A Tracer Test to Characterize Treatment of TCE in a Permeable Reactive Barrier

A tracer test was conducted to characterize the flow of groundwater across a permeable reactive barrier constructed with plant mulch (a biowall) at the OU‐1 site on Altus Air Force Base, Oklahoma. This biowall is intended to intercept and treat groundwater contaminated by trichloroethylene (TCE) in a shallow aquifer. The biowall is 139‐m long, 7.3‐m deep, and 0.5‐m wide. Bromide was injected from an upgradient well into the groundwater as a conservative tracer, and was subsequently observed breaking through in monitoring wells within and downgradient of the biowall. The bromide breakthrough data demonstrate that groundwater entering the biowall migrated across it, following the slope of the local groundwater surface. The average seepage velocity of groundwater was approximately 0.06 m/d. On the basis of the Darcy velocity of groundwater and geometry of the biowall, the average residence time of groundwater in the biowall was estimated at 10 d. Assuming all TCE removal occurred in the biowall, the reduction in TCE concentrations in groundwater across the biowall corresponds to a first‐order attenuation rate constant in the range of 0.38 to 0.15 per d. As an independent estimate of the degradation rate constant, STANMOD software was used to fit curves through data on the breakthrough of bromide and TCE in selected wells downgradient of the injection wells. Best fits to the data required a first‐order degradation rate constant for TCE removal in the range of 0.13 to 0.17 per d. The approach used in this study provides an objective evaluation of the remedial performance of the biowall that can provide a basis for design of other biowalls that are intended to remediate TCE‐contaminated groundwater.     

Mineral Precipitation Upgradient from a Zero-Valent Iron Permeable Reactive Barrier

Core samples taken from a zero-valent iron permeable reactive barrier (ZVI PRB) at Cornhusker Army Ammunition Plant, Nebraska, were analyzed for physical and chemical characteristics. Precipitates containing iron and sulfide were present at much higher concentrations in native aquifer materials just upgradient of the PRB than in the PRB itself. Sulfur mass balance on core solids coupled with trends in ground water sulfate concentrations indicates that the average ground water flow after 20 months of PRB operation was approximately twenty fold less than the regional ground water velocity. Transport and reaction modeling of the aquifer PRB interface suggests that, at the calculated velocity, both iron and hydrogen could diffuse upgradient against ground water flow and thereby contribute to precipitation in the native aquifer materials. The initial hydraulic conductivity ( K ) of the native materials is less than that of the PRB and, given the observed precipitation in the upgradient native materials, it is likely that K reduction occurred upgradient to rather than within the PRB. Although not directly implicated, guar gum used during installation of the PRB is believed to have played a role in the precipitation and flow reduction processes by enhancing microbial activity.     

Field Evidence for Flow Reduction through a Zero-Valent Iron Permeable Reactive Barrier

The combination of detailed multilevel ground water geochemistry samples, a natural-gradient tracer test, minislug tests, and a numerical flow and transport model was used to examine flow through a zero-valent iron permeable reactive barrier (PRB) installed to remove explosives from ground water. After 20 months of operation, the PRB continued to completely remove explosives from the ground water flowing through it. However, the data indicate that a portion of ground water flow was being diverted beneath the PRB. Ground water geochemistry was significantly altered by the PRB, and concentrations of some ions, including sulfate, carbonate, and calcium, were substantially reduced due to precipitation. Field data and numerical model results indicate that, after 20 months of operation, flow through the PRB was reduced to approximately one-third of its expected value.     

Nitrate Removal Rates in a 15-Year-Old Permeable Reactive Barrier Treating Septic System Nitrate

Permeable reactive barriers (PRBs) have gained popularity in recent years as a low-cost method for ground water remediation. However, their cost advantage usually requires that these barriers remain maintenance free for a number of years after installation. In this study, sediment cores were retrieved from a pilot-scale PRB consisting of a sand and wood particle (sawdust) mixture that has been in continuous operation for 15 years treating nitrate from a septic system plume in southern Ontario (Long Point site). Reaction rates for the 15-year-old media were measured in dynamic flow column tests and were compared to rates measured in year 1 using the same reactive mixture. Nitrate removal rates in the 15-year-old media varied, as expected, with temperature in the range of 0.22 to 1.1 mg N/L/d at 6 °C to 10 °C to 3.5 to 6.0 mg N/L/d at 20 °C to 22 °C. The latter rates remained within about 50% of the year 1 rates (10.2 ± 2.7 mg N/L/d at 22 °C). Near the end of the year 15 column test, media particles >0.5 mm in diameter, containing most of the wood particles, were removed from the reactive media by sieving. Nitrate removal subsequently declined by about 80%, indicating that the wood particles were the principal energy source for denitrification. This example shows that some denitrifying PRBs can remain maintenance free and be adequately reactive for decades.     

