvent. c) Hydrocarbons- easy; Fluorinated greases- difficult. d) Fluorinated component may be needed in replacement solvent. e) Process may need to make up for shortcoming of the solvent. f) Plasma and SCC02 warrant further testing.

Preferential solvation of Brooker's merocyanine in binary solvent mixtures composed of formamides and hydroxylic solvents.

PubMed

Bevilaqua, Tharly; da Silva, Domingas C; Machado, Vanderlei G

2004-03-01

The ET polarity values of 4-[(1-methyl-4(1H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (Brooker's merocyanine) were collected in mixed-solvent systems comprising a formamide [N,N-dimethylformamide (DMF), N-methylformamide (NMF) or formamide (FA)] and a hydroxylic (water, methanol, ethanol, propan-2-ol or butan-1-ol) solvent. Binary mixtures involving DMF and the other formamides (NMF and FA) as well as NMF and FA were also studied. These data were employed in the investigation of the preferential solvation (PS) of the probe. Each solvent system was analyzed in terms of both solute-solvent and solvent-solvent interactions. These latter interactions were responsible for the synergism observed in many binary mixtures. This synergistic behaviour was observed for DMF-propan-2-ol, DMF-butan-1-ol, FA-methanol, FA-ethanol and for the mixtures of the alcohols with NMF. All data were successfully fitted to a model based on solvent-exchange equilibria, which allowed the separation of the different contributions of the solvent species in the solvation shell of the dye. The results suggest that both hydrogen bonding and solvophobic interactions contribute to the formation of the solvent complexes responsible for the observed synergistic effects in the PS of the dye.

Water table dynamics and biogeochemical cycling in a shallow, variably-saturated floodplain

DOE PAGES

Yabusaki, Steven B.; Wilkins, Michael J.; Fang, Yilin; ...

2017-02-20

Three-dimensional variably saturated flow and multicomponent biogeochemical reactive transport modeling, based on published and newly generated data, is used to better understand the interplay of hydrology, geochemistry, and biology controlling the cycling of carbon, nitrogen, oxygen, iron, sulfur, and uranium in a shallow floodplain. In this system, aerobic respiration generally maintains anoxic groundwater below an oxic vadose zone until seasonal snowmelt-driven water table peaking transports dissolved oxygen (DO) and nitrate from the vadose zone into the alluvial aquifer. The response to this perturbation is localized due to distinct physico-biogeochemical environments and relatively long time scales for transport through the floodplainmore » aquifer and vadose zone. Naturally reduced zones (NRZs) containing sediments higher in organic matter, iron sulfides, and non-crystalline U(IV) rapidly consume DO and nitrate to maintain anoxic conditions, yielding Fe(II) from FeS oxidative dissolution, nitrite from denitrification, and U(VI) from nitrite-promoted U(IV) oxidation. Redox cycling is a key factor for sustaining the observed aquifer behaviors despite continuous oxygen influx and the annual hydrologically induced oxidation event. Furthermore, depth-dependent activity of fermenters, aerobes, nitrate reducers, sulfate reducers, and chemolithoautotrophs (e.g., oxidizing Fe(II), S compounds, and ammonium) is linked to the presence of DO, which has higher concentrations near the water table.« less

Natural Attenuation of Nonvolatile Contaminants in the Capillary Fringe.

PubMed

Kurt, Zohre; Mack, E Erin; Spain, Jim C

2016-09-20

When anoxic polluted groundwater encounters the overlying vadose zone an oxic/anoxic interface is created, often near the capillary fringe. Biodegradation of volatile contaminants in the capillary fringe can prevent vapor migration. In contrast, the biodegradation of nonvolatile contaminants in the vadose zone has received comparatively little attention. Nonvolatile compounds do not cause vapor intrusion, but they still move with the groundwater and are major contaminants. Aniline (AN) and diphenylamine (DPA) are examples of toxic nonvolatile contaminants found often at dye and munitions manufacturing sites. In this study, we tested the hypothesis that bacteria can aerobically biodegrade AN and DPA in the capillary fringe and decrease the contaminant concentrations in the anoxic plume beneath the vadose zone. Laboratory multiport columns that represented the unsaturated zone were used to evaluate degradation of AN or DPA in contaminated water. The biodegradation fluxes of the contaminants were estimated to be 113 ± 26 mg AN·m(-2)·h(-1) and 76 ± 18 mg DPA·m(-2)·h(-1) in the presence of bacteria known to degrade AN and DPA. Oxygen and contaminant profiles along with enumeration of bacterial populations indicated that most of the biodegradation took place within the lower part of the capillary fringe. The results indicate that bacteria capable of contaminant biodegradation in the capillary fringe can create a sink for nonvolatile contaminants.

Preparative separation of six rhynchophylla alkaloids from Uncaria macrophylla wall by pH-zone refining counter-current chromatography.

PubMed

Zhang, Qinghai; Lin, Changhu; Duan, Wenjuan; Wang, Xiao; Luo, Aiqin

2013-12-12

pH-Zone refining counter-current chromatography was successfully applied to the preparative isolation and purification of six alkaloids from the ethanol extracts of Uncaria macrophylla Wall. Because of the low content of alkaloids (about 0.2%, w/w) in U. macrophylla Wall, the target compounds were enriched by pH-zone refining counter-current chromatography using a two-phase solvent system composed of petroleum ether-ethyl acetate-isopropanol-water (2:6:3:9, v/v), adding 10 mM triethylamine in organic stationary phase and 5 mM hydrochloric acid in aqueous mobile phase. Then pH-zone refining counter-current chromatography using the other two-phase solvent system was used for final purification. Six target compounds were finally isolated and purified by following two-phase solvent system composed of methyl tert-butyl ether (MTBE)-acetonitrile-water (4:0.5:5, v/v), adding triethylamine (TEA) (10 mM) to the organic phase and HCl (5 mM) to aqueous mobile phase. The separation of 2.8 g enriched total alkaloids yielded 36 mg hirsutine, 48 mg hirsuteine, 82 mg uncarine C, 73 mg uncarine E, 163 mg rhynchophylline, and 149 mg corynoxeine, all with purities above 96% as verified by HPLC Their structures were identified by electrospray ionization-mass spectrometry (ESI-MS) and 1H-NMR spectroscopy.

Solvent-free synthesis

EPA Science Inventory

This chapter gives a brief introduction about solvent-free reactions whose importance can be gauged by the increasing number of publications every year during the last decade. The mechanistic aspects of the reactions under solvent-free conditions have been highlighted. Our observ...

pH-zone-refining elution-extrusion countercurrent chromatography: Separation of hydroxyanthraquinones from Cassiae semen.

PubMed

Bu, Zhisi; Lv, Liqiong; Li, Xingnuo; Chu, Chu; Tong, Shengqiang

2017-11-01

Seven hydroxyanthraquinones were successfully separated from the traditional Chinese medicinal herb Cassiae semen by conventional and pH-zone-refining countercurrent chromatography with an environmentally friendly biphasic solvent system, in which elution-extrusion mode was investigated for pH-zone-refining countercurrent chromatography for the first time. A two-phase solvent system composed of n-hexane/ethyl acetate/ethanol/water (5:3:4:4, v/v/v/v) was used for the conventional countercurrent chromatography while the same system with a different volume ratio n-hexane/ethyl acetate/ethanol/water (3:5:2:6, v/v/v/v) was used for pH-zone-refining countercurrent chromatography, in which 20 mmol/L of trifluoroacetic acid was added in the organic phase as a retainer and 15 mmol/L of ammonia was added to the aqueous phase as an eluter. A 400 mg crude sample could be well separated by pH-zone-refining countercurrent chromatography, yielding 53 mg of aurantio-obtusin, 40 mg of chryso-obtusin, 18 mg of obtusin, 24 mg of obtusifolin, 10 mg of emodin, and 105 mg of the mixture of chrysophanol and physcion with a purity of over 95.8, 95.7, 96.9, 93.5, 97.4, 77.1, and 19.8%, as determined by high-performance liquid chromatography. Furthermore, the difference in elution sequence between conventional and pH-zone-refining mode was observed and discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Geomicrobiology of High-Level Nuclear Waste-Contaminated Vadose Sediments at the Hanford Site, Washington State

PubMed Central

Fredrickson, James K.; Zachara, John M.; Balkwill, David L.; Kennedy, David; Li, Shu-mei W.; Kostandarithes, Heather M.; Daly, Michael J.; Romine, Margaret F.; Brockman, Fred J.

2004-01-01

Sediments from a high-level nuclear waste plume were collected as part of investigations to evaluate the potential fate and migration of contaminants in the subsurface. The plume originated from a leak that occurred in 1962 from a waste tank consisting of high concentrations of alkali, nitrate, aluminate, Cr(VI), 137Cs, and 99Tc. Investigations were initiated to determine the distribution of viable microorganisms in the vadose sediment samples, probe the phylogeny of cultivated and uncultivated members, and evaluate the ability of the cultivated organisms to survive acute doses of ionizing radiation. The populations of viable aerobic heterotrophic bacteria were generally low, from below detection to ∼104 CFU g−1, but viable microorganisms were recovered from 11 of 16 samples, including several of the most radioactive ones (e.g., >10 μCi of 137Cs/g). The isolates from the contaminated sediments and clone libraries from sediment DNA extracts were dominated by members related to known gram-positive bacteria. Gram-positive bacteria most closely related to Arthrobacter species were the most common isolates among all samples, but other phyla high in G+C content were also represented, including Rhodococcus and Nocardia. Two isolates from the second-most radioactive sample (>20 μCi of 137Cs g−1) were closely related to Deinococcus radiodurans and were able to survive acute doses of ionizing radiation approaching 20 kGy. Many of the gram-positive isolates were resistant to lower levels of gamma radiation. These results demonstrate that gram-positive bacteria, predominantly from phyla high in G+C content, are indigenous to Hanford vadose sediments and that some are effective at surviving the extreme physical and chemical stress associated with radioactive waste. PMID:15240306

Numerical simulation of infiltration and groundwater recharge using the Hydrus for Modflow package and the BEST model of soil hydraulic properties

NASA Astrophysics Data System (ADS)

Gumuła-Kawęcka, Anna; Szymkiewicz, Adam; Angulo-Jaramillo, Rafael; Šimůnek, Jirka; Jaworska-Szulc, Beata; Pruszkowska-Caceres, Małgorzata; Gorczewska-Langner, Wioletta; Leterme, Bertrand; Jacques, Diederik

2017-04-01

ABSTRACT Groundwater recharge is a complex process, which depends on several factors, including the hydraulic properties of soils in the vadose zone. On the other hand, the rate of recharge is one of the main input data in hydrogeological models for saturated groundwater flow. Thus, there is an increasing understanding of the need for more complete representation of vadose zone processes in groundwater modeling. One of the possible approaches is to use a 1D model of water flow in the unsaturated zone coupled with 3D groundwater model for the saturated zone. Such an approach was implemented in the Hydrus for Modflow package (Seo et al. 2007), which combines two well-known and thoroughly tested modeling tools: groundwater flow simulator MODFLOW (Harbaugh 2005) and one-dimensional vadose zone simulator HYDRUS 1D (Šimůnek et al. 2016), based on the Richards equation. The Hydrus for Modflow package has been recently enhanced by implementing the BEST model of soil hydraulic properties (Lassabatere et al. 2006), which is a combination of van Genuchten - type retention function with Brooks-Corey type hydraulic conductivity function. The parameters of these functions can be divided into texture-related and structure-related and can be obtained from relatively simple lab and field tests. The method appears a promising tool for obtaining input data for vadose zone flow models. The main objective of this work is to evaluate the sensitivity of the recharge rates to the values of various parameters of the BEST model. Simulations are performed for a range of soil textural classes and plant covers, using meteorological data typical for northern Poland. ACKNOWLEDGEMENTS This work has been supported by National Science Centre, Poland in the framework of the project 2015/17/B/ST10/03233 "Groundwater recharge on outwash plain". REFERENCES [1]Harbaugh, A.W. (2005) MODFLOW-2005, the US Geological Survey modular ground-water model: the ground-water flow process. Reston, VA, USA. [2

Cleaning without chlorinated solvents

NASA Technical Reports Server (NTRS)

Thompson, L. M.; Simandl, R. F.

1995-01-01

Because of health and environmental concerns, many regulations have been passed in recent years regarding the use of chlorinated solvents. The Oak Ridge Y-12 Plant has had an active program to find alternatives for these solvents used in cleaning applications for the past 7 years. During this time frame, the quantity of solvents purchased has been reduced by 92 percent. The program has been a twofold effort. Vapor degreasers used in batch cleaning operations have been replaced by ultrasonic cleaning with aqueous detergent, and other organic solvents have been identified for use in hand-wiping or specialty operations. In order to qualify these alternatives for use, experimentation was conducted on cleaning ability as well as effects on subsequent operations such as welding, painting, and bonding. Cleaning ability was determined using techniques such as x-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) which are capable of examining monolayer levels of contamination on a surface. Solvents have been identified for removal of rust preventative oils, lapping oils, machining coolants, lubricants, greases, and mold releases. Solvents have also been evaluated for cleaning urethane foam spray guns, swelling of urethanes, and swelling of epoxies.

Solvolysis kinetics of three components of biomass using polyhydric alcohols as solvents.

PubMed

Shi, Yan; Xia, Xueying; Li, Jingdan; Wang, Jing; Zhao, Tiantian; Yang, Hongmin; Jiang, Jianchun; Jiang, Xiaoxiang

2016-12-01

The solvolysis behavior and reaction kinetics of the three components of biomass (cellulose, hemicelluloses and lignin) liquefied in polyhydric alcohols (PEG 400 or glycerol) were investigated in this paper. Three stages were observed during the solvolysis process and the main degradation stage could be further divided into two zones. The influences of solvents on the liquefaction process of three main components were compared. Based on Starink and Malek methods, kinetic parameters and mechanism functions were obtained. The derived average activation energy of cellulose, hemicellulose and lignin were 108.73, 95.66 and 94.13kJmol -1 in PEG 400, while the values were 102.16, 77.43 and 89.10kJmol -1 in glycerol, respectively. Higher efficiency was observed when using glycerol as solvent, which could be ascribed to the higher polarity value of glycerol. The conversion curves calculated with obtained mechanism models and kinetic parameters were in good agreement with the experimental data. Copyright © 2016 Elsevier Ltd. All rights reserved.

