Remediation of DNAPL contaminated sites in fractured rock has proven to be very difficult. No current technology can be used to remediate such sites in a timely and economic manner due to the inherent heterogeneity of fractured rock and back diffusion of contaminants stored in the rock matrix. This study was conducted in order to evaluate the viability of biostimulation of native biofilm as a means to control flow and back diffusion at fractured rock sites. A field trial was conducted at an uncontaminated site in southern Ontario. The site is underlain by dolomites of the Lockport formation. Three major fracture zones have been identified in the study area. Two closely spaced (5.04 m) boreholes were used to isolate a fracture zone at a depth of 17 m with straddle packers. These boreholes were used to create an injection-withdrawal system with recirculation, which was used for tracer injection in order to load the rock matrix with a conservative dye tracer and to inject nutrients for 21 days in order to stimulate the growth of biofilm in the fracture. Evaluation of the ability of the biofilm to control flow through the fracture was conducted through pulse interference tests. Pulse interference tests were conducted before and after the injection of nutrients. The results from the pulse interference tests showed a maximum 65% reduction in transmissivity, which is equivalent to a 28% reduction in fracture aperture shortly after the cessation of biostimulation. In order to investigate the effect of the biofilm stimulation on matrix diffusion the rock matrix was loaded with Lissamine, a conservative fluorescent dye tracer prior to biostimulation and its concentration was monitored at injection and withdrawal wells. The effect that biostimulation had on matrix diffusion was determined by comparing field concentration measurements with a model that simulates a system unaffected by biofilm stimulation. The biostimulation lowered the concentration of tracer attributable to back diffusion at the withdrawal well by about 20% for approximately 30 days following the cessation of biostimulation. It is also thought that large amounts of tracer might have been trapped in the biofilm as it formed and was then released back into the fracture as the biofilm deteriorated. / Thesis (Master, Civil Engineering) -- Queen's University, 2009-08-11 19:27:44.232

Natural attenuation of trichloroethene (TCE) and technetium (99Tc) was studied for five consecutive seasons (from January 2002 to January 2003) in Little Bayou Creek. The stream receives ground water discharge from an aquifer contaminated by past waste disposal activities at the Paducah Gaseous Diffusion Plant (PGDP), a uranium enrichment facility near Paducah, Kentucky. Results from stream gaging, contaminant monitoring, tracer tests (with bromide, nitrate, rhodamine WT and propane) and simulation modeling indicate the TCE is naturally attenuated by volatilization and dilution, with volatilization rates related to the ambient temperature and surface discharge rate. The only apparent mechanism of 99Tc attenuation is dilution. Travel times of non-gaseous tracers were found to be similar and have highest values in October and lowest in June. It was also estimated from modeling that the transport of the solutes in the stream was mostly one-dimensional with insignificant secondary storage.

The most common method of monitoring and mapping groundwatercontaminants is to extract and analyse a number of groundwatersamples from wells in the investigation area. However, thereare a number of limitations with this type of point-wiseinvestigation, as it is hard to acquire an adequate picture ofa heterogeneous and anisotropic subsurface using a fewpoints. To overcome the limitations of point investigations and toimprove ground monitoring investigations in a cost-effectiveway, support can be provided by direct current resistivitymeasurements, which give a characterisation of the electricalproperties of a ground volume. The main objective with this work was to investigate theusability of the resistivity method as a support in monitoringgroundwater contaminants in glaciated terrains and underdifferent seasons, both in long-term monitoring programmes andintracer tests. The work comprised field investigations at several differentsanitary landfills and four tracer tests in differentgeological environments, around the Stockholm region. The maininvestigations have been done at Högbytorp, Stockholmwhich has been used for long-term investigations of theresistivity variation, together with a field set up formonitoring and measurements on seasonal variation in soilmoisture, ground temperature and precipitation. It can be concluded that the use of resistivity measurementssupplies valuable information in the case of mapping andmonitoring conductive groundwater contaminants andfurthermore: The variation in resistivity (in shallow investigations<1 m) can be extensive between different seasons (around30 % compared to a mean value in till and clay soils) andshould be considered, so that anthropogenic affects can beseparated from natural resistivity variation. For deeperinvestigations (>5 m) the seasonal resistivity variationwas more moderate (around 15% compared to a mean value intill and clay soils). Soil moisture variation shows a strong relationship toresistivity variation in the investigated clay and tillsoils. Together with temperature correction 47 to 65% of thevariation has been explained. Three types of monitoring systems can be applied:Permanently installed, partly installed and fully mobilesystems. For the actual measurements, all three types can useeither high-density techniques such as CVES (ContinuousVertical Electrical Sounding) or low-density measuring withone or some different electrode spacings. The suggested evaluation tool for monitoring programmesshowed that it was possible to detect a decrease of 15 % inthe mean value at a specific site using Modified Double Masscalculations between resistivity time series and time seriesat a reference site with a comparable seasonalvariation. Resistivity measurements may be used as a valuablecomplement to groundwater sampling in tracer tests. Adecrease in resistivity, a minimum and a recovery phasereflect the passage of a NaCl-solution, which can be used toestimate flow velocity and flow patterns of the investigatedaquifer. The achieved recovery of NaCl in the tracer testscarried out was estimated to 20 to 70 %. The measurement system for long-term monitoring or tracertests, which should be chosen with regard to layout andfrequency, depends on the purpose of measurement and onsite-specific conditions and therefore no standard solutioncan be proposed. Key words:Resistivity, Direct Current, Monitoring,Groundwater, Contaminant, Tracer test, Geophysics.