An Injectable Apatite Permeable Reactive Barrier for In Situ 90Sr Immobilization

An injectable permeable reactive barrier (PRB) technology was developed to sequester ⁹⁰Sr in groundwater through the in situ formation of calcium‐phosphate mineral phases, specifically apatite that incorporates ⁹⁰Sr into the chemical structure. This injectable barrier technology extends the PRB concept to sites where groundwater contaminants are too deep or where site conditions otherwise preclude the application of more traditional trench‐emplaced barriers. An integrated, multiscale development and testing approach was used that included laboratory bench‐scale experiments, an initial pilot‐scale field test, and the emplacement and evaluation of a 300‐feet‐long treatability‐test‐scale PRB. The apatite amendment formulation uses two separate precursor solutions, one containing a Ca‐citrate complex and the other a Na‐phosphate solution, to form apatite precipitate in situ. Citrate is needed to keep calcium in solution long enough to achieve a more uniform and areally extensive distribution of precipitate formation. In the summer of 2008, the apatite PRB technology was applied as a 91‐m‐long (300 feet) PRB on the downgradient edge of a ⁹⁰Sr plume beneath the Hanford Site in Washington State. The technology was deployed to reduce ⁹⁰Sr flux discharging to the Columbia River. Performance assessment monitoring data collected to date indicate that the barrier is meeting treatment objectives (i.e., 90% reduction in ⁹⁰Sr concentration). The average reduction in ⁹⁰Sr concentrations at four downgradient compliance monitoring locations was 95% relative to the high end of the baseline range approximately 1 year after treatment, and continues to meet remedial objectives more than 4 years after treatment.     

Monitoring the Removal of Phosphate from Ground Water Discharging through a Pond-Bottom Permeable Reactive Barrier

Installation of a permeable reactive barrier to intercept a phosphate (PO₄) plume where it discharges to a pond provided an opportunity to develop and test methods for monitoring the barrier's performance in the shallow pond-bottom sediments. The barrier is composed of zero-valent-iron mixed with the native sediments to a 0.6-m depth over a 1100-m² area. Permanent suction, diffusion, and seepage samplers were installed to monitor PO₄ and other chemical species along vertical transects through the barrier and horizontal transects below and near the top of the barrier. Analysis of pore water sampled at about 3-cm vertical intervals by using multilevel diffusion and suction samplers indicated steep decreases in PO₄ concentrations in ground water flowing upward through the barrier. Samples from vertically aligned pairs of horizontal multiport suction samplers also indicated substantial decreases in PO₄ concentrations and lateral shifts in the plume's discharge area as a result of varying pond stage. Measurements from Lee-style seepage meters indicated substantially decreased PO₄ concentrations in discharging ground water in the treated area; temporal trends in water flux were related to pond stage. The advantages and limitations of each sampling device are described. Preliminary analysis of the first 2 years of data indicates that the barrier reduced PO₄ flux by as much as 95%.     

Evaluating TCE Abiotic and Biotic Degradation Pathways in a Permeable Reactive Barrier Using Compound Specific Isotope Analysis

A pilot‐scale zero valent iron (ZVI) Permeable Reactive Barrier (PRB) was installed using an azimuth‐controlled ‐vertical hydrofracturing at an industrial facility to treat a chlorinated Volatile Organic Compound (VOC) plume. Following ZVI injection, no significant reduction in concentration was observed to occur with the exception of some multilevel monitoring wells, which also showed high levels of total organic carbon (TOC). These patterns suggested that the zero valent iron was not well distributed in the PRB creating leaky conditions. The geochemical data indicated reducing conditions in these areas where VOC reduction was observed, suggesting that biotic processes, associated to the guar used in the injection of the iron, could be a major mechanism of VOC degradation. Compound‐Specific Isotope Analysis (CSIA) using both carbon and chlorine stable isotopes were used as a complementary tool for evaluating the contribution of abiotic and biotic processes to VOC trends in the vicinity of the PRB. The isotopic data showed enriched isotope values around the PRB compared to the isotope composition of the VOC source confirming that VOC degradation is occurring along the PRB. A batch experiment using site groundwater collected near the VOC source and the ZVI used in the PRB was performed to evaluate the site‐specific abiotic isotopic fractionation patterns. Field isotopic trends, typical of biodegradations were observed at the site and were different from those obtained during the batch abiotic experiment. These differences in isotopic trends combined with changes in VOC concentrations and redox parameters suggested that biotic processes are the predominant pathways involved in the degradation of VOCs in the vicinity of the PRB.     