A method and example of seismically imaging near‐surface fault zones in geologically complex areas using Vp, Vs, and their ratios

USGS Publications Warehouse

Catchings, Rufus D.; Rymer, Michael J.; Goldman, Mark R.; Sickler, Robert R.; Criley, Coyn J.

2014-01-01

The determination of near‐surface (vadose zone and slightly below) fault locations and geometries is important because assessment of ground rupture, strong shaking, geologic slip rates, and rupture histories occurs at shallow depths. However, seismic imaging of fault zones at shallow depths can be difficult due to near‐surface complexities, such as weathering, groundwater saturation, massive (nonlayered) rocks, and vertically layered strata. Combined P‐ and S‐wave seismic‐refraction tomography data can overcome many of the near‐surface, fault‐zone seismic‐imaging problems because of differences in the responses of elastic (bulk and shear) moduli of P and S waves to shallow‐depth, fault‐zone properties. We show that high‐resolution refraction tomography images of P‐ to S‐wave velocity ratios (VP/VS) can reliably identify near‐surface faults. We demonstrate this method using tomography images of the San Andreas fault (SAF) surface‐rupture zone associated with the 18 April 1906 ∼M 7.9 San Francisco earthquake on the San Francisco peninsula in California. There, the SAF cuts through Franciscan mélange, which consists of an incoherent assemblage of greywacke, chert, greenstone, and serpentinite. A near‐vertical zone (∼75° northeast dip) of high P‐wave velocities (up to 3000  m/s), low S‐wave velocities (∼150–600  m/s), high VP/VS ratios (4–8.8), and high Poisson’s ratios (0.44–0.49) characterizes the main surface‐rupture zone to a depth of about 20 m and is consistent with nearby trench observations. We suggest that the combined VP/VSimaging approach can reliably identify most near‐surface fault zones in locations where many other seismic methods cannot be applied.

Solvent/non-solvent sintering: a novel route to create porous microsphere scaffolds for tissue regeneration.

PubMed

Brown, Justin L; Nair, Lakshmi S; Laurencin, Cato T

2008-08-01

Solvent/non-solvent sintering creates porous polymeric microsphere scaffolds suitable for tissue engineering purposes with control over the resulting porosity, average pore diameter, and mechanical properties. Five different biodegradable biocompatible polyphosphazenes exhibiting glass transition temperatures from -8 to 41 degrees C and poly (lactide-co-glycolide), (PLAGA) a degradable polymer used in a number of biomedical settings, were examined to study the versatility of the process and benchmark the process to heat sintering. Parameters such as: solvent/non-solvent sintering solution composition and submersion time effect the sintering process. PLAGA microsphere scaffolds fabricated with solvent/non-solvent sintering exhibited an interconnected porosity and pore size of 31.9% and 179.1 mum, respectively which was analogous to that of conventional heat sintered PLAGA microsphere scaffolds. Biodegradable polyphosphazene microsphere scaffolds exhibited a maximum interconnected porosity of 37.6% and a maximum compressive modulus of 94.3 MPa. Solvent/non-solvent sintering is an effective strategy for sintering polymeric microspheres, with a broad spectrum of glass transition temperatures, under ambient conditions making it an excellent fabrication route for developing tissue engineering scaffolds and drug delivery vehicles. (c) 2007 Wiley Periodicals, Inc.

Solvent/Non-Solvent Sintering: A Novel Route to Create Porous Microsphere Scaffolds For Tissue Regeneration

PubMed Central

Brown, Justin L.; Nair, Lakshmi S.; Laurencin, Cato T.

2009-01-01

Solvent/non-solvent sintering creates porous polymeric microsphere scaffolds suitable for tissue engineering purposes with control over the resulting porosity, average pore diameter and mechanical properties. Five different biodegradable biocompatible polyphosphazenes exhibiting glass transition temperatures from −8°C to 41oC and poly(lactide-co-glycolide), (PLAGA) a degradable polymer used in a number of biomedical settings, were examined to study the versatility of the process and benchmark the process to heat sintering. Parameters such as: solvent/non-solvent sintering solution composition and submersion time effect the sintering process. PLAGA microsphere scaffolds fabricated with solvent/non-solvent sintering exhibited an interconnected porosity and pore size of 31.9% and 179.1µm respectively which was analogous to that of conventional heat sintered PLAGA microsphere scaffolds. Biodegradable polyphosphazene microsphere scaffolds exhibited a maximum interconnected porosity of 37.6% and a maximum compressive modulus of 94.3MPa. Solvent/non-solvent sintering is an effective strategy for sintering polymeric microspheres, with a broad spectrum of glass transition temperatures, under ambient conditions making it an excellent fabrication route for developing tissue engineering scaffolds and drug delivery vehicles. PMID:18161819

Estimating ammonium and nitrate load from septic systems to surface water bodies within ArcGIS environments

NASA Astrophysics Data System (ADS)

Zhu, Yan; Ye, Ming; Roeder, Eberhard; Hicks, Richard W.; Shi, Liangsheng; Yang, Jinzhong

2016-01-01

This paper presents a recently developed software, ArcGIS-based Nitrogen Load Estimation Toolkit (ArcNLET), for estimating nitrogen loading from septic systems to surface water bodies. The load estimation is important for managing nitrogen pollution, a world-wide challenge to water resources and environmental management. ArcNLET simulates coupled transport of ammonium and nitrate in both vadose zone and groundwater. This is a unique feature that cannot be found in other ArcGIS-based software for nitrogen modeling. ArcNLET is designed to be flexible for the following four simulating scenarios: (1) nitrate transport alone in groundwater; (2) ammonium and nitrate transport in groundwater; (3) ammonium and nitrate transport in vadose zone; and (4) ammonium and nitrate transport in both vadose zone and groundwater. With this flexibility, ArcNLET can be used as an efficient screening tool in a wide range of management projects related to nitrogen pollution. From the modeling perspective, this paper shows that in areas with high water table (e.g. river and lake shores), it may not be correct to assume a completed nitrification process that converts all ammonium to nitrate in the vadose zone, because observation data can indicate that substantial amount of ammonium enters groundwater. Therefore, in areas with high water table, simulating ammonium transport and estimating ammonium loading, in addition to nitrate transport and loading, are important for avoiding underestimation of nitrogen loading. This is demonstrated in the Eggleston Heights neighborhood in the City of Jacksonville, FL, USA, where monitoring well observations included a well with predominant ammonium concentrations. The ammonium loading given by the calibrated ArcNLET model can be 10-18% of the total nitrogen load, depending on various factors discussed in the paper.

Numerical Treatment of Stokes Solvent Flow and Solute-Solvent Interfacial Dynamics for Nonpolar Molecules.

PubMed

Sun, Hui; Zhou, Shenggao; Moore, David K; Cheng, Li-Tien; Li, Bo

2016-05-01

We design and implement numerical methods for the incompressible Stokes solvent flow and solute-solvent interface motion for nonpolar molecules in aqueous solvent. The balance of viscous force, surface tension, and van der Waals type dispersive force leads to a traction boundary condition on the solute-solvent interface. To allow the change of solute volume, we design special numerical boundary conditions on the boundary of a computational domain through a consistency condition. We use a finite difference ghost fluid scheme to discretize the Stokes equation with such boundary conditions. The method is tested to have a second-order accuracy. We combine this ghost fluid method with the level-set method to simulate the motion of the solute-solvent interface that is governed by the solvent fluid velocity. Numerical examples show that our method can predict accurately the blow up time for a test example of curvature flow and reproduce the polymodal (e.g., dry and wet) states of hydration of some simple model molecular systems.

Numerical Treatment of Stokes Solvent Flow and Solute-Solvent Interfacial Dynamics for Nonpolar Molecules

PubMed Central

Sun, Hui; Zhou, Shenggao; Moore, David K.; Cheng, Li-Tien; Li, Bo

2015-01-01

We design and implement numerical methods for the incompressible Stokes solvent flow and solute-solvent interface motion for nonpolar molecules in aqueous solvent. The balance of viscous force, surface tension, and van der Waals type dispersive force leads to a traction boundary condition on the solute-solvent interface. To allow the change of solute volume, we design special numerical boundary conditions on the boundary of a computational domain through a consistency condition. We use a finite difference ghost fluid scheme to discretize the Stokes equation with such boundary conditions. The method is tested to have a second-order accuracy. We combine this ghost fluid method with the level-set method to simulate the motion of the solute-solvent interface that is governed by the solvent fluid velocity. Numerical examples show that our method can predict accurately the blow up time for a test example of curvature flow and reproduce the polymodal (e.g., dry and wet) states of hydration of some simple model molecular systems. PMID:27365866

Fingering dynamics on the adsorbed solute with influence of less viscous and strong sample solvent.

PubMed

Rana, Chinar; Mishra, Manoranjan

2014-12-07

Viscous fingering is a hydrodynamic instability that sets in when a low viscous fluid displaces a high viscous fluid and creates complex patterns in porous media flows. Fundamental facets of the displacement process, such as the solute concentration distribution, spreading length, and the solute mixing, depend strongly on the type of pattern created by the unstable interface of the underlying fluids. In the present study, the frontal interface of the sample shows viscous fingering and the strong solvent causes the retention of the solute to depend on the solvent concentration. This work presents a computational investigation to explore the effect of the underlying physico-chemical phenomena, (i.e., the combined effects of solvent strength, retention, and viscous fingering) on the dynamics of the adsorbed solute. A linear adsorption isotherm has been assumed between the mobile and stationary phases of the solute. We carried out the numerical simulations by considering a rectangular Hele-Shaw cell as an analog to 2D-porous media containing a three component system (displacing fluid, sample solvent, solute) to map out the evolution of the solute concentration. We observed that viscous fingering at the frontal interface of the strong sample solvent intensifies the band broadening of the solute zone. Also notable increase in the spreading dynamics of the solute has been observed for less viscous and strong sample solvent as compared to the high viscous sample slices or in the pure dispersive case. On the contrary, the solute gets intensively mixed at early times for more viscous sample in comparison to less viscous one. The results of the simulations are in qualitative agreement with the behavior observed in the liquid chromatography column experiments.

From the surface to the deep critical zone: Linking soil carbon, fluid saturation and weathering rate

NASA Astrophysics Data System (ADS)

Druhan, Jennifer; Lawrence, Corey; Oster, Jessica; Rempe, Daniella; Dietrich, William

2017-04-01

Shallow soils from a wide range of ecosystems demonstrate a clear and consistent relationship between effective fluid saturation and the rate at which organic carbon is converted to CO2. While the underlying mechanisms contributing to this dependence are diverse, a consistent pattern of maximum CO2 production at intermediate soil moisture supports a generalized functional relationship, which may be incorporated into a quantitative reactive transport framework. A key result of this model development is a prediction of the extent to which the inorganic carbon content of water in biologically active soils varies as a function of hydrologic parameters (i.e. moisture content and residence time), and in turn influences weathering reactions. Deeper in the CZ, the consistency of this relationship and the influence of hydrologically - regulated CO2 production on the rates of water - rock interaction are largely unknown. Here, we use a novel reactive transport model incorporating this functional relationship to consider how variations in the reactive potential of water entering the vadose zone influences subsurface weathering rates. We leverage two examples of variably saturated natural systems to consider (1) CO2 production and associated weathering potential regulated by seasonal hydrologic shifts and (2) the preservation of soil carbon signatures in the deep CZ over millennial timescales. First, at the Eel River CZ Observatory in Northern California, USA, a novel Vadose Zone Monitoring System (VMS) installed in a 14 - 20 m thick unsaturated section offers an unprecedented view into the physical, chemical and biological behavior of the depth profile separating soils from groundwater. Based on soil moisture, gas and fluid phase samples, we demonstrate a predictive relationship between seasonal hydrologic variations and the location and magnitude of geochemical weathering rates. Second, an environmental monitoring project in the Blue Springs Cave, Sparta, TN, USA, provides

Next Generation Solvent Development for Caustic-Side Solvent Extraction of Cesium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moyer, Bruce A.; Birdwell, Joseph F.; Bonnesen, Peter V.

This report summarizes the FY 2010 and 2011 accomplishments at Oak Ridge National Laboratory (ORNL) in developing the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process, referred to commonly as the Next Generation Solvent (NGS), under funding from the U.S. Department of Energy, Office of Environmental Management (DOE-EM), Office of Technology Innovation and Development. The primary product of this effort is a process solvent and preliminary flowsheet capable of meeting a target decontamination factor (DF) of 40,000 for worst-case Savannah River Site (SRS) waste with a concentration factor of 15 or higher in the 18-stage equipment configuration of the SRS Modularmore » Caustic-Side Solvent Extraction Unit (MCU). In addition, the NG-CSSX process may be readily adapted for use in the SRS Salt Waste Processing Facility (SWPF) or in supplemental tank-waste treatment at Hanford upon appropriate solvent or flowsheet modifications. Efforts in FY 2010 focused on developing a solvent composition and process flowsheet for MCU implementation. In FY 2011 accomplishments at ORNL involved a wide array of chemical-development activities and testing up through single-stage hydraulic and mass-transfer tests in 5-cm centrifugal contactors. Under subcontract from ORNL, Argonne National Laboratory (ANL) designed a preliminary flowsheet using ORNL cesium distribution data, and Tennessee Technological University confirmed a chemical model for cesium distribution ratios (DCs) as a function of feed composition. Inter laboratory efforts were coordinated with complementary engineering tests carried out (and reported separately) by personnel at Savannah River National Laboratory (SRNL) and Savannah River Remediation (SRR) with helpful advice by Parsons Engineering and General Atomics on aspects of possible SWPF implementation.« less

PARIS II: DESIGNING GREENER SOLVENTS

EPA Science Inventory

PARIS II (the program for assisting the replacement of industrial solvents, version II), developed at the USEPA, is a unique software tool that can be used for customizing the design of replacement solvents and for the formulation of new solvents. This program helps users avoid ...

Competition between hardwood hammocks and mangroves

USGS Publications Warehouse

Sternberg, L.D.S.L.; Teh, S.Y.; Ewe, S.M.L.; Miralles-Wilhelm, F.; DeAngelis, D.L.