Groundwater plays a fundamental role in water resource sustainability in Virginia (USA), but overpumping has caused significant declines in the potentiometric surface in the Potomac Aquifer System (PAS). With water levels falling, communities are at risk of wells running dry, saltwater intrusion, and land subsidence. The Sustainable Water Initiative for Tomorrow (SWIFT) project is an aquifer long-term replenishment (ALTR) project that uses continuous recharge into the multi-layered confined aquifer system to restore the potentiometric surface over space and time and increase storage in the system. The SWIFT Research Center (SWIFT-RC) is a 1 million gallon per day (MGD) demonstration facility in Suffolk, Virginia that recharges the PAS through a multi-screen well. Addressing research questions about the impact of continuous, sustained recharge on aquifer systems is crucial to the long-term sustainability of an ALTR project. Quantifying how flow moves through the multi-layered system is necessary to communicate travel times and water quality impacts on the aquifer system. This work uses injectate as an intrinsic tracer, an in-situ flowmeter, and a bromide tracer test to evaluate how flow is distributed through the eleven screens in the recharge well and to assess how flow distribution changes over time. Typically, flow distribution in multi-screen wells is estimated only once over the length of a project and assumed to remain constant for modeling purposes; by measuring flow distribution using multiple methods over the course of the project, this work shows that flow distribution is not constant. In future ALTR projects, developing a consistent and robust monitoring plan to use injectate as an indicator of movement through the aquifer system, paired with other methods to monitor changes in flow distribution, will be a critical part of effectively evaluating how flow moves through the groundwater system. / Doctor of Philosophy / Groundwater plays a fundamental role in water resource sustainability in Virginia (USA), but overpumping has left the Potomac Aquifer System (PAS) depleted. With water levels falling, communities are at risk of wells running dry, adverse water quality changes, and even changes to the land surface due to subsurface settling. The Sustainable Water Initiative for Tomorrow (SWIFT) project is an aquifer long-term replenishment (ALTR) project that uses continuous recharge into the deep aquifer system to restore water levels and increase storage in the system. The SWIFT Research Center (SWIFT-RC) is a 1 million gallon per day (MGD) demonstration facility in Suffolk, Virginia that recharges the PAS through a multi-screen well. Addressing research questions about the impact of continuous, sustained recharge on aquifer systems is crucial to the long-term sustainability of an ALTR project. Quantifying how flow moves through the multi-layered system is necessary to communicate travel times and water quality impacts on the aquifer system. This work uses multiple methods to evaluate how flow is distributed through the eleven screens in the recharge well and to assess how flow distribution changes over time. Typically, flow distribution in multi-screen wells is estimated only once over the length of a project and is assumed to remain constant for modeling purposes; by measuring flow distribution using multiple methods over the course of the project, this work shows that flow distribution is not constant. In future ALTR projects, developing a consistent and robust monitoring plan to use recharge water itself as an indicator of movement through the aquifer system, paired with other methods to monitor changes in flow distribution, will be a critical part of effectively evaluating how flow moves through the groundwater system.