Bench‐Scaled Nano‐Fe0 Permeable Reactive Barrier for Nitrate Removal

There are many fundamental problems with the injection of nano‐zero‐valent iron (NZVI) particles to create permeable reactive barrier (PRB) treatment zone. Among them the loss of medium porosity or pore blocking over time can be considered which leads to reduction of permeability and bypass of the flow and contaminant plume up‐gradient of the PRB. Present study provides a solution for such problems by confining the target zone for injection to the gate in a funnel‐and‐gate configuration. A laboratory‐scale experimental setup is used in this work. In the designed PRB gate, no additional material from porous media exists. NZVI (d₅₀ = 52 ± 5 nm) particles are synthesized in water mixed with ethanol solvent system. A steady‐state condition is considered for the design of PRB size based on the concept of required contact time to obtain optimum width of PRB gate. Batch experiment is carried out and the results are used in the design of PRB gate width (~50 mm). Effect of high initial NO₃^–‐N concentration, NZVI concentration, and pore velocity of water in the range of laminar groundwater flow through porous media are evaluated on nitrate‐N reduction in PRB system. Results of PRB indicate that increasing the initial NO₃^–‐N concentration and pore velocity has inhibitor effect—against the effect of NZVI concentration—on the process of NO₃^–‐N removal. Settlement velocity (S.V.) of injected NZVI with different concentrations in the PRB is also investigated. Results indicate that the proposed PRB can solve the low permeability of medium in down‐gradient but increasing of the S.V. especially at higher concentration is one of the problems with this system that needs further investigations.     

Direct Push Methods for Locating and Collecting Cores of Aquifer Sediment and Zero-Valent Iron from a Permeable Reactive Barrier

It is often necessary to collect core samples that are not accommodated by standard sampling protocols, This paper describes innovative techniques using existing technology that enables researchers to collect samples at upgradient and downgradient interfaces from a zero-valent iron wall so that the most active zone of chromium remediation and biologic activity can be studied. It describes the methodology used and how the direct-push technology was adapted so that the desired samples could be collected. It also explains why new methods were needed and demonstrates the results of these efforts.     

Control of BTEX Migration Using a Biologically Enhanced Permeable Barrier

A permeable barrier system. consisting of a line of closely spaced wclls. was installed perpendicular to ground water flow to control the migration of a dissolved hydrocarhon plume. The wells were charged wiih concrete briquets that release oxygen and nitrate at a controlled rate. enhancing aerobic bio-degradation in the downgradient aquifer.
Laboratory batch reactor experiments were conducted to identify concrete mixtures that slowly released oxygcn over an extended time period. Concretes prepared with urea hydrogen peroxide were unsatisfactory, while concretes prepared with calcium peroxide and a proprietary formalation of magnesium peroxide (ORC®) gradually released oxygen at a steadily declining rate. The 21 percent MgO₂ conerete cylinders and briquets released oxygen at measurable rates for up to 300 days, while the 14 percent CaO₂ briquets were exhausted by 100 days.
A full-scale permeable barrier system using ORC was constructed at a gasoline-spill site. During the first 242 days of operation. total BTFX decreased from 17 to 3.4 mg/L. and dissolved oxygen increased from 0.4 to 1.8 mg/L. during transport through the barrier. Over time, BTEX treatment efficiencies declined. indicating the barrier system had becomc less effective in releasing oxygen and nutrients to the highly contaminated portion of the aquifer. Point dilution tests and sediment analyses performed at the conclusion of the project indicated that ihc aquifer in the vicinity of the remediation wells had been clogged by precipitation with iron minerals. This clogging is believed to result from high pH from the concrete and oxygen released by ihc ORC. Oxygen-releasing permeable barriers and other aerobic bioremediation processes should be used with caution in aquifers with high levels of dissolved iron.     

一致概率谱衰减指数的取值方法探讨

在重大工程的地震安全性评价工作中,根据概率法地震危险性分析得到的一致概率反应谱,与建筑抗震设计规范给出的设计反应谱常常不一致,特别是在长周期部分,一致概率谱一般均低于相应的规范谱。为解决地震安全性评价得到的一致概率谱在抗震设计中的应用,本文通过比较、分析一致概率谱和规范谱,针对一致概率谱标定得到的衰减指数γ较规范谱明显偏大的特点,提出了一致概率谱衰减指数的取值方法。     

Time and Magnitude of Peak Concentration of Reactive Groundwater Contaminants Discharged to a River

An analytical solution for calculating the contaminant discharge rate in an aquifer following an instantaneous release of reactive contaminant mass to groundwater is used to derive relationships for the time and magnitude of peak concentration in a river receiving the transported material. Relationships are developed for the time of peak concentration relative to the time of travel for the contaminant, and the magnitude of peak concentration relative to the concentration calculated at the time of travel. Both quantities are found to be a function of two dimensionless parameters characterizing advective‐dispersive‐reactive transport—the Peclet number and the Damkohler number. It is shown that the time to peak concentration may occur before the time of travel, considering advection and retardation only, depending on the magnitudes of the Peclet and Damkohler numbers. Similarly, the magnitude of peak concentration may exceed the concentration calculated assuming that the time of peak concentration coincides with time of travel for the contaminant. For large Damkohler numbers, equating the time of peak concentration with the time of travel for the contaminant can significantly underestimate peak concentrations.     