2007-01-01

The boundaries between mangroves and freshwater hammocks in coastal ecotones of South Florida are sharp. Further, previous studies indicate that there is a discontinuity in plant predawn water potentials, with woody plants either showing predawn water potentials reflecting exposure to saline water or exposure to freshwater. This abrupt concurrent change in community type and plant water status suggests that there might be feedback dynamics between vegetation and salinity. A model examining the salinity of the aerated zone of soil overlying a saline body of water, known as the vadose layer, as a function of precipitation, evaporation and plant water uptake is presented here. The model predicts that mixtures of saline and freshwater vegetative species represent unstable states. Depending on the initial vegetation composition, subsequent vegetative change will lead either to patches of mangrove coverage having a high salinity vadose zone or to freshwater hammock coverage having a low salinity vadose zone. Complete or nearly complete coverage by either freshwater or saltwater vegetation represents two stable steady-state points. This model can explain many of the previous observations of vegetation patterns in coastal South Florida as well as observations on the dynamics of vegetation shifts caused by sea level rise and climate change. ?? 2007 Springer Science+Business Media, LLC.

Controls on the chemical composition of saline surface crusts and emitted dust from a wet playa in the Mojave Desert (USA)

USGS Publications Warehouse

Goldstein, Harland L.; Breit, George N.; Reynolds, Richard L.

2017-01-01

Saline-surface crusts and their compositions at ephemeral, dry, and drying lakes are important products of arid-land processes. Detailed understanding is lacking, however, about interactions among locally variable hydrogeologic conditions, compositional control of groundwater on vadose zone and surface salts, and dust composition. Chemical and physical data from groundwater, sediments, and salts reveal compositional controls on saline-surface crusts across a wet playa, Mojave Desert, with bearing on similar settings elsewhere. The compositions of chemically and isotopically distinctive shallow (<3 m) water masses are recorded in the composition of associated salts. In areas with deeper and more saline groundwater, however, not all ions are transported through the vadose zone. Retention of arsenic and other elements in the vadose zone diminishes the concentrations of potentially toxic elements in surface salts, but creates a reservoir of these elements that may be brought to the surface during wetter conditions or by human disturbance. Selective wind-erosion loss of sulfate salts was identified by the compositional contrast between surface salt crusts and underlying groundwater. At the sub-basin scale, compositional links exist among groundwater, salt crusts, and dust from wet playas. Across the study basin, however, lateral variations in groundwater and solid-salt compositions are produced by hydrogeologic heterogeneity.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wellman, Dawn M.; Triplett, Mark B.; Freshley, Mark D.

DOE-EM, Office of Groundwater and Soil Remediation and DOE Richland, in collaboration with the Hanford site and Pacific Northwest National Laboratory, have established the Deep Vadose Zone Applied Field Research Center (DVZ-AFRC). The DVZ-AFRC leverages DOE investments in basic science from the Office of Science, applied research from DOE EM Office of Technology Innovation and Development, and site operation (e.g., site contractors [CH2M HILL Plateau Remediation Contractor and Washington River Protection Solutions], DOE-EM RL and ORP) in a collaborative effort to address the complex region of the deep vadose zone. Although the aim, goal, motivation, and contractual obligation of eachmore » organization is different, the integration of these activities into the framework of the DVZ-AFRC brings the resources and creativity of many to provide sites with viable alternative remedial strategies to current baseline approaches for persistent contaminants and deep vadose zone contamination. This cooperative strategy removes stove pipes, prevents duplication of efforts, maximizes resources, and facilitates development of the scientific foundation needed to make sound and defensible remedial decisions that will successfully meet the target cleanup goals for one of DOE EM's most intractable problems, in a manner that is acceptable by regulators.« less

Face-Dependent Solvent Adsorption: A Comparative Study on the Interfaces of HMX Crystal with Three Solvents.

PubMed

Liu, Yingzhe; Lai, Weipeng; Ma, Yiding; Yu, Tao; Kang, Ying; Ge, Zhongxue

2017-07-27

To understand the crystal-solvent interfacial interactions on the molecular scale, the interfaces between three solvents, that is, acetone, γ-butyrolactone, and cyclohexanone, and three growth faces of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) crystal have been investigated with the aid of theoretical chemistry. The results show that the structural features of crystal faces play a critical role in the energetic, structural, and dynamic properties at the interfaces. For each solvent, the same change trend of some properties among the three faces of HMX crystal is observed, including adsorption affinity, local mass density, and solvent diffusion. For example, the rate of solvent diffusion at the three faces ranks as (011) > (110) > (020) regardless of solvent species. This can be attributed to the similar adsorption sites for solvent incorporation at the same face, which are concentrated at the cavities formed by surficial HMX molecules.

Prediction of Bicarbonate Requirements for Enhanced Reductive Bioremediation of Chlorinated Solvent-Contaminated Sites

NASA Astrophysics Data System (ADS)

Robinson, C.; Barry, D. A.

2008-12-01

Enhanced anaerobic dechlorination is a promising technology for in situ remediation of chlorinated ethene DNAPL source areas. However, the build-up of organic acids and HCl in the source zone can lead to significant groundwater acidification. The resulting pH drop inhibits the activity of the dechlorinating microorganisms and thus may stall the remediation process. Source zone remediation requires extensive dechlorination, such that it may be common for soil's natural buffering capacity to be exceeded, and for acidic conditions to develop. In these cases bicarbonate addition (e.g., NaHCO3, KHCO3) is required for pH control. As a design tool for treatment strategies, we have developed BUCHLORAC, a Windows Graphical User Interface based on an abiotic geochemical model that allows the user to predict the acidity generated during dechlorination and associated buffer requirements for their specific operating conditions. BUCHLORAC was motivated by the SABRE (Source Area BioREmediation) project, which aims to evaluate the effectiveness of enhanced reductive dechlorination in the treatment of chlorinated solvent source zones.

Preliminary conceptual models of the occurrence, fate, and transport of chlorinated solvents in karst regions of Tennessee

USGS Publications Warehouse

Wolfe, W.J.; Haugh, C.J.; Webbers, Ank; Diehl, T.H.

1997-01-01

Published and unpublished reports and data from 22 contaminated sites in Tennessee were reviewed to develop preliminary conceptual models of the behavior of chlorinated solvents in karst aquifers. Chlorinated solvents are widely used in many industrial operations. High density and volatility, low viscosity, and solubilities that are low in absolute terms but high relative to drinkingwater standards make chlorinated solvents mobile and persistent contaminants that are difficult to find or remove when released into the groundwater system. The major obstacle to the downward migration of chlorinated solvents in the subsurface is the capillary pressure of small openings. In karst aquifers, chemical dissolution has enlarged joints, bedding planes, and other openings that transmit water. Because the resulting karst conduits are commonly too large to develop significant capillary pressures, chlorinated solvents can migrate to considerable depth in karst aquifers as dense nonaqueous-phase liquids (DNAPL?s). Once chlorinated DNAPL accumulates in a karst aquifer, it becomes a source for dissolved-phase contamination of ground water. A relatively small amount of chlorinated DNAPL has the potential to contaminate ground water over a significant area for decades or longer. Conceptual models are needed to assist regulators and site managers in characterizing chlorinated-solvent contamination in karst settings and in evaluating clean-up alternatives. Five preliminary conceptual models were developed, emphasizing accumulation sites for chlorinated DNAPL in karst aquifers. The models were developed for the karst regions of Tennessee, but are intended to be transferable to similar karst settings elsewhere. The five models of DNAPL accumulation in karst settings are (1) trapping in regolith, (2) pooling at the top of bedrock, (3) pooling in bedrock diffuse-flow zones, (4) pooling in karst conduits, and (5) pooling in isolation from active ground-water flow. More than one conceptual

Direct Push Optical Screening Tool for High Resolution, Real-Time Mapping of Chlorinated Solvent DNAPL Architecture

DTIC Science & Technology

2016-07-01

petroleum hydrocarbon fuels due to higher densities, lower viscosities , and increased weathering (mass depletion) of residual chlorinated solvent DNAPL...generally classified as stratified layers of fine sand and silt with few clay layers. A silt layer was penetrated consistently at a depth of about 45...e.g., stiff clays ) there is potential for the thickness of the dye interaction zone to increase to approximately 1-2 mm. Intuition suggests that this

Solvent vapor collector

DOEpatents

Ellison, Kenneth; Whike, Alan S.

1979-01-30

A solvent vapor collector is mounted on the upstream inlet end of an oven having a gas-circulating means and intended for curing a coating applied to a strip sheet metal at a coating station. The strip sheet metal may be hot and solvent vapors are evaporated at the coating station and from the strip as it passes from the coating station to the oven. Upper and lower plenums within a housing of the collector are supplied with oven gases or air from the gas-circulating means and such gases or air are discharged within the collector obliquely in a downstream direction against the strip passing through that collector to establish downstream gas flows along the top and under surfaces of the strip so as, in turn, to induct solvent vapors into the collector at the coating station. A telescopic multi-piece shroud is usefully provided on the housing for movement between an extended position in which it overlies the coating station to collect solvent vapors released thereat and a retracted position permitting ready cleaning and adjustment of that coating station.

Solvent Reaction Field Potential inside an Uncharged Globular Protein: A Bridge between Implicit and Explicit Solvent Models?

PubMed Central

Baker, Nathan A.; McCammon, J. Andrew

2008-01-01

The solvent reaction field potential of an uncharged protein immersed in Simple Point Charge/Extended (SPC/E) explicit solvent was computed over a series of molecular dynamics trajectories, intotal 1560 ns of simulation time. A finite, positive potential of 13 to 24 kbTec−1 (where T = 300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0 Å from the solute surface, on average 0.008 ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit-solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99. PMID:17949217

Solvent reaction field potential inside an uncharged globular protein: A bridge between implicit and explicit solvent models?

NASA Astrophysics Data System (ADS)

Cerutti, David S.; Baker, Nathan A.; McCammon, J. Andrew

2007-10-01

The solvent reaction field potential of an uncharged protein immersed in simple point charge/extended explicit solvent was computed over a series of molecular dynamics trajectories, in total 1560ns of simulation time. A finite, positive potential of 13-24 kbTec-1 (where T =300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0Å from the solute surface, on average 0.008ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99.

Organic solvent desorption from two tegafur polymorphs.

PubMed

Bobrovs, Raitis; Actiņš, Andris

2013-11-30

Desorption behavior of 8 different solvents from α and β tegafur (5-fluoro-1-(tetrahydro-2-furyl)uracil) has been studied in this work. Solvent desorption from samples stored at 95% and 50% relative solvent vapor pressure was studied in isothermal conditions at 30 °C. The results of this study demonstrated that: solvent desorption rate did not differ significantly for both phases; solvent desorption in all cases occurred faster from samples with the largest particle size; and solvent desorption in most cases occurred in two steps. Structure differences and their surface properties were not of great importance on the solvent desorption rates because the main factor affecting desorption rate was sample particle size and sample morphology. Inspection of the structure packing showed that solvent desorption rate and amount of solvent adsorbed were mainly affected by surface molecule arrangement and ability to form short contacts between solvent molecule electron donor groups and freely accessible tegafur tetrahydrofuran group hydrogens, as well as between solvents molecule proton donor groups and fluorouracil ring carbonyl and fluoro groups. Solvent desorption rates of acetone, acetonitrile, ethyl acetate and tetrahydrofuran multilayers from α and β tegafur were approximately 30 times higher than those of solvent monolayers. Scanning electron micrographs showed that sample storage in solvent vapor atmosphere promotes small tegafur particles recrystallization to larger particles. Copyright © 2013 Elsevier B.V. All rights reserved.

Clay with Desiccation Cracks is an Advection Dominated Environment

NASA Astrophysics Data System (ADS)

Baram, S.; Kurtzman, D.; Sher, Y.; Ronen, Z.; Dahan, O.

2012-04-01

Heavy clay sediments are regarded "safe" from the hydrological point of view due to their low hydraulic conductivities. However, the formation of desiccation cracks in dispersive clays may dramatically change their bulk hydraulic properties. The impact of desiccation cracks on water percolation, dissolved salts and contaminants transport and redox related reactions (microbial ammonium oxidation and denitrification) were investigated in 6 -12 m clay layer near a diary farm waste lagoon. The study implemented unique vadose-zone monitoring systems that enable in-situ measurements of the temporal variation of the sediment's water content along with frequent sampling of the sediment's pore water along the entire vadose zone (> 30 m). Results from four years of continuous measurements showed quick rises in sediment water content following rain events and temporal wastewater overflows. The percolation pattern indicated dominance of preferential flow through a desiccation-cracks network crossing the entire clay sediment layer. High water-propagation velocities (0.4 - 23.6 m h-1) were observed, indicating that the desiccation-crack network remains open and serves as a preferential flow pathway year-round, even at high sediment water content (~0.50 m3 m-3). The rapid percolation bypassed the most bio-geo-active parts of the soil, transporting even highly sorptive contaminants (testosterone and estrogen) in to the deep sections of the vadose zone, accelerating the underlying groundwater contamination. The ammonium and nitrate concentrations in the vadose zone and the high number of nitrifying and denitrifying bacteria (~108 gene copies gdry-sediemt-1, each) found in the sediment indicated that the entire vadose zone is aerated even at high water content conditions (~0.55 m3 m-3). The dissolved salts concentration in the pore-water and the δ2H-H2O and δ18O-H2O values of the pore-water substantially increased with depth (becoming less depleted) in the clay sediment

DOE-EPSCOR SPONSORED PROJECT FINAL REPORT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jianting

Concern over the quality of environmental management and restoration has motivated the model development for predicting water and solute transport in the vadose zone. Soil hydraulic properties are required inputs to subsurface models of water flow and contaminant transport in the vadose zone. Computer models are now routinely used in research and management to predict the movement of water and solutes into and through the vadose zone of soils. Such models can be used successfully only if reliable estimates of the soil hydraulic parameters are available. The hydraulic parameters considered in this project consist of the saturated hydraulic conductivity andmore » four parameters of the water retention curves. To quantify hydraulic parameters for heterogeneous soils is both difficult and time consuming. The overall objective of this project was to better quantify soil hydraulic parameters which are critical in predicting water flows and contaminant transport in the vadose zone through a comprehensive and quantitative study to predict heterogeneous soil hydraulic properties and the associated uncertainties. Systematic and quantitative consideration of the parametric heterogeneity and uncertainty can properly address and further reduce predictive uncertainty for contamination characterization and environmental restoration at DOE-managed sites. We conducted a comprehensive study to assess soil hydraulic parameter heterogeneity and uncertainty. We have addressed a number of important issues related to the soil hydraulic property characterizations. The main focus centered on new methods to characterize anisotropy of unsaturated hydraulic property typical of layered soil formations, uncertainty updating method, and artificial neural network base pedo-transfer functions to predict hydraulic parameters from easily available data. The work also involved upscaling of hydraulic properties applicable to large scale flow and contaminant transport modeling in the vadose zone and

The Extent of Denitrification in Long Island Groundwater using MIMS

NASA Astrophysics Data System (ADS)

Young, C.; Hanson, G. N.; Kroeger, K. D.