<p>When establishing a groundwater protection area it is of great interest to be able to estimate the transit time of the groundwater from different places of the aquifer to the withdrawal well. These estimates can be uncertain due to heterogeneities in the aquifer. As a part of the work to develop methods for a more certain delineation of protection areas, a tracer test was performed in an esker located 25 kilometres NW of the town Uppsala.</p><p>The purpose of this master thesis was to perform, describe and evaluate the tracer test. Travel times from the tracer test should then enable comparison against stochastic simulated travel times of the groundwater in the area.</p><p>Three dyes (rhodamine WT, uranine and naphtionate) and a salt (NaBr) were used in the tracer test. The tracers were injected in four different wells located 25 meters from a pumping well. The pumping well was pumped at a rate of 1.7 L/s and water samples were collected from the pumped water. The calculated mass recovery was large for bromide (101 %) but considerably lower for the dyes rhodamine WT (70 %), uranine (61 %) and Naphthionate (19 %). The low mass recovery for the dyes is probably due to degradation and maybe also adsorption.</p><p>An analytical solution to the advection – dispersion equation in one dimension for radial converging flow was used for the interpretation of the breakthrough curves. Smallest and largest transit time that was received from the model fitting was 1,9 days and 5,1 days respectively and without exception large longitudinal dispersivities (9-35 m). Point dilution tests were performed in the injection wells in order to determine the ground water flow at these wells. The tests gave information about the magnitude of the ground water flow, differences between the wells and the flow change at pumping.</p><p>Travel times were estimated from the received breakthrough curves and the travel time distributions can be used for comparison against stochastic simulated travel times of the groundwater.</p> / <p>Vid utformningen av skyddsområden för grundvattentäkter är det av stor vikt att kunna uppskatta grundvattnets transporttid (uppehållstid) från olika partier av akviferen till uttagsplatsen. Dessa bedömningar har en tendens att bli osäkra på grund av heterogeniteter i akviferen. Som ett led i arbetet att utveckla metoder för en säkrare avgränsning av skyddsområden genomfördes ett spårämnesförsök i en isälvsavlagring (Järlåsaåsen) belägen cirka 2,5 mil nordväst om Uppsala.</p><p>Syftet med examensarbetet var att genomföra, beskriva och utvärdera spårämnesförsöket. Bestämda transporttider från spårämnesförsöket skulle sedan kunna användas för jämförelse med stokastiskt simulerade transporttider för grundvattnet i området.</p><p>Tre färgspårämnen (rhodamin WT, uranin och naphtionat) och ett salt (NaBr) användes vid spårämnesförsöken. Spårämnena injicerades i fyra olika grundvattenrör belägna 25 meter från en uttagsbrunn. Pumpflödet ur uttagsbrunnen var 1,7 L/s och med en automatprovtagare togs vattenprover från det uppumpade vattnet. Resultatet från massbalansberäkningarna visade på att all injicerad bromid återfanns i uttagsbrunnen, men andelen återfunnen spårämnesmassa var betydligt lägre för färgspårämnena rhodamin WT (70 %), uranin (61 %) och naphtionat (19 %). Den låga andelen återfunnen massa beror troligtvis främst på nedbrytning och kanske även på adsorption.</p><p>En analytisk lösning till advektions- dispersionsekvationen i en dimension för radiellt konvergerande strömning användes vid utvärderingen av genombrottskurvorna. En minsta och största uppehållstid på 1,9 dygn respektive 5,1 dygn och överlag oväntat stora dispersiviteter (9 – 35 m) erhölls från kurvanpassningen. Den första ankomsttiden till uttagsbrunnen hade ett minsta och största värde på 3,8 respektive 13 timmar. Utspädningsförsök genomfördes också för att bestämma storleken på flödet vid injektionsrören. Dessa försök gav en bild av flödets storlek, skillnader mellan de olika injektionsrören och flödets förändring vid pumpning.</p><p>De bestämda transporttiderna visar på relativt stora tidsskillnader och ett heterogent försöksområde. Transporttidsfördelningarna utgör också ett underlag för en jämförelse mot stokastiskt simulerade transporttider av grundvattnet.</p>