Mass Discharge in a Tracer Plume: Evaluation of the Theissen Polygon Method

A tracer plume was created within a thin aquifer by injection for 299 d of two adjacent “sub‐plumes” to represent one type of plume heterogeneity encountered in practice. The plume was monitored by snapshot sampling of transects of fully screened wells. The mass injection rate and total mass injected were known. Using all wells in each transect (0.77 m well spacing, 1.4 points/m² sampling density), the Theissen Polygon Method (TPM) yielded apparently accurate mass discharge (M_d) estimates at three transects for 12 snapshots. When applied to hypothetical sparser transects using subsets of the wells with average spacing and sampling density from 1.55 to 5.39 m and 0.70 to 0.20 points/m², respectively, the TPM accuracy depended on well spacing and location of the wells in the hypothesized transect with respect to the sub‐plumes. Potential error was relatively low when the well spacing was less than the widths of the sub‐plumes (>0.35 points/m²). Potential error increased for well spacing similar to or greater than the sub‐plume widths, or when less than 1% of the plume area was sampled. For low density sampling of laterally heterogeneous plumes, small changes in groundwater flow direction can lead to wide fluctuations in M_d estimates by the TPM. However, sampling conducted when flow is known or likely to be in a preferred direction can potentially allow more useful comparisons of M_d over multiyear time frames, such as required for performance evaluation of natural attenuation or engineered remediation systems.     

A Tool for Forecasting the Arrival Time of a Tracer or a Pollutant at a Karst Spring

Karst aquifers are a groundwater resource of global importance. Protection and contamination of karst water resources are often tackled by means of land-use planning and monitoring of physico-chemical and microbial water properties coupled to early-warning systems. However, these solutions of management do not integrate observational data on karst hydrodynamic, for example, tracer tests. Thus, this technical note aims at introducing a straightforward method for forecasting the arrival time of a tracer or a pollutant at a karst spring. Deliverables from the proposed method can assist professionals in the case of a pollution involving a swallow hole of the karst network. The approach is based on repeated tracer testing, gauging of spring flow rate and mathematical curve fitting. Tracer tests and gauging of spring flow rates are repeated under low, middle, and high flow periods. Arrival times of tracer from a given swallow hole of the network are plotted as a function of measured flow rates at the karst spring. The observational data are finally fitted by a mathematical function. Flow rate monitoring at high-temporal resolution at the karst spring and the mathematical functions allow forecasting the arrival of a tracer or a pollutant at the spring in the case of an accident involving a swallow hole of the network or estimating the duration of a pollution if hydrodynamic conditions do not change abruptly. The applicability of the method is documented by three study sites in Switzerland.     

An Analytical Method to Determine Ground Water Supply Well Network Designs

An analytical method is provided where the ground water practitioner can quickly determine the size (number of wells) and spacing of a well network capable of meeting a known ground water demand. In order to apply the method, two new parameters are derived that relate theoretical drawdown to the maximum drawdown that is achievable without mining the aquifer. The size of a well network is shown to be proportional to the ground water demand and inversely proportional to the transmissivity and available head. The spacing between wells in a supply well network is shown to be most sensitive to a derived parameter r _{HA/ 3}, which is related to the available head and the propagation of drawdown away from a theoretical well if the total ground water demand was applied to that well. The method can be used to quickly determine the required spacing between wells in well networks of various sizes that are completed in confined aquifers with no leakance.     

Implementing a Method of Screening One-Well Hydraulic Barrier Design Alternatives

This article provides details of applying the method developed by the authors ( Rubin et al. 2008b ) for screening one-well hydraulic barrier design alternatives. The present article with its supporting information (manual and electronic spreadsheets with a case history example) provides the reader complete details and examples of solving the set of nonlinear equations developed by Rubin et al. (2008b) . It allows proper use of the analytical solutions and also depicting the various charts given by Rubin et al. (2008b) . The final outputs of the calculations are the required position and the discharge of the pumping well. If the contaminant source is nonaqueous phase liquid (NAPL) entrapped within the aquifer, then the method provides an estimate of the aquifer remediation progress (which is a by-product) due to operating the hydraulic barrier.