2009-12-01

Long Island drinking water is provided by a sole source aquifer with nitrate levels in some North Shore communities approaching or exceeding the drinking water standard of 10 mgL-1. Previous workers, using mass balance approaches, suggested that the primary source of nitrogen is sewage effluent and observed a 50% deficit of nitrate in Long Island’s groundwater system. We analyzed dissolved N2/Ar ratios in groundwater from wells to determine if groundwater denitrification is the cause of the nitrogen deficit at two locations where septic tanks are used for sewage treatment and the effluent leaches to the groundwater; a suburban community on the north shore of Long Island (Northport, NY) and parkland on a barrier island at the south shore of Long Island (Watch Hill, Fire Island National Seashore). In Northport we found 0 to 20 % of the nitrate in groundwater denitrified with excess N-NO3- concentrations ranging from 0 to 1.5 mgL-1. These samples had concentrations high in dissolved oxygen (DO), 6 to 11 mgL-1, and low in dissolved organic carbon (DOC), 0.4 to 2.8 mgL-1. At Watch Hill nitrogen is primarily retained as ammonium or dissolved organic nitrogen. Where nitrate is formed, we found up to 99% denitrification. Excess N-NO3- ranged from 0 to 8 mgL-1 with concentrations low in DO, 0.3 to 3.4 mgL-1, and high in DOC, 5.3 to 18.4 mgL-1. The vadose zone in the Northport area has an average thickness of 10-100 feet whereas at Watch Hill it is 1 - 2 feet thick. We hypothesize that the vadose zone thickness affects the extent of denitrification by controlling the amount of DOC and DO that reaches the groundwater. A thick vadose zone allows for more extensive interaction of infiltrating sewage effluent with atmospheric oxygen in the vadose zone which oxidizes DOC. In Northport groundwater has high DO, low DOC and essentially no denitrification leaving 2 to 11 mgL-1 N-NO3- remaining. At the Watch Hill site a thin vadose zone below the sewage leach field provides

COMPUTER AIDED SOLVENT DESIGN FOR THE ENVIRONMENT

EPA Science Inventory

Solvent substitution is an effective and useful means of eliminating the use of harmful solvents, but finding substitute solvents which are less harmful and as effective as currently used solvents presents significant difficulties. Solvent substitution is a form of reverse engin...

Towards ultra-fast solvent evaporation, the development of a computer controlled solvent vapor annealing chamber

NASA Astrophysics Data System (ADS)

Nelson, Gunnar; Wong, J.; Drapes, C.; Grant, M.; Baruth, A.

Despite the promise of cheap and fast nanoscale ordering of block polymer thin films via solvent vapor annealing, a standardized, scalable production scheme remains elusive. Solvent vapor annealing exposes a nano-thin film to the vapors of one or more solvents with the goal of forming a swollen and mobile state to direct the self-assembly process by tuning surface energies and mediating unfavorable chain interactions. We have shown that optimized annealing conditions, where kinetic and thermal properties for crystal growth are extremely fast (<1s), exist at solvent concentrations just below the order-disorder transition of the film. However, when investigating the propagation of a given morphology into the bulk of a film during drying, the role of solvent evaporation comes under great scrutiny. During this process, the film undergoes a competition between two fronts; phase separation and kinetic trapping. Recent results in both theory and experiment point toward this critical element in controlling the resultant morphologies; however, no current method includes a controllable solvent evaporation rate at ultra-fast time scales. We report on a computer-controlled, pneumatically actuated chamber that provides control over solvent evaporation down to 15 ms. Furthermore, in situ spectral reflectance monitors solvent concentration with 10 ms temporal resolution and reveals several possible evaporation trajectories, ranging from linear to exponential to logarithmic. Funded by Dr. Randolph Ferlic Summer Research Scholarship and NASA Nebraska Space Grant.

Anionic microemulsion to solvent stacking for on-line sample concentration of cationic analytes in capillary electrophoresis.

PubMed

Kukusamude, Chunyapuk; Srijaranai, Supalax; Quirino, Joselito P

2014-05-01

The common SDS microemulsion (i.e. 3.3% SDS, 0.8% octane, and 6.6% butanol) and organic solvents were investigated for the stacking of cationic drugs in capillary zone electrophoresis using a low pH separation electrolyte. The sample was prepared in the acidic microemulsion and a high percentage of organic solvent was included in the electrolyte at anodic end of capillary. The stacking mechanism was similar to micelle to solvent stacking where the micelles were replaced by the microemulsion for the transport of analytes to the organic solvent rich boundary. This boundary is found between the microemulsion and anodic electrolyte. The effective electrophoretic mobility of the cations reversed from the direction of the anode in the microemulsion to the cathode in the boundary. Microemulsion to solvent stacking was successfully achieved with 40% ACN in the anodic electrolyte and hydrodynamic sample injection of 21 s at 1000 mbar (equivalent to 30% of the effective length). The sensitivity enhancement factors in terms of peak height and corrected peak area were 15 to 35 and 21 to 47, respectively. The linearity R(2) in terms of corrected peak area were >0.999. Interday precisions (%RSD, n = 6) were 3.3-4.0% for corrected peak area and 2.0-3.0% for migration time. Application to spiked real sample is also presented. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

METHOD FOR SOLVENT-ISOSTATIC PRESSING

DOEpatents

Archibald, P.B.

1962-09-18

This invention provides a method for producing densely compacted bodies having relatively large dimensions. The method comprises the addition of a small quantity of a suitable solvent to a powder which is to be compacted. The solvent- moistened powder is placed inside a flexible bag, and the bag is suspended in an isostatic press. The solvent is squeezed out of the powder by the isostatic pressure, and the resulting compacted body is recovered. The presence of the solvent markedly decreases the proportion of void space in the powder, thereby resulting in a denser, more homogeneous compact. Another effect of the solvent is that it allows the isostatic pressing operation to be conducted at substantially lower pressures than are conventionally employed. (AEC)

Nitrous oxide fluxes from cultivated areas and rangeland: U.S. High Plains

USGS Publications Warehouse

Weeks, Edwin P.; McMahon, Peter B.

2007-01-01

Concentration profiles of N2O, a greenhouse gas, and the conservative trace gases SF6 and the chlorofluorocarbons CFC-11, CFC-12, CFC-113, and were measured periodically through thick vadose zones at nine sites in the U.S. High Plains. The CFC and SF6 measurements were used to calibrate a one-dimensional gas diffusion model, using the parameter identification program UCODE. The calibrated model was used with N2O measurements to estimate average annual N2O flux from both the root zone and the deep vadose zone to the atmosphere. Estimates of root-zone N 2O fluxes from three rangeland sites ranged from near 0 to about 0.2 kg N2O-N ha-1 yr-1, values near the low end of the ranges determined for native grass from other studies. Estimates of root-zone N2O fluxes from two fields planted to corn (Zea mays L.) of about 2 to 6 kg N2O-N ha-1 yr-1 are similar to those determined for corn in other studies. Estimates of N2O flux from Conservation Reserve grassland converted from irrigated corn indicate that production of N2O is substantially reduced following conversion from cropland. Small N2O fluxes from the water table or from deep in the vadose zone occurred at three sites, ranging from 0.004 to 0.02 kg N 2O-N ha-1 yr-1. Our estimates of N2O flux represent space- and time-averaged values that should be useful to more fully evaluate the significance of instantaneous point flux measurements. ?? Soil Science Society of America.

Moving zone Marangoni drying of wet objects using naturally evaporated solvent vapor

DOEpatents

Britten, Jerald A.

1997-01-01

A surface tension gradient driven flow (a Marangoni flow) is used to remove the thin film of water remaining on the surface of an object following rinsing. The process passively introduces by natural evaporation and diffusion of minute amounts of alcohol (or other suitable material) vapor in the immediate vicinity of a continuously refreshed meniscus of deionized water or another aqueous-based, nonsurfactant rinsing agent. Used in conjunction with cleaning, developing or wet etching application, rinsing coupled with Marangoni drying provides a single-step process for 1) cleaning, developing or etching, 2) rinsing, and 3) drying objects such as flat substrates or coatings on flat substrates without necessarily using heat, forced air flow, contact wiping, centrifugation or large amounts of flammable solvents. This process is useful in one-step cleaning and drying of large flat optical substrates, one-step developing/rinsing and drying or etching/rinsing/drying of large flat patterned substrates and flat panel displays during lithographic processing, and room-temperature rinsing/drying of other large parts, sheets or continuous rolls of material.

Moving zone Marangoni drying of wet objects using naturally evaporated solvent vapor

DOEpatents

Britten, J.A.

1997-08-26

A surface tension gradient driven flow (a Marangoni flow) is used to remove the thin film of water remaining on the surface of an object following rinsing. The process passively introduces by natural evaporation and diffusion of minute amounts of alcohol (or other suitable material) vapor in the immediate vicinity of a continuously refreshed meniscus of deionized water or another aqueous-based, nonsurfactant rinsing agent. Used in conjunction with cleaning, developing or wet etching application, rinsing coupled with Marangoni drying provides a single-step process for (1) cleaning, developing or etching, (2) rinsing, and (3) drying objects such as flat substrates or coatings on flat substrates without necessarily using heat, forced air flow, contact wiping, centrifugation or large amounts of flammable solvents. This process is useful in one-step cleaning and drying of large flat optical substrates, one-step developing/rinsing and drying or etching/rinsing/drying of large flat patterned substrates and flat panel displays during lithographic processing, and room-temperature rinsing/drying of other large parts, sheets or continuous rolls of material. 5 figs.

Enhanced Amendment Delivery to Low Permeability Zones for Chlorinated Solvent Source Area Bioremediation

DTIC Science & Technology

2014-10-01

enhanced amendments delivery process, a non-toxic biodegradable polymer, such as xanthan gum, is added to the injection solution to form a non- Newtonian...Once injection stops, the injected fluid viscosity increases and creates a more stable zone for biodegradation reactions because the amendment-laden...electron acceptors and biodegradation of the shear-thinning agent. • Determine the cost factors for applying the STF enhanced delivery technology

Enhanced Amendment Delivery to Low Permeability Zones for Chlorinated Solvent Source Area Bioremediation

DTIC Science & Technology

2014-09-01

suspend manganese dioxide particles produced from oxidation of permanganate in aqueous phase (Crimi and Ko, 2009). Xanthan gum is a biopolymer that...shear-thinning fluids for improving treatment of low-k zones. This study established that combinations of xanthan gum and potassium permanganate ...flow cell experiments using xanthan gum solution to deliver permanganate , Chokejaroenrat et al. (2013, 2014) presented a set of data supporting that

Solvent extraction of diatomite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, W.

1984-07-24

There is provided a method of extracting hydrocarbons from a diatomite ore. The particle size of the ore is first reduced to form a processed ore. The processed ore is then mixed with a substantially irregular granular material to form an unstratified ore mixture having increased permeability to an extracting solvent. The unstratified ore mixture is then permeated with an extracting solvent to obtain a hydrocarbon-solvent stream from which hydrocarbons are subsequently separated. The irregular granular material may be sand.

Organic Solvent Effects in Biomass Conversion Reactions.

PubMed

Shuai, Li; Luterbacher, Jeremy

2016-01-01

Transforming lignocellulosic biomass into fuels and chemicals has been intensely studied in recent years. A large amount of work has been dedicated to finding suitable solvent systems, which can improve the transformation of biomass into value-added chemicals. These efforts have been undertaken based on numerous research results that have shown that organic solvents can improve both conversion and selectivity of biomass to platform molecules. We present an overview of these organic solvent effects, which are harnessed in biomass conversion processes, including conversion of biomass to sugars, conversion of sugars to furanic compounds, and production of lignin monomers. A special emphasis is placed on comparing the solvent effects on conversion and product selectivity in water with those in organic solvents while discussing the origins of the differences that arise. We have categorized results as benefiting from two major types of effects: solvent effects on solubility of biomass components including cellulose and lignin and solvent effects on chemical thermodynamics including those affecting reactants, intermediates, products, and/or catalysts. Finally, the challenges of using organic solvents in industrial processes are discussed from the perspective of solvent cost, solvent stability, and solvent safety. We suggest that a holistic view of solvent effects, the mechanistic elucidation of these effects, and the careful consideration of the challenges associated with solvent use could assist researchers in choosing and designing improved solvent systems for targeted biomass conversion processes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessing controls on perched saturated zones beneath the Idaho Nuclear Technology and Engineering Center, Idaho

USGS Publications Warehouse

Mirus, Benjamin B.; Perkins, Kim S.; Nimmo, John R.

2011-01-01

Waste byproducts associated with operations at the Idaho Nuclear Technology and Engineering Center (INTEC) have the potential to contaminate the eastern Snake River Plain (ESRP) aquifer. Recharge to the ESRP aquifer is controlled largely by the alternating stratigraphy of fractured volcanic rocks and sedimentary interbeds within the overlying vadose zone and by the availability of water at the surface. Beneath the INTEC facilities, localized zones of saturation perched on the sedimentary interbeds are of particular concern because they may facilitate accelerated transport of contaminants. The sources and timing of natural and anthropogenic recharge to the perched zones are poorly understood. Simple approaches for quantitative characterization of this complex, variably saturated flow system are needed to assess potential scenarios for contaminant transport under alternative remediation strategies. During 2009-2011, the U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, employed data analysis and numerical simulations with a recently developed model of preferential flow to evaluate the sources and quantity of recharge to the perched zones. Piezometer, tensiometer, temperature, precipitation, and stream-discharge data were analyzed, with particular focus on the possibility of contributions to the perched zones from snowmelt and flow in the neighboring Big Lost River (BLR). Analysis of the timing and magnitude of subsurface dynamics indicate that streamflow provides local recharge to the shallow, intermediate, and deep perched saturated zones within 150 m of the BLR; at greater distances from the BLR the influence of streamflow on recharge is unclear. Perched water-level dynamics in most wells analyzed are consistent with findings from previous geochemical analyses, which suggest that a combination of annual snowmelt and anthropogenic sources (for example, leaky pipes and drainage ditches) contribute to recharge of shallow and

Green Remediation Best Management Practices: Soil Vapor Extraction & Air Sparging

EPA Pesticide Factsheets

Historically, approximately one-quarter of Superfund source control projects have involved soil vapor extraction (SVE) to remove volatile organic compounds (VOCs) sorbed to soil in the unsaturated (vadose) zone.