The effective and efficient remediation of contaminated groundwater sites requires site specific information regarding the physical, chemical and biological properties of the aquifer. Building on the dipole flow test (DFT) and the dipole flow and tracer test (DFTT), the dipole flow and reactive tracer test (DFRTT) has been proposed as an alternative to current aquifer parameter estimation methods. A steady-state dipole flow field is created by circulating groundwater between chambers isolated by the dipole tool. A tracer is released into the injection chamber and the breakthrough curve at the extraction chamber is interpreted with the DFRTT specific model. The overall goal of this thesis was to demonstrate the ability of a prototype dipole system to produce tracer BTCs in conventional wells installed in an unconfined sandy aquifer. The Waterloo dipole probe was constructed and field tested at CFB Borden. DFTs conducted along the length of the screen of non-filter packed monitoring wells provided similar estimates of radial hydraulic conductivity (Kr) to slug tests and literature values. The geometric mean Kr estimated in the filter packed wells was approximately an order of magnitude greater than the mean Kr estimate for the non-filter packed wells due to short-circuiting through the filter pack. A total of 46 DFTTs were completed in the monitoring wells at CFB Borden to investigate the properties of the BTCs. The shape of the BTC for a conservative tracer is affected by test set up parameters, well construction, and aquifer formation properties. The BTCs from the DFTTs completed in the non-filter pack monitoring wells were categorized into four “type curves” based on the BTC properties. The differences between the type curves were largely defined by the ratio of K between the skin zone and the aquifer (Ks/Kr). Now that a series of DFTT BTCs have been generated, the DFRTT model will be used to estimate the aquifer parameters. To continue the work outlined in this thesis, DFRTTs are planned for well-documented contaminated sites.

The effective and efficient remediation of contaminated groundwater sites requires site specific information regarding the physical, chemical and biological properties of the aquifer. Building on the dipole flow test (DFT) and the dipole flow and tracer test (DFTT), the dipole flow and reactive tracer test (DFRTT) has been proposed as an alternative to current aquifer parameter estimation methods. A steady-state dipole flow field is created by circulating groundwater between chambers isolated by the dipole tool. A tracer is released into the injection chamber and the breakthrough curve at the extraction chamber is interpreted with the DFRTT specific model. The overall goal of this thesis was to demonstrate the ability of a prototype dipole system to produce tracer BTCs in conventional wells installed in an unconfined sandy aquifer. The Waterloo dipole probe was constructed and field tested at CFB Borden. DFTs conducted along the length of the screen of non-filter packed monitoring wells provided similar estimates of radial hydraulic conductivity (Kr) to slug tests and literature values. The geometric mean Kr estimated in the filter packed wells was approximately an order of magnitude greater than the mean Kr estimate for the non-filter packed wells due to short-circuiting through the filter pack. A total of 46 DFTTs were completed in the monitoring wells at CFB Borden to investigate the properties of the BTCs. The shape of the BTC for a conservative tracer is affected by test set up parameters, well construction, and aquifer formation properties. The BTCs from the DFTTs completed in the non-filter pack monitoring wells were categorized into four “type curves” based on the BTC properties. The differences between the type curves were largely defined by the ratio of K between the skin zone and the aquifer (Ks/Kr). Now that a series of DFTT BTCs have been generated, the DFRTT model will be used to estimate the aquifer parameters. To continue the work outlined in this thesis, DFRTTs are planned for well-documented contaminated sites.

Anthraquinone dyes constitute the second largest class of textile dyes, and are used extensively in the textile industry. A high fraction of the initial reactive dye mass used in the dyeing process remains in the spent dyebath. Reactive dyes are not readily removed by typical wastewater treatment processes and the high salt concentration typical of reactive dyeing further complicates the management of spent reactive dyebaths. Investigation of the reductive transformation of reactive anthraquinone dyes and their decolorization products has been very limited. Additionally, very limited research has been conducted on the decolorization of spent reactive dyebaths. Research was conducted to investigate the key operational parameters of batch and continuous-flow ZVI decolorization of a reactive anthraquinone dye, Reactive Blue 4 (RB4), under anoxic conditions, as well as the potential for the biodegradation of its decolorization products in a halophilic culture under aerobic conditions. The effect of two operational parameters, such as mixing intensity and initial dye concentration, on the ZVI batch decolorization kinetics indicates that ZVI decolorization of RB4 is a surface-catalyzed, mass transfer-limited process. The high salt and base concentrations enhanced the rate of RB4 decolorization. Based on parameters such as porosity, hydraulic conductivity, pore water velocity, and dispersion coefficient, non-ideal transport characteristics were observed in a continuous-flow ZVI column. The results of a long-term continuous-flow ZVI decolorization kinetics demonstrated that continuous-flow ZVI decolorization is feasible. However, column porosity losses and a shift of reaction kinetics occur in long-term column operation. ZVI decolorization of RB4 was successfully described with a pseudo first-order or a site saturation model. Lastly, the RB4 decolorization products generated by ZVI treatment had no inhibitory effect on the halophilic culture. However, biodegradation and/or mineralization of RB4 decolorization products was not observed after a long-term incubation of the culture. This research demonstrated the feasibility of ZVI decolorization of reactive anthraquinone dyes, which will help in the development of a continuous-flow, dyebath decolorization process and the possible reuse of the renovated dyebath in the dyeing operation. Such a system could lead to substantial reduction of water usage, as well as a decrease of salt and dye discharges.