Biodegradation of Petroleum Hydrocarbon in the Vadose Zone

EPA Science Inventory

There are two major impediments to a better understanding of the influence of biodegradation on the risk of intrusion of petroleum vapors. We describe the contribution of biodegradation as an attenuation factor between the source and the receptor. The use of attenuation factors...

IDENTIFICATION AND COMPILATION OF UNSATURATED/VADOSE ZONE MODELS

EPA Science Inventory

Many ground-water contamination problems are derived from sources at or near the soil surface. Consequently, the physical and (bio-)chemical behavior of contaminants in the shallow subsurface is of critical importance to the development of protection and remediation strategies. M...

Insecticide solvents: interference with insecticidal action.

PubMed

Brattsten, L B; Wilkinson, C F

1977-06-10

Several commercial solvent mixtures commonly used as insecticide carriers in spray formulations increase by more than threefold the microsomal N-demethylation of p-chloro N-methylaniline in midgut preparations of southern army-worm (Spodoptera eridania) larvae exposed orally to the test solvents. Under laboratory conditions, the same solvent mixtures exhibit a protective action against the in vivo toxicity of the insecticide carbaryl to the larvae. The data are discussed with respect to possible solvent-insecticide interactions occurring under field conditions and, more broadly, to potential toxicological hazards of these solvents to humans.

Monitoring CO2 Intrusion in shallow aquifer using complex electrical methods and a novel CO2 sensitive Lidar-based sensor

NASA Astrophysics Data System (ADS)

Leger, E.; Dafflon, B.; Thorpe, M.; Kreitinger, A.; Laura, D.; Haivala, J.; Peterson, J.; Spangler, L.; Hubbard, S. S.

2016-12-01

While subsurface storage of CO2 in geological formations offers significant potential to mitigate atmospheric greenhouse gasses, approaches are needed to monitor the efficacy of the strategy as well as possible negative consequences, such as leakage of CO2 or brine into groundwater or release of fugitive gaseous CO2. Groundwater leakages can cause subsequent reactions that may also be deleterious. For example, a release of dissolved CO2 into shallow groundwatersystems can decrease groundwater pH which can potentiallymobilize naturally occurring trace metals and ions. In this perspective, detecting and assessing potential leak requires development of novel monitoring techniques.We present the results of using surface electrical resistivity tomography (ERT) and a novel CO2 sensitive Lidar-based sensor to monitor a controlled CO2 release at the ZeroEmission Research and Technology Center (Bozeman, Montana). Soil temperature and moisture sensors, wellbore water quality measurements as well as chamber-based CO2 flux measurements were used in addition to the ERT and a novel Lidar-based sensor to detect and assess potential leakage into groundwater, vadose zone and atmosphere. The three-week release wascarried out in the vadose and the saturated zones. Well sampling of pH and conductivity and surface CO2 fluxes and concentrations measurements were acquired during the release and are compared with complex electricalresistivity time-lapse measurements. The novel Lidar-based image of the CO2 plume were compared to chamber-based CO2 flux and concentration measurements. While a continuous increase in subsurface ERT and above ground CO2 was documented, joint analysis of the above and below ground data revealed distinct transport behavior in the vadose and saturated zones. Two type of transport were observed, one in the vadoze zone, monitored by CO2 flux chamber and ERT, and the other one in the saturated zone, were ERT and wellsampling were carried. The experiment suggests how

Organic solvents in the pharmaceutical industry.

PubMed

Grodowska, Katarzyna; Parczewski, Andrzej

2010-01-01

Organic solvents are commonly used in the pharmaceutical industry as reaction media, in separation and purification of synthesis products and also for cleaning of equipment. This paper presents some aspects of organic solvents utilization in an active pharmaceutical ingredient and a drug product manufacturing process. As residual solvents are not desirable substances in a final product, different methods for their removal may be used, provided they fulfill safety criteria. After the drying process, analyses need to be performed to check if amounts of solvents used at any step of the production do not exceed acceptable limits (taken from ICH Guideline or from pharmacopoeias). Also new solvents like supercritical fluids or ionic liquids are developed to replace "traditional" organic solvents in the pharmaceutical production processes.

The legacy of chlorinated solvents in the Birmingham aquifer, UK: Observations spanning three decades and the challenge of future urban groundwater development

NASA Astrophysics Data System (ADS)

Rivett, Michael O.; Turner, Ryan J.; Glibbery (née Murcott), Penny; Cuthbert, Mark O.

2012-10-01

Licensed abstraction well data collected during 1986-2008 from a total of 77 wells mainly located at industrial sites combined with historic land use data from 1975 has allowed insight into the legacy of chlorinated solvent contamination in the Birmingham aquifer that underlies the UK's second largest city. This legacy, expected to be reasonably symptomatic of those occurring in other urban aquifers, was characterised by: dominance of parent solvents, particularly TCE (trichloroethene) that widely exceeded drinking-water quality criteria; greater TCE occurrence in wells in proximity to increased historic land use by the metal/engineering solvent-user industry (the relationship providing a first-pass indicator of future resource development potential); regional groundwater vulnerability controls; well abstraction changes (over months to decades) influential of observed concentration transients and anticipated plume capture or release; persistence of contamination over decades (with less soluble PCE (perchloroethene) showing increased persistence relative to TCE) that was reasonably ascribed to slow contaminant release from DNAPL (dense non-aqueous phase liquid) sources and, or low permeability layers; presence of dechlorination products arising from solvent (bio)degradation, although this key attenuation process appeared to have moderate to weak influence regionally on plumes; and, inadvertent, but significant solvent mass removal from the aquifer by industrial abstractions. Key challenges to realising future urban groundwater development were identified based on the observed legacy and well capture zone simulations. Despite the extensive contamination of the aquifer, it should still be possible to develop wells of high (several megalitres per day) capacity for drinking water supply (or other lower grade uses) without the requirement for solvent treatment. In those areas with higher risk of contamination, our dataset, together with application of emergent risk

Next Generation Solvent (NGS): Development for Caustic-Side Solvent Extraction of Cesium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moyer, Bruce A.; Birdwell, Jr, Joseph F.; Bonnesen, Peter V.

This report summarizes the FY 2010 and 2011 accomplishments at Oak Ridge National Laboratory (ORNL) in developing the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process, referred to commonly as the Next Generation Solvent (NGS), under funding from the U.S. Department of Energy, Office of Environmental Management (DOE-EM), Office of Technology Innovation and Development. The primary product of this effort is a process solvent and preliminary flowsheet capable of meeting a target decontamination factor (DF) of 40,000 for worst-case Savannah River Site (SRS) waste with a concentration factor of 15 or higher in the 18-stage equipment configuration of the SRS Modularmore » Caustic-Side Solvent Extraction Unit (MCU). In addition, the NG-CSSX process may be readily adapted for use in the SRS Salt Waste Processing Facility (SWPF) or in supplemental tank-waste treatment at Hanford upon appropriate solvent or flowsheet modifications. Efforts in FY 2010 focused on developing a solvent composition and process flowsheet for MCU implementation. In FY 2011 accomplishments at ORNL involved a wide array of chemical-development activities and testing up through single-stage hydraulic and mass-transfer tests in 5-cm centrifugal contactors. Under subcontract from ORNL, Argonne National Laboratory (ANL) designed a preliminary flowsheet using ORNL cesium distribution data, and Tennessee Technological University confirmed a chemical model for cesium distribution ratios (DCs) as a function of feed composition. Interlaboratory efforts were coordinated with complementary engineering tests carried out (and reported separately) by personnel at Savannah River National Laboratory (SRNL) and Savannah River Remediation (SRR) with helpful advice by Parsons Engineering and General Atomics on aspects of possible SWPF implementation.« less

UV-Vis spectroscopic study and DFT calculation on the solvent effect of trimethoprim in neat solvents and aqueous mixtures.

PubMed

Almandoz, M C; Sancho, M I; Duchowicz, P R; Blanco, S E

2014-08-14

The solvatochromic behavior of trimethoprim (TMP) was analyzed using UV-Vis spectroscopy and DFT methods in neat and binary aqueous solvent mixtures. The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding interactions on the absorption maxima were evaluated by means of the linear solvation energy relationship concept of Kamlet and Taft. This analysis indicated that both interactions play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra of TMP and TMP:(solvent)n complexes in ACN and H2O using TD-DFT methods were in agreement with the experimental ones. Binary aqueous mixtures containing as co-solvents DMSO, ACN and EtOH were studied. Preferential solvation was detected as a nonideal behavior of the wavenumber curve respective to the analytical mole fraction of co-solvent in all binary systems. TMP molecules were preferentially solvated by the organic solvent over the whole composition range. Index of preferential solvation, as well as the influence of solvent parameters were calculated as a function of solvent composition. Copyright © 2014 Elsevier B.V. All rights reserved.

A QSPR study on the solvent-induced frequency shifts of acetone and dimethyl sulfoxide in organic solvents.

PubMed

Ou, Yu Heng; Chang, Chia Ming; Chen, Ying Shao

2016-06-05

In this study, solvent-induced frequency shifts (SIFS) in the infrared spectrum of acetone and dimethyl sulfoxide in organic solvents were investigated by using four types of quantum-chemical reactivity descriptors. The results showed that the SIFS of acetone is mainly affected by the electron-acceptance chemical potential and the maximum nucleophilic condensed local softness of organic solvents, which represent the electron flow and the polarization between acetone and solvent molecules. On the other hand, the SIFS of dimethyl sulfoxide changes with the maximum positive charge of hydrogen atom and the inverse of apolar surface area of solvent molecules, showing that the electrostatic and hydrophilic interactions are main mechanisms between dimethyl sulfoxide and solvent molecules. The introduction of the four-element theory model-based quantitative structure-property relationship approach improved the assessing quality and provided a basis for interpreting the solute-solvent interactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Biodegradation of Chlorinated Solvents: Reactions near DNAPL and Enzyme Function

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCarty, P. L.; Spormann, Alfred M.; Criddle, Craig, S.

factors of three to five times, leading to a more rapid clean-up of the DNAPL zone. The most favored electron donor to add is one which partitions well with the chlorinated solvent or can be concentrated near it. Unfortunately, an ideal electron donor, such as vegetable oil, is difficult to introduce and mix with DNAPL in the ground, doing this properly remains an engineering challenge. Numerical model studies have indicated that several factors may significantly influence the rate and extent of enhancement, including the inhibitory effects of PCE and cDCE, the level of ED concentration, DNAPL configuration, and competition for ED. Such factors need to be considered when contemplating engineered DNAPL bioremediation. Pseudomonas stuzeri KC is an organism that transforms CT to carbon dioxide and chloride without the formation of the hazardous intermediate, chloroform. This is accomplished by production and secretion of a molecule called PDTC. This study was direct ed towards determining how PDTC works. Cu (II) at a ratio of 1:1 Cu to PDTC was found to result in the most rapid CT transformation, confirming that the PDTC-Cu complex is both a reactant and a catalyst in CT transformation. CT degradation requires that the PDTC be in a reduced form, which is generated by contact with cell components. Fe(II) inhibits CT transformation by PDTC. Studies indicated that this inhibition is enhanced by some compound or factor in the supernatant with molecular weight greater than 10,000 Da. We have made progress in determining what this factor might be, but have not yet been able to identify it. In related studies, we found that CT transformation by another organism, Shewanella oneidensis MR1, also involves an excreted factor, but this factor is different from PDTC and results in chloroform transformation as an intermediate. Our studies have indicated that this factor is similar to vitamin K2, and we have also confirmed that vitamin K2 does transform C T into chloroform.« less

Halogenated solvent remediation

DOEpatents

Sorenson, Jr., Kent S.

2008-11-11

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

Gas separation by composite solvent-swollen membranes

DOEpatents

Matson, S.L.; Lee, E.K.L.; Friesen, D.T.; Kelly, D.J.

1989-04-25

There is disclosed a composite immobilized liquid membrane of a solvent-swollen polymer and a microporous organic or inorganic support, the solvent being at least one highly polar solvent containing at least one nitrogen, oxygen, phosphorus or sulfur atom, and having a boiling point of at least 100 C and a specified solubility parameter. The solvent or solvent mixture is homogeneously distributed through the solvent-swollen polymer from 20% to 95% by weight. The membrane is suitable for acid gas scrubbing and oxygen/nitrogen separation. 3 figs.

Gas separation by composite solvent-swollen membranes

DOEpatents

Matson, Stephen L.; Lee, Eric K. L.; Friesen, Dwayne T.; Kelly, Donald J.

1989-01-01

There is disclosed a composite immobulized liquid membrane of a solvent-swollen polymer and a microporous organic or inorganic support, the solvent being at least one highly polar solvent containing at least one nitrogen, oxygen, phosphorous or sulfur atom, and having a boiling point of at least 100.degree. C. and a specified solubility parameter. The solvent or solvent mixture is homogeneously distributed through the solvent-swollen polymer from 20% to 95% by weight. The membrane is suitable for acid gas scrubbing and oxygen/nitrogen separation.

Solvent effects on infrared spectra of progesterone in CHCl 3/ cyclo-C 6H 12 binary solvent systems

NASA Astrophysics Data System (ADS)

Liu, Qing; Wang, Xiao-yan; Zhang, Hui

2007-01-01

The infrared spectroscopy studies of the C 3 and C 20 carbonyl stretching vibrations ( υ(C dbnd O)) of progesterone in CHCl 3/ cyclo-C 6H 12 binary solvent systems were undertaken to investigate the solute-solvent interactions. With the mole fraction of CHC1 3 in the binary solvent mixtures increase, three types of C 3 and C 20 carbonyl stretching vibration band of progesterone are observed, respectively. The assignments of υ(C dbnd O) of progesterone are discussed in detail. In the CHCl 3-rich binary solvent systems or pure CHCl 3 solvent, two kinds of solute-solvent hydrogen bonding interactions coexist for C 20 C dbnd O. Comparisons are drawn for the solvent sensitivities of υ(C dbnd O) for acetophenone and 5α-androstan-3,17-dione, respectively.

Role of solvent in metal-on-metal surface diffusion: A case for rational solvent selection for materials synthesis

NASA Astrophysics Data System (ADS)

Imandi, Venkataramana; Jagannath, Mantha Sai Pavan; Chatterjee, Abhijit

2018-09-01

The effect of solvent on diffusion at metal surfaces is poorly understood despite its importance to morphological evolution during materials processing, corrosion and catalysis. In this article, we probe the metal-solvent interfacial structure, effective nature of interactions and dynamics when a solvent is in contact with a metal using a novel accelerated molecular dynamics simulation technique called temperature programmed molecular dynamics (TPMD). TPMD simulations reveal that surface diffusion of metal-on-metal can be made to vary over orders-of-magnitude by tuning the metal-solvent interaction. Ultimately, the solvent can have an indirect effect on diffusion. As the solvent tugs at the metal surface the separation between the adsorbed metal atom (adatom) and the surface layer can be modulated via metal-solvent interactions. The resulting adatom-surface separation can cause stronger/weaker binding of the adatom to the metal surface, which in turn results in the observed slower/enhanced diffusion in the presence of solvent. We believe this effect is ubiquitous in pure metal and metal alloys and in principle one could rationally select solvent to control the material structural evolution. Implications on materials synthesis are discussed in the context of formation of nanoporous materials.

Replacement solvents for use in chemical synthesis

DOEpatents

Molnar, Linda K.; Hatton, T. Alan; Buchwald, Stephen L.

2001-05-15

Replacement solvents for use in chemical synthesis include polymer-immobilized solvents having a flexible polymer backbone and a plurality of pendant groups attached onto the polymer backbone, the pendant groups comprising a flexible linking unit bound to the polymer backbone and to a terminal solvating moiety. The polymer-immobilized solvent may be dissolved in a benign medium. Replacement solvents for chemical reactions for which tetrahydrofuran or diethyl may be a solvent include substituted tetrahydrofurfuryl ethers and substituted tetrahydro-3-furan ethers. The replacement solvents may be readily recovered from the reaction train using conventional methods.

Antioxidant and antimicrobial activities of solvent fractions of Vernonia cinerea (L.) Less leaf extract.

PubMed

Sonibare, Mubo A; Aremu, Oluwafunmilola T; Okorie, Patricia N

2016-06-01

Vernonia cinerea (L.) Less is used in folk medicine as a remedy for various diseases. The present study reports antioxidant and antimicrobial activities of solvent fractions of Vernonia cinerea. The antioxidant properties of solvent fractions of V. cinerea were evaluated by determining radicals scavenging activity, total flavonoid and phenolic contents measured with the 2,2-diphenyl-1-picryl hydrazyl (DPPH) test, the aluminum chloride and the Folin-ciocalteau methods, respectively. Antimicrobial activities were tested against human pathogenic microorganisms using agar diffusion method. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of each active extract were determined. The ethyl acetate fraction having the IC50 value of 6.50 µg/mL demonstrated comparable DPPH radical-scavenging activity with standard antioxidants, gallic acid and quercetin included in the study. All fractions displayed moderate antimicrobial potential against the tested pathogens with the zone of inhibition that ranged from 9.0 to 13.5 mm. The MIC (1.56 mg/mL) and MBC (3.13 mg/mL) indicated highest susceptibility of Candida albicans in all fractions. The results of this study showed that the solvent fractions of V. cinerea possess antioxidant and antimicrobial activities, hence justifying the folkloric use of the plant for the treatment of various ailments in traditional medicine.

Radiative Convective Transfer Calculations for Effective Stellar Fluxes of Habitable and Life Supporting Zones

NASA Astrophysics Data System (ADS)

Ludwig, Wolfgang; Eggl, Siegfried; Neubauer, David; Leitner, Johannes; Firneis, Maria; Hitzenberger, Regina

2014-05-01

Recent fields of interest in exoplanetary research include studies of potentially habitable planets orbiting stars outside of our Solar System. Habitable Zones (HZs) are currently defined by calculating the inner and the outer limits of the mean distance between exoplanets and their central stars based on effective solar fluxes that allow for maintaining liquid water on the planet's surface. Kasting et al. (1993), Selsis et al. (2007), and recently Kopparapu et al. (2013) provided stellar flux limits for such scenarios. We compute effective solar fluxes for Earth-like planets using Earth-like and other atmospheric scenarios including atmospheres with high level and low level clouds. Furthermore we provide habitability limits for solvents other than water, i.e. limits for the so called Life Supporting Zone, introduced by Leitner et al. (2010). The Life Supporting Zone (LSZ) encompasses many habitable zones based on a variety of liquid solvents. Solvents like ammonia and sulfuric acid have been identified for instance by Leitner et al (2012) as possibly life supporting. Assuming planets on circular orbits, the extent of the individual HZ is then calculated via the following equation, d(i,o) = [L/Lsun*1/S(i,o)]**0.5 au, where L is the star's luminosity, and d(i,o) and S(i,o) are the distances to the central star for the inner and the outer edge and effective insolation for inner and the outer edge of the HZ, respectively. After generating S(i,o) values for a selection of solvents, we provide the means to determine LSZ boundaries for main sequence stars. Effective flux calculations are done using a one dimensional radiative convective model (Neubauer et al. 2011) based on a modified version of the open source radiative transfer software Streamer (Key and Schweiger, 1998). Modifications include convective adjustments, additional gases for absorption and the use of an offline cloud model, which allow us to observe the influence of clouds on effective stellar fluxes

Safe battery solvents

DOEpatents

Harrup, Mason K.; Delmastro, Joseph R.; Stewart, Frederick F.; Luther, Thomas A.

2007-10-23

An ion transporting solvent maintains very low vapor pressure, contains flame retarding elements, and is nontoxic. The solvent in combination with common battery electrolyte salts can be used to replace the current carbonate electrolyte solution, creating a safer battery. It can also be used in combination with polymer gels or solid polymer electrolytes to produce polymer batteries with enhanced conductivity characteristics. The solvents may comprise a class of cyclic and acyclic low molecular weight phosphazenes compounds, comprising repeating phosphorus and nitrogen units forming a core backbone and ion-carrying pendent groups bound to the phosphorus. In preferred embodiments, the cyclic phosphazene comprises at least 3 phosphorus and nitrogen units, and the pendent groups are polyethers, polythioethers, polyether/polythioethers or any combination thereof, and/or other groups preferably comprising other atoms from Group 6B of the periodic table of elements.

Green and Bio-Based Solvents.

PubMed

Calvo-Flores, Francisco G; Monteagudo-Arrebola, María José; Dobado, José A; Isac-García, Joaquín

2018-04-24

Chemical reactions and many of the procedures of separation and purification employed in industry, research or chemistry teaching utilize solvents massively. In the last decades, with the birth of Green Chemistry, concerns about the employment of solvents and the effects on human health, as well as its environmental impacts and its dependence on non-renewable raw materials for manufacturing most of them, has drawn the attention of the scientific community. In this work, we review the concept of green solvent and the properties and characteristics to be considered green. Additionally, we discuss the different possible routes to prepare many solvents from biomass, as an alternative way to those methods currently applied in the petrochemical industry.

Discussion of pore pressure transmission under rain infiltration in a soil layer

NASA Astrophysics Data System (ADS)

Yang, S. Y.; Jan, C. D.

2017-12-01

The vadose zone (or unsaturated zone) denotes the geologic media between ground surface and the water table in situ where the openings, or pores, in the soil (rock) layers are partially filled with water and air. In this landscape, rainwater infiltrates into soils advancing through this vadose zone and could generates a shallow saturation zone at soil bedrock boundary due to permeability contrast. This saturation zone leads to downslope shallow subsurface storm runoff that contributes to a part of saturation overland flow, dominating water reaching river channels. Hence, unsaturated processes (e.g., rain infiltration) is an important issue that can determine the timing and magnitude of positive pore pressure and discharge peaks, and the characteristics of runoff, water chemistry, hillslope stability is also tie to the processes. In this study, we investigated the transmission of pore pressure evolution in the vadose zone for diverse soil materials based on poroelasticity theory. Commonly, a traditional way is to utilize the Richard's equation to predict pore pressure evolution under unsaturated rain infiltration, ignoring the inertial effect on the process. Here we relax this limitation and propose two reference time tk and tep that can represent the arriving time at a certain depth of wave propagation and dissipation, respectively. Form ground surface to a depth of 1 m, tk has significant differences under nearly unsaturated conditions for diverse soil properties; however, no evident variations in tk can be observed under nearly saturated conditions. Values of tep for loose, cohesionless soils are much greater but decreases to the smallest one (within 1 day) than those for other soil properties under a nearly saturated condition. Results indicate that transient pore pressure transmission is mainly dominated by dynamic wave propagation but the effect of dissipation could become more important with increase in water saturation.

Advanced Polymer Technology for Containing and Immobilizing Strontium-90 in the Subsurface - 8361

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. Baker; G. Heath; C. Scott

2008-02-01

Many Department of Energy (DOE) sites, including Idaho and Hanford, have heavy metals and/or radionuclides (e.g. strontium-90) present that are strongly adsorbed in the vadose zone, but which nevertheless are propagating toward the water table. A key challenge for immobilization of these contaminants is bringing the chosen amendment or remediation technology into contact with the contaminated porous medium, while ensuring that contaminated water and colloids do not escape. This is particularly challenging when the subsurface geology is complex and highly heterogeneous, as is the case at many DOE sites. The Idaho National Laboratory (INL) in collaboration with the University ofmore » Texas at Austin (UT) has conducted research sponsored through the DOE Office of Environmental Management (EM) Advanced Remediation Technologies Phase I program that successfully demonstrated application of a novel, pH-triggered advanced polymer for creating a physical barrier that prevents heavy metals and radionuclides in vadose zone soil and soil-pore water from migrating to the groundwater. The focus of this paper is on the column and sandbox experiments conducted by researchers at the Idaho National Laboratory in support of the Phase I program objectives. Proof of these concepts provides a technology basis for confining or isolating a volume of contaminated groundwater, to be implemented in future investigations at the Vadose Zone Research Park (VZRP) at INL.« less

A model of oscillatory transport in granular soils, with application to barometric pumping and earth tides.

PubMed

Neeper, D A

2001-04-01

A simple algebraic model is proposed to estimate the transport of a volatile or soluble chemical caused by oscillatory flow of fluid in a porous medium. The model is applied to the barometric pumping of vapors in the vadose zone, and to the transport of dissolved species by earth tides in an aquifer. In the model, the fluid moves sinusoidally with time in the porosity of the soil. The chemical concentration in the mobile fluid is considered to equilibrate with the concentration in the surrounding matrix according to a characteristic time governed by diffusion, sorption, or other rate processes. The model provides a closed form solution, to which barometric pressure data are applied in an example of pore gas motion in the vadose zone. The model predicts that the additional diffusivity due barometric pumping in an unfractured vadose zone would be comparable to the diffusivity in stagnant pore gas if the equilibration time is 1 day or longer. Water motion due to the M2 lunar tide is examined as an example of oscillatory transport in an aquifer. It is shown that the tidal motion of the water in an aquifer might significantly increase the vertical diffusivity of dissolved species when compared to diffusion in an absolutely stagnant aquifer, but the hydrodynamic dispersivity due to tidal motion or gravitational flow would probably exceed the diffusivity due to oscillatory advection.

Solvent Extraction of Furfural From Biomass

NASA Technical Reports Server (NTRS)

Humphrey, M. F.

1984-01-01

Solvent-extraction method reduces energy required to remove furfural produced during acid hydrolysis of biomass. Acid hydrolysis performed in vessel containing both solvents and reacting ingredients. With intimate contact between solvents and aqueous hydrolyis liqour, furfural removed form liquor almost as fast as it forms.

Coal liquefaction process with enhanced process solvent

DOEpatents

Givens, Edwin N.; Kang, Dohee

1984-01-01

In an improved coal liquefaction process, including a critical solvent deashing stage, high value product recovery is improved and enhanced process-derived solvent is provided by recycling second separator underflow in the critical solvent deashing stage to the coal slurry mix, for inclusion in the process solvent pool.

Biodiesel production from ethanolysis of palm oil using deep eutectic solvent (DES) as co-solvent

NASA Astrophysics Data System (ADS)

Manurung, R.; Winarta, A.; Taslim; Indra, L.

2017-06-01

Biodiesel produced from ethanolysis is more renewable and have better properties (higher oxidation stability, lower cloud and pour point) compared to methanolysis, but it has a disadvantage such as complicated purification. To improve ethanolysis process, deep eutectic solvent (DES) can be prepared from choline chloride and glycerol and used as co-solvent in ethanolysis. The deep eutectic solvent is formed from a quaternary ammonium salt (choline chloride) and a hydrogen bond donor (Glycerol), it is a non-toxic, biodegradable solvent compared to a conventional volatile organic solvent such as hexane. The deep eutectic solvent is prepared by mixing choline chloride and glycerol with molar ratio 1:2 at temperature 80 °C, stirring speed 300 rpm for 1 hour. The DES is characterized by its density and viscosity. The ethanolysis is performed at a reaction temperature of 70 °C, ethanol to oil molar ratio of 9:1, potassium hydroxide as catalyst concentration of 1.2 wt. DES as co-solvent with concentration 0.5 to 3 wt. stirring speed 400 rpm, and a reaction time 1 hour. The obtained biodiesel is then characterized by its density, viscosity, and ester content. The oil - ethanol phase condition is observed in the reaction tube. The oil - ethanol phase with DES tends to form meniscus compared to without DES, showed that oil and ethanol become more slightly miscible, which favors the reaction. Using DES as co-solvent in ethanolysis showed increasing in yield and easier purification. The esters properties meet the international standards ASTM D6751, with the highest yield achieved 83,67 with 99,77 conversion at DES concentration 2 . Increasing DES concentration above 2 in ethanolysis decrease the conversion and yield, because of the excessive glycerol in the systems makes the reaction equilibrium moves to the reactant side.

Comparison of different filter methods for data assimilation in the unsaturated zone

NASA Astrophysics Data System (ADS)

Lange, Natascha; Berkhahn, Simon; Erdal, Daniel; Neuweiler, Insa

2016-04-01

as the quality of open loop model predictions and the estimated parameters. Bocquet, M. and P. Sakov, 2013: Joint state and parameter estimation with an iterative ensemble Kalman smoother, Nonlinear Processes in Geophysics 20(5): 803-818. Evensen, G., 2009: Data assimilation: The ensemble Kalman filter. Springer Science & Business Media. Song, X.H., L.S. Shi, M. Ye, J.Z. Yang and I.M. Navon, 2014: Numerical comparison of iterative ensemble Kalman filters for unsaturated flow inverse modeling. Vadose Zone Journal 13(2), 10.2136/vzj2013.05.0083.