The intra-continental movement of waterborne contaminants is governed by the distribution of solute load in the landscape along with the characteristics and distribution of the hydrological pathways that transport the solutes. An understanding of the processes affecting the transport and fate of the contaminants is crucial for assessments of solute concentrations and their environmental effect on downstream recipients. Elevated concentration of nutrients and the presence of anthropogenic substances, such as pharmaceutical residues, are two examples of the current problems related to hydrological transport. The overall objective of this thesis is to increase the mechanistic understanding of the governing hydrological transport processes and their links to geomorphological and biogeochemical retention and attenuation processes. Specifically, this study aims to quantify the processes governing the transport and fate of waterborne contaminants on the point, stream reach, and watershed scales by evaluating time series obtained from stream tracer tests and water quality monitoring data. The process quantification was achieved by deriving formal expressions for the key transport characteristics, such as the central temporal moments of a unit solute response function and the spectral scaling function for time series of solute responses, which attributes the solute response in the Laplace and Fourier domains to the governing processes and spatial regions within the watershed. The results demonstrate that in addition to the hydrological and biogeochemical processes, the distribution of the load in the landscape and the geomorphological properties in terms of the distribution of transport pathway distances have defined effects on the solute response. Furthermore, the spatial variability between and along the transport pathways significantly affect the solute response. The results indicate that environments with high retention and attenuation intensity, such as stream-reaches with pronounced hyporheic zones, may often dominate the solute flux in the watershed effluent, especially for reactive solutes. The mechanistic-based framework along with the evaluation methodologies presented within this study describes how the results can be generalized in terms of model parameters that reflect the hydrology, geomorphology and biogeochemistry in the studied area. This procedure is demonstrated by the parameterization of a compartment-in-series model for phosphorous transport. / <p>QC 20140826</p>

The phenomenon of plume persistence was observed for five federal Superfund sites by analysis of historical groundwater-withdrawal and contaminant-concentration data collected from long-term pump-and-treat operations. The potential factors contributing to plume persistence are generally recognized to include incomplete isolation of the source zone, permeability heterogeneity, well-field hydraulics, and non-ideal (rate-limited, nonlinear) desorption. However, the significance of each factor, especially the site-specific contribution is undetermined, which is very important for site development and management. One objective of this study is to quantify the impacts of different factors on mass-removal efficiency. Three-dimensional (3D) numerical models were used to simulate the impact of different well-field configurations on pump-and-treat mass removal. The relationship between reduction in contaminant mass discharge (CMDR) and mass removal (MR) was used as the metric to examine remediation efficiency. Results indicate that (1) even with effort to control the source, residual impact of source can still be a factor causing plume persistence, (2) the well-field configuration has a measurable impact on mass-removal efficiency, which can be muted by the influence of permeability heterogeneity, (3) in terms of permeability heterogeneity, both variance and correlation scale influence the overall mass-removal behavior, (4) the CMDR-MR relationship can be used to quantify the impacts of different factors on mass-removal efficiency at the plume scale. It has been recognized that the use of pump and treat for groundwater remediation will require many decades to attain site closure at most complex sites. Thus, monitored natural attenuation (MNA) and enhanced attenuation (EA) have been widely accepted as alternatives because of their lower cost and sustainable management for large, complex plumes. However, the planning and evaluation of MNA/EA applications require greater levels of characterization data than typically collected. Advanced, innovative methods are required to characterize specific attenuation processes and associated rates to evaluate the feasibility of MNA/EA. Contaminant elution and tracer (CET) tests have been proposed as one such advanced method. Another objective of this study is to investigate the use of modified well-field configurations to enhance the performance of CET tests to collect critical site-specific data that can be used to better delineate attenuation processes and quantify the associated rate coefficients. Three-dimensional numerical models were used to simulate the CET test with specific well-field configurations under different conditions. The results show that the CET test with a nested (two-couplet) well-field configuration can be used to characterize transport and attenuation processes by eliminating the impact of the surrounding plume. The results also show that applying select analytical mass-removal functions can be an efficient method for parameter estimation, as it does not require the use of mathematical transport modeling and does not require the attendant input data that are costly and time-consuming to obtain.