Acetone-based cellulose solvent.

PubMed

Kostag, Marc; Liebert, Tim; Heinze, Thomas

2014-08-01

Acetone containing tetraalkylammonium chloride is found to be an efficient solvent for cellulose. The addition of an amount of 10 mol% (based on acetone) of well-soluble salt triethyloctylammonium chloride (Et3 OctN Cl) adjusts the solvent's properties (increases the polarity) to promote cellulose dissolution. Cellulose solutions in acetone/Et3 OctN Cl have the lowest viscosity reported for comparable aprotic solutions making it a promising system for shaping processes and homogeneous chemical modification of the biopolymer. Recovery of the polymer and recycling of the solvent components can be easily achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling water infiltration and pesticides transport in unsaturated zone of a sedimentary aquifer

NASA Astrophysics Data System (ADS)

Sidoli, Pauline; Angulo-Jaramillo, Rafael; Baran, Nicole; Lassabatère, Laurent

2015-04-01

Groundwater quality monitoring has become an important environmental, economic and community issue since increasing needs drinking water at the same time with high anthropic pressure on aquifers. Leaching of various contaminants as pesticide into the groundwater is closely bound to water infiltration in the unsaturated zone which whom solute transport can occur. Knowledge's about mechanisms involved in the transfer of pesticides in the deep unsaturated zone are lacking today. This study aims to evaluate and to model leaching of pesticides and metabolites in the unsaturated zone, very heterogeneous, of a fluvio-glacial aquifer, in the South-East of France, where contamination of groundwater resources by pesticides is frequently observed as a consequence of intensive agricultural activities. Water flow and pesticide transport were evaluated from column tests under unsaturated conditions and from adsorption batch experiments onto the predominant lithofacies collected, composed of a mixture of sand and gravel. A maize herbicide, S-metolachlor, applied on the study site and worldwide and its two major degradation products (metolachlor ethanesulfonic acid and metolachlor oxanilic acid) were studied here. A conservative tracer, bromide ion, was used to determine water dispersive parameters of porous media. Elution curves were obtained from pesticide concentrations analyzed by an ultra-performance liquid chromatography system interfaced to a triple quadrupole mass spectrometer and from bromide concentrations measured by ionic chromatography system. Experimental data were implemented into Hydrus to model flow and solute transfer through a 1D profile in the vadose zone. Nonequilibrium solute transport model based on dual-porosity model with mobile and immobile water is fitting correctly elution curves. Water dispersive parameters show flow pattern realized in the mobile phase. Exchanges between mobile and immobile water are very limited. Because of low adsorptions onto

COUPLED FREE AND DISSOLVED PHASE TRANSPORT: NEW SIMULATION CAPABILITIES AND PARAMETER INVERSION

EPA Science Inventory

The vadose zone free-phase simulation capabilities of the US EPA Hydrocarbon Spill Screening Model (HSSM)have been linked with the 3-D multi-species dissolved-phase contaminant transport simulator MT3DMS.

Halogenated solvent remediation

DOEpatents

Sorenson, Kent S.

2004-08-31

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

Effects of solvent evaporation conditions on solvent vapor annealed cylinder-forming block polymer thin films

NASA Astrophysics Data System (ADS)

Grant, Meagan; Jakubowski, William; Nelson, Gunnar; Drapes, Chloe; Baruth, A.

Solvent vapor annealing is a less time and energy intensive method compared to thermal annealing, to direct the self-assembly of block polymer thin films. Periodic nanostructures have applications in ultrafiltration, magnetic arrays, or other structures with nanometer dimensions, driving its continued interest. Our goal is to create thin films with hexagonally packed, perpendicular aligned cylinders of poly(lactide) in a poly(styrene) matrix that span the thickness of the film with low anneal times and low defect densities, all with high reproducibility, where the latter is paramount. Through the use of our computer-controlled, pneumatically-actuated, purpose-built solvent vapor annealing chamber, we have the ability to monitor and control vapor pressure, solvent concentration within the film, and solvent evaporation rate with unprecedented precision and reliability. Focusing on evaporation, we report on two previously unexplored areas, chamber pressure during solvent evaporation and the flow rate of purging gas aiding the evaporation. We will report our exhaustive results following atomic force microscopy analysis of films exposed to a wide range of pressures and flow rates. Reliably achieving well-ordered films, while occurring within a large section of this parameter space, was correlated with high-flow evaporation rates and low chamber pressures. These results have significant implications on other methods of solvent annealing, including ``jar'' techniques.

Modeling Raw Sewage Leakage and Transport in the Unsaturated Zone of Carbonate Aquifer Using Carbamazepine as an Indicator

NASA Astrophysics Data System (ADS)

Yakirevich, A.; Kuznetsov, M.; Livshitz, Y.; Gasser, G.; Pankratov, I.; Lev, O.; Adar, E.; Dvory, N. Z.

2016-12-01

Fast contamination of groundwater in karstic aquifers can be caused due to leaky sewers, for example, or overflow from sewer networks. When flowing through a karst system, wastewater has the potential to reach the aquifer in a relatively short time. The Western Mountain Aquifer (Yarkon-Taninim) of Israel is one of the country's major water resources. During late winter 2013, maintenance actions were performed on a central sewage pipe that caused raw sewage to leak into the creek located in the study area. The subsequent infiltration of sewage through the thick ( 100 m) fractured/karst unsaturated zone led to a sharp increase in contaminant concentrations in the groundwater, which was monitored in a well located 29 meters from the center of the creek. Carbamazepine (CBZ) was used as an indicator for the presence of untreated raw sewage and its quantification in groundwater. The ultimate research goal was to develop a mathematical model for quantifying flow and contaminant transport processes in the fractured-porous unsaturated zone and karstified groundwater system. A quasi-3D dual permeability numerical model, representing the 'vadose zone - aquifer' system, was developed by a series of 1D equations solved in variably-saturated zone and by 3D-saturated flow and transport equation in groundwater. The 1D and 3D equations were coupled at the moving phreatic surface. The model was calibrated and applied to a simulated water flow scenario and CBZ transport during and after the observed sewage leakage event. The results of simulation showed that after the leakage stopped, significant amounts of CBZ were retained in the porous matrix of the unsaturated zone below the creek. Water redistribution and slow recharge during the dry summer season contributed to elevated CBZ concentrations in the groundwater in the vicinity of the creek and tens of meters downstream. The resumption of autumn rains enhanced flushing of CBZ from the unsaturated zone and led to an increase in

Batch extracting process using magneticparticle held solvents

DOEpatents

Nunez, Luis; Vandergrift, George F.

1995-01-01

A process for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents.

Case Study: del Amo Bioventing

EPA Science Inventory

The attached presentation discusses the fundamentals of bioventing in the vadose zone. The basics of bioventing are presented. The experience to date with the del Amo Superfund Site is presented as a case study.

Wide electrochemical window solvents for use in electrochemical devices and electrolyte solutions incorporating such solvents

DOEpatents

Angell, Charles Austen; Zhang, Sheng-Shui; Xu, Kang

1998-01-01

The present invention relates to electrolyte solvents for use in liquid or rubbery electrolyte solutions. Specifically, this invention is directed to boron-containing electrolyte solvents and boron-containing electrolyte solutions.

pH Control for Effective Anaerobic Bioremediation of Chlorinated Solvents

NASA Astrophysics Data System (ADS)

Robinson, C.; Barry, D.; Gerhard, J. I.; Kouznetsova, I.

2007-12-01

SABRE (Source Area BioREmediation) is a 4-year collaborative project that aims to evaluate the performance of enhanced anaerobic bioremediation for the treatment of chlorinated solvent DNAPL source areas. The project focuses on a pilot scale demonstration at a trichloroethene (TCE) DNAPL field site, and includes complementary laboratory and modelling studies. Organic acids and hydrogen ions (HCl) typically build up in the treatment zone during anaerobic bioremediation. In aquifer systems with relatively low buffering capacity the generation of these products can cause significant groundwater acidification thereby inhibiting dehalogenating activity. Where the soil buffering capacity is exceeded, addition of buffer may be needed for the effective continuation of TCE degradation. As an aid to the design of remediation schemes, a geochemical model was designed to predict the amount of buffer required to maintain the source zone pH at a suitable level for dechlorinating bacteria (i.e. > 6.5). The model accounts for the amount of TCE to be degraded, site water chemistry, type of organic amendment and soil mineralogy. It assumes complete dechlorination of TCE, and further considers mineral dissolution and precipitation kinetics. The model is applicable to a wide range of sites. For illustration we present results pertinent to the SABRE field site. Model results indicate that, for the extensive dechlorination expected in proximity to the SABRE DNAPL source zone, significant buffer addition may be necessary. Additional simulations are performed to identify buffer requirements over a wider range of field conditions.

AN EVALUATION OF HANFORD SITE TANK FARM SUBSURFACE CONTAMINATION FY2007

DOE Office of Scientific and Technical Information (OSTI.GOV)

MANN, F.M.

2007-07-10

The Tank Farm Vadose Zone (TFVZ) Project conducts activities to characterize and analyze the long-term environmental and human health impacts from tank waste releases to the vadose zone. The project also implements interim measures to mitigate impacts, and plans the remediation of waste releases from tank farms and associated facilities. The scope of this document is to report data needs that are important to estimating long-term human health and environmental risks. The scope does not include technologies needed to remediate contaminated soils and facilities, technologies needed to close tank farms, or management and regulatory decisions that will impact remediation andmore » closure. This document is an update of ''A Summary and Evaluation of Hanford Site Tank Farm Subsurface Contamination''. That 1998 document summarized knowledge of subsurface contamination beneath the tank farms at the time. It included a preliminary conceptual model for migration of tank wastes through the vadose zone and an assessment of data and analysis gaps needed to update the conceptual model. This document provides a status of the data and analysis gaps previously defined and discussion of the gaps and needs that currently exist to support the stated mission of the TFVZ Project. The first data-gaps document provided the basis for TFVZ Project activities over the previous eight years. Fourteen of the nineteen knowledge gaps identified in the previous document have been investigated to the point that the project defines the current status as acceptable. In the process of filling these gaps, significant accomplishments were made in field work and characterization, laboratory investigations, modeling, and implementation of interim measures. The current data gaps are organized in groups that reflect Components of the tank farm vadose zone conceptual model: inventory, release, recharge, geohydrology, geochemistry, and modeling. The inventory and release components address residual wastes

Auditory dysfunction associated with solvent exposure

PubMed Central

2013-01-01

Background A number of studies have demonstrated that solvents may induce auditory dysfunction. However, there is still little knowledge regarding the main signs and symptoms of solvent-induced hearing loss (SIHL). The aim of this research was to investigate the association between solvent exposure and adverse effects on peripheral and central auditory functioning with a comprehensive audiological test battery. Methods Seventy-two solvent-exposed workers and 72 non-exposed workers were selected to participate in the study. The test battery comprised pure-tone audiometry (PTA), transient evoked otoacoustic emissions (TEOAE), Random Gap Detection (RGD) and Hearing-in-Noise test (HINT). Results Solvent-exposed subjects presented with poorer mean test results than non-exposed subjects. A bivariate and multivariate linear regression model analysis was performed. One model for each auditory outcome (PTA, TEOAE, RGD and HINT) was independently constructed. For all of the models solvent exposure was significantly associated with the auditory outcome. Age also appeared significantly associated with some auditory outcomes. Conclusions This study provides further evidence of the possible adverse effect of solvents on the peripheral and central auditory functioning. A discussion of these effects and the utility of selected hearing tests to assess SIHL is addressed. PMID:23324255

Firing of pulverized solvent refined coal

DOEpatents

Derbidge, T. Craig; Mulholland, James A.; Foster, Edward P.

1986-01-01

An air-purged burner for the firing of pulverized solvent refined coal is constructed and operated such that the solvent refined coal can be fired without the coking thereof on the burner components. The air-purged burner is designed for the firing of pulverized solvent refined coal in a tangentially fired boiler.

Uranium speciation as a function of depth in contaminated hanford sediments--a micro-XRF, micro-XRD, and micro- and bulk-XAFS study.

PubMed

Singer, David M; Zachara, John M; Brown, Gordon E

2009-02-01

The distribution and speciation of U and Cu in contaminated vadose zone and aquifer sediments from the U.S. DOE Hanford site (300 Area) were determined using a combination of synchrotron-based micro-X-ray fluorescence (microXRF) imaging, micro-X-ray absorption near edge structure (microXANES) spectroscopy, and micro-X-ray diffraction (microXRD) techniques combined with bulk U LIII-edge X-ray absorption fine structure (XAFS) spectroscopy. Samples were collected from within the inactive North Process Pond (NPP2) at 8 ft (2.4 m, NPP2-8) depth and 12 ft (3.7 m, NPP2-12) depth in the vadose zone, and fines were isolated from turbid groundwater just below the water Table (12-14 ft, approximately 4 m, NPP2-GW). microXRF imaging, microXRD, and microXANES spectroscopy revealed two major U occurrences within the vadose and groundwater zones: (1) low to moderate concentrations of U(VI) associated with fine-textured grain coatings that were consistently found to contain clinochlore (referred to here as chlorite) observed in all three samples, and (2) U(VI)-Cu(II) hotspots consisting of micrometer-sized particles associated with surface coatings on grains of muscovite and chlorite observed in samples NPP2-8' and NPP2-GW. In the aquifer fines (NPP2-GW), these particles were identified as cuprosklodowskite (cps: Cu[(UO2)(SiO2OH)]2 x 6H2O) and metatorbernite (mtb: Cu(UO2)2(PO4)2 x 8H2O). In contrast, the U-Cu-containing particles in the vadose zone were X-ray amorphous. Analyses of U LIII-edge XAFS spectra by linear-combination fitting indicated that U speciation consisted of (1) approximately 75% uranyl sorbed to chlorite and approximately 25% mtb-like X-ray amorphous U-Cu-phosphates (8 ft depth), (2) nearly 100% sorbed uranyl (12 ft depth), and (3) approximately 70% uranyl sorbed to chlorite and approximately 30% cps/mtb (groundwater zone). These findings suggest that dissolution of U(VI)-Cu(II)-bearing solids as well as desorption of U(VI), mainly from phyllosilicates, are

Aminosilicone solvent recovery methods and systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spiry, Irina Pavlovna; Perry, Robert James; Wood, Benjamin Rue

The present invention is directed to aminosilicone solvent recovery methods and systems. The methods and systems disclosed herein may be used to recover aminosilicone solvent from a carbon dioxide containing vapor stream, for example, a vapor stream that leaves an aminosilicone solvent desorber apparatus. The methods and systems of the invention utilize a first condensation process at a temperature from about 80.degree. C. to about 150.degree. C. and a second condensation process at a temperature from about 5.degree. C. to about 75.degree. C. The first condensation process yields recovered aminosilicone solvent. The second condensation process yields water.

Zone fluidics for measurement of octanol-water partition coefficient of drugs.

PubMed

Wattanasin, Panwadee; Saetear, Phoonthawee; Wilairat, Prapin; Nacapricha, Duangjai; Teerasong, Saowapak

2015-02-20

A novel zone fluidics (ZF) system for the determination of the octanol-water partition coefficient (Pow) of drugs was developed. The ZF system consisted of a syringe pump with a selection valve, a holding column, a silica capillary flow-cell and an in-line spectrophotometer. Exact microliter volumes of solvents (octanol and phosphate buffer saline) and a solution of the drug, sandwiched between air segments, were sequentially loaded into the vertically aligned holding column. Distribution of the drug between the aqueous and octanol phases occurred by the oscillation movement of the syringe pump piston. Phase separation occurred due to the difference in densities. The liquid zones were then pushed into the detection flow cell. In this method, absorbance measurements in only one of the phase (octanol or aqueous) were employed, which together with the volumes of the solvents and pure drug sample, allowed the calculation of the Pow. The developed system was applied to the determination of the Pow of some common drugs. The log (Pow) values agreed well with a batch method (R(2)=0.999) and literature (R(2)=0.997). Standard deviations for intra- and inter-day analyses were both less than 0.1log unit. This ZF system provides a robust and automated method for screening of Pow values in the drug discovery process. Copyright © 2014 Elsevier B.V. All rights reserved.

Isolation of mesophilic solvent-producing clostridia from Colombian sources: physiological characterization, solvent production and polysaccharide hydrolysis.

PubMed

Montoya, D; Spitia, S; Silva, E; Schwarz, W H

2000-04-28

One hundred and seventy-eight new butanol-acetone producing bacteria related to saccharolytic clostridia were isolated from agricultural sources in Colombia and their fermentation potential was evaluated. Thirteen isolates produced more total solvents from glucose than Clostridium acetobutylicum ATCC 824. The isolates with the highest single solvent production were IBUN 125C and IBUN 18A with 0.46 mol butanol and 0.96 mol ethanol formed from 1 mol glucose, yielding 25. 2 and 29.1 g l(-1) total solvents, respectively, which is close to the maximum values described to date. Most of the new isolates produced exoenzymes for the hydrolysis of starch, carboxymethyl cellulose, xylan, polygalacturonic acid, inulin and chitosan. Together with the high efficiency of solvent production, these hydrolytic isolates may be useful for the direct fermentation of biomass. According to their physiological profile, the most solvent-productive isolates could be classified as strains of C. acetobutylicum, Clostridium beijerinckii, and Clostridium NCP262.

Work ability score of solvent-exposed workers.

PubMed

Furu, Heidi; Sainio, Markku; Hyvärinen, Hanna-Kaisa; Kaukiainen, Ari

2018-03-28

Occupational chronic solvent encephalopathy (CSE), characterized by neurocognitive dysfunction, often leads to early retirement. However, only the more severe cases are diagnosed with CSE, and little is known about the work ability of solvent-exposed workers in general. The aim was to study memory and concentration symptoms, work ability and the effect of both solvent-related and non-occupational factors on work ability, in an actively working solvent-exposed population. A questionnaire on exposure and health was sent to 3640 workers in four solvent-exposed fields, i.e. painters and floor-layers, boat builders, printers, and metal workers. The total number of responses was 1730. We determined the work ability score (WAS), a single question item of the Work Ability Index, and studied solvent exposure, demographic factors, Euroquest memory and concentration symptoms, chronic diseases, and employment status using univariate and multivariate analyses. The findings were compared to those of a corresponding national blue-collar reference population (n = 221), and a small cohort of workers with CSE (n = 18). The proportion of workers with memory and concentration symptoms was significantly associated with solvent exposure. The WAS of solvent-exposed workers was lower than that of the national blue-collar reference group, and the difference was significant in the oldest age group (those aged over 60). Solvent-exposed worker's WAS were higher than those of workers diagnosed with CSE. The WAS were lowest among painters and floor-layers, followed by metal workers and printers, and highest among boat builders. The strongest explanatory factors for poor work ability were the number of chronic diseases, age and employment status. Solvent exposure was a weak independent risk factor for reduced WAS, comparable to a level of high alcohol consumption. Even if memory and concentration symptoms were associated with higher solvent exposure, the effect of solvents on self

Femtosecond dynamics in hydrogen-bonded solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Castner, E.W. Jr.; Chang, Y.J.

1993-09-01

We present results on the ultrafast dynamics of pure hydrogen-bonding solvents, obtained using femtosecond Fourier-transform optical-heterodyne-detected, Raman-induced Kerr effect spectroscopy. Solvent systems we have studied include the formamides, water, ethylene glycol, and acetic acid. Inertial and diffusive motions are clearly resolved. We comment on the effect that such ultrafast solvent motions have on chemical reactions in solution.

Quantitation of buried contamination by use of solvents. [degradation of silicone polymers by amine solvents

NASA Technical Reports Server (NTRS)

Pappas, S. P.; Hsiao, Y. C.; Hill, L. W.

1973-01-01

Spore recovery form cured silicone potting compounds using amine solvents to degrade the cured polymers was investigated. A complete list of solvents and a description of the effect of each on two different silicone polymers is provided.

DESIGNING ENVIRONMENTALLY BENIGN SOLVENT SUBSTITUTES

EPA Science Inventory

Since the signing of 1987 Montreal Protocol, reducing and eliminating the use of harmful solvents has become an internationally imminent environmental protection mission. Solvent substitution is an effective way to achieve this goal. The Program for Assisting the Replacement of...

Remediating pesticide contaminated soils using solvent extraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sahle-Demessie, E.; Meckes, M.C.; Richardson, T.L.

Bench-scale solvent extraction studies were performed on soil samples obtained from a Superfund site contaminated with high levels of p,p{prime}-DDT, p,p{prime}-DDE and toxaphene. The effectiveness of the solvent extraction process was assessed using methanol and 2-propanol as solvents over a wide range of operating conditions. It was demonstrated that a six-stage methanol extraction using a solvent-to-soil ratio of 1.6 can decrease pesticide levels in the soil by more than 99% and reduce the volume of material requiring further treatment by 25 times or more. The high solubility of the pesticides in methanol resulted in rapid extraction rates, with the systemmore » reaching quasi-equilibrium state in 30 minutes. The extraction efficiency was influenced by the number of extraction stages, the solvent-to-soil ratio, and the soil moisture content. Various methods were investigated to regenerate and recycle the solvent. Evaporation and solvent stripping are low cost and reliable methods for removing high pesticide concentrations from the solvent. For low concentrations, GAC adsorption may be used. Precipitating and filtering pesticides by adding water to the methanol/pesticide solution was not successful when tested with soil extracts. 26 refs., 10 figs., 6 tabs.« less

Sleep disturbances and exposure to organic solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindelof, B.; Almkvist, O.; Goethe, C.

An inquiry about sleep habits and sleep disturbances revealed a significantly higher prevalence of insomnia in a solvent-exposed group than in a comparable group that had no occupational exposure to organic solvents. The solvent-exposed group has also registered an increased consumption of hypnotics, and a significant increase occurred in the number of individuals who had consulted physicians because of sleep disorders. The results indicate that solvent exposure could induce sleep disturbances.

Recovery, Reuse, and Recycle of Solvents.

DTIC Science & Technology

1985-12-01

Program ------------------------------------------------------ 1I In e t v s P o r m - - - - - - - - - - - - - - - - - - - - - - - - Soncentves Pr ogram...not known. . . ,o. .’* • . .~i 8 A M FIGURE 1 WORKSHEET FOR DETERMINING WASTE SOLVENT ECONOMIC ANALYSIS Activity/Complex: Preparer:_________ Location...annual f. operating cost of $890 18 V-7 C.6 M . SOLVENT RENTAL APPLICATIONS Solvent rental may be the most cost effective method for complying with both

Extraction, scrub, and strip test results for the salt waste processing facility caustic side solvent extraction solvent example

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, T. B.

An Extraction, Scrub, and Strip (ESS) test was performed on a sample of Salt Waste Processing Facility (SWPF) Caustic-Side Solvent Extraction (CSSX) solvent and salt simulant to determine cesium distribution ratios (D(Cs)), and cesium concentration in the strip effluent (SE) and decontaminated salt solution (DSS) streams; this data will be used by Parsons to help determine if the solvent is qualified for use at the SWPF. The ESS test showed acceptable performance of the solvent for extraction, scrub, and strip operations. The extraction D(Cs) measured 12.9, exceeding the required value of 8. This value is consistent with results from previousmore » ESS tests using similar solvent formulations. Similarly, scrub and strip cesium distribution ratios fell within acceptable ranges.« less

EXPERIENCES IN DESIGNING SOLVENTS FOR THE ENVIRONMENT

EPA Science Inventory

To meet the great need of replacing many harmful solvents commonly used by industry and the public with environmentally benign substitute solvents, the PARIS II solvent design software has been developed. Although the difficulty of successfully finding replacements increases with...

VAPOR PHASE TREATMENT OF PCE IN A SOIL COLUMN BY LAB-SCALE ANAEROBIC BIOVENTING

EPA Science Inventory

Microbial destruction of highly chlorinated organic compounds must be initiated by anaerobic followed by aerobic dechlorination. In-situ dechlorination of vadose zone soil contaminated with these compounds requires, among other factors, the establishment of highly reductive anaer...

Linking chloride mass balance infiltration rates with chlorofluorocarbon and SF6 groundwater dating in semi-arid settings: potential and limitations.

PubMed

Stadler, Susanne; Osenbruck, Karsten; Duijnisveld, Wilhelmus H M; Schwiede, Martin; Bottcher, Jurgen

2010-09-01

In the framework of the investigation of enrichment processes of nitrate in groundwater of the Kalahari of Botswana near Serowe, recharge processes were investigated. The thick unsaturated zone extending to up to 100 m of mostly unconsolidated sediments and very low recharge rates pose a serious challenge to study solute transport related to infiltration and recharge processes, as this extends past the conventional depths of soil scientific investigations and is difficult to describe using evidence from the groundwater due to the limitations imposed by available tracers. To determine the link between nitrate in the vadose zone and in the uppermost groundwater, sediment from the vadose zone was sampled up to a depth of 15-20 m (in one case also to 65 m) on several sites with natural vegetation in the research area. Among other parameters, sediment and water were analysed to determine chloride and nitrate concentration depth profiles. Using the chloride mass balance method, an estimation of groundwater infiltration rates produced values of 0.2-4 mm a(-1). The uncertainty of these values is, however, high. Because of the extreme thickness of the vadose zone, the travel time in the unsaturated zone might reach extreme values of up to 500 years and more. For investigations using groundwater, we applied the chlorofluorocarbons CFC-113, CFC-12, sulphur hexafluoride (SF(6)) and tritium to identify potential recharge, and found indications for some advective transport of the CFCs and SF(6), which we accounted for as constituting potential active localised recharge. In our contribution, we show the potential and limitations of the applied methods to determine groundwater recharge and coupled solute transport in semi-arid settings, and compare travel time ranges derived from soil science and groundwater investigations.

Non-aqueous cleaning solvent substitution

NASA Technical Reports Server (NTRS)

Meier, Gerald J.

1994-01-01

A variety of environmental, safety, and health concerns exist over use of chlorinated and fluorinated cleaning solvents. Sandia National Laboratories, Lawrence Livermore National Laboratories, and the Kansas City Division of AlliedSignal have combined efforts to focus on finding alternative cleaning solvents and processes which are effective, environmentally safe, and compliant with local, state, and federal regulations. An alternative solvent has been identified, qualified, and implemented into production of complex electronic assemblies, where aqueous and semi-aqueous cleaning processes are not allowed. Extensive compatibility studies were performed with components, piece-parts, and materials. Electrical testing and accelerated aging were used to screen for detrimental, long-term effects. A terpene, d-limonene, was selected as the solvent of choice, and it was found to be compatible with the components and materials tested. A brief history of the overall project will be presented, along with representative cleaning efficiency results, compatibility results, and residual solvent data. The electronics industry is constantly searching for proven methods and environmentally-safe materials to use in manufacturing processes. The information in this presentation will provide another option to consider on future projects for applications requiring high levels of quality, reliability, and cleanliness from non-aqueous cleaning processes.

Biochemical alterations in duckweed and algae induced by carrier solvents: Selection of an appropriate solvent in toxicity testing.

PubMed

Hu, Li-Xin; Tian, Fei; Martin, Francis L; Ying, Guang-Guo

2017-10-01

Carrier solvents are often used in aquatic toxicity testing for test chemicals with hydrophobic properties. However, the knowledge of solvent effects on test organisms remains limited. The present study aimed to determine the biochemical effects of the 4 common solvents methanol, ethanol, acetone, and dimethyl sulfoxide (DMSO) on 2 test species, Lemna minor and Raphidocelis subcapitata, by applying Fourier transform infrared spectroscopy (FTIR) coupled with multivariate analysis to select appropriate solvents for toxicity testing. The results showed biochemical variations associated with solvent treatments at different doses on test species. From the infrared spectra obtained, the structures of lipid membrane and protein phosphorylation in the test species were found to be sensitive to the solvents. Methanol and ethanol mainly affected the protein secondary structure, whereas acetone and DMSO primarily induced alterations in carbohydrates and proteins in the test species. The FTIR results demonstrated that methanol and ethanol showed higher biochemical alterations in the test species than acetone and DMSO, especially at the high doses (0.1 and 1% v/v). Based on the growth inhibition displayed and FTIR spectroscopy, acetone, and DMSO can be used as carrier solvents in toxicity testing when their doses are lower than 0.1% v/v. Environ Toxicol Chem 2017;36:2631-2639. © 2017 SETAC. © 2017 SETAC.