Use of Single‐Well Tracer Dilution Tests to Evaluate LNAPL Flux at Seven Field Sites

Petroleum liquids, referred to as light non‐aqueous phase liquids (LNAPLs), are commonly found beneath petroleum facilities. Concerns with LNAPLs include migration into clean soils, migration beyond property boundaries, and discharges to surface water. Single‐well tracer dilution techniques were used to measure LNAPL fluxes through 50 wells at 7 field sites. A hydrophobic tracer was mixed into LNAPL in a well. Intensities of fluorescence associated with the tracer were measured over time using a spectrometer and a fiber optic cable. LNAPL fluxes were estimated using observed changes in the tracer concentrations over time. Measured LNAPL fluxes range from 0.006 to 2.6 m/year with a mean and median of 0.15 and 0.064 m/year, respectively. Measured LNAPL fluxes are two to four orders of magnitude smaller than a common groundwater flux of 30 m/year. Relationships between LNAPL fluxes and possible governing parameters were evaluated. Observed LNAPL fluxes are largely independent of LNAPL thickness in wells. Natural losses of LNAPL through dissolution, evaporation, and subsequent biodegradation, were estimated using a simple mass balance, measured LNAPL fluxes in wells, and an assumed stable LNAPL extent. The mean and median of the calculated loss rates were found to be 24.0 and 5.0 m³/ha/year, respectively. Mean and median losses are similar to values reported by others. Coupling observed LNAPL fluxes to observed rates of natural LNAPL depletion suggests that natural losses of LNAPL may be an important parameter controlling the overall extent of LNAPL bodies.     

Application of Four Measurement Techniques to Understand Natural Source Zone Depletion Processes at an LNAPL Site

There are several key data gaps in our understanding of Natural Source Zone Depletion (NSZD) processes at sites impacted by light nonaqueous phase liquid (LNAPL), and quantifying NSZD rates can be challenging due to the inherent differences in measurement methods. In this study, four different NSZD measurement methods (oxygen influx measured by the Gradient Method, long-term carbon dioxide efflux measured with Carbon Traps, instantaneous carbon dioxide efflux measured with Dynamic Closed Chambers (DCC LI-COR), and the long-term heat flux from biodegradation measured by Thermal NSZD monitoring), as well as LNAPL composition and dissolved gas sampling, were applied at a site in Southern California. These techniques were used to evaluate key questions such as: (1) how do different NSZD rate measurement methods compare, and what causes variability in NSZD results?; (2) to what extent NSZD processes are occurring in LNAPL within the saturated zone?; and (3) how is NSZD related to LNAPL composition change over time? Carbon Traps and Thermal NSZD monitoring measurement methods provided the most consistent NSZD data at this geologically heterogeneous site, with two location average NSZD rates of 540 and 480 gal/acre/year, respectively. Overall, comparisons of NSZD rates between methods were challenging due to different measurement timeframes, significant temporal and spatial heterogeneity, and operational challenges with two of the NSZD methods. Finally, samples of subsurface LNAPL were collected for analysis in 2007 and 2016; results indicated that diesel-range constituents were already very degraded and anaerobic degradation of gasoline-range constituents was ongoing. A LNAPL depletion model (Douglas et al. 1996) applied to the measured LNAPL composition change appeared to greatly overestimate the amount of LNAPL depletion compared to the measured NSZD rate, but did provide an independent semiqualitative line of evidence that LNAPL was being depleted by active NSZD processes at the site.     

Comparative Evaluation of Single‐Well LNAPL Tracer Testing at Five Sites

Light nonaqueous phase liquid (LNAPL) tracer testing is a technique used to directly measure LNAPL flow in situ and evaluate LNAPL mobility and recoverability. The test method consists of adding a fluorescent oil‐soluble tracer to LNAPL within a well, isolating small volumes of LNAPL with known tracer concentrations for use as in‐well calibration standards, and measuring the rate of tracer concentration decline in the well over time. The test measures LNAPL flux through the well, which is directly related to LNAPL mobility and recoverability in the surrounding formation. Test results for a total of 29 wells at five sites are presented. Results from LNAPL tracer testing were comparable to results obtained through other methods, and the method offers a time‐averaged result measured over a relatively long period, in ambient conditions, and reflects the influences of heterogeneity and hydraulic changes. In some cases, tracer concentration decline followed unexpected patterns, and these data have led to a better understanding of test assumptions, mechanisms influencing tracer distribution, and options to improve test execution and data interpretation. Method improvements developed over the course of the field studies included refinement of pre‐test screening of LNAPL fluorescence and improvements to measurement equipment. Overall, the field studies confirmed the technical validity and usefulness of the LNAPL tracing technique to support LNAPL mobility and recoverability assessments.     

222Rn as Natural Tracer for LNAPL Recovery in a Crude Oil‐Contaminated Aquifer

The objective of this study was to investigate whether ²²²Rn in groundwater can be used as a tracer for light non‐aqueous phase liquid (LNAPL) quantification at a field site treated by dual‐phase LNAPL removal. After the break of a pipeline, 5 ha of soil in the nature reserve Coussouls de Crau in southern France was contaminated by 5100 m³ of crude oil. Part of this oil seeped into the underlying gravel aquifer and formed a floating oil body of about 3.9 ha. The remediation consists of plume management by hydraulic groundwater barriers and LNAPL extraction in the source zone. ²²²Rn measurements were performed in 21 wells in and outside the source zone during 15 months. In uncontaminated groundwater, the radon activity was relatively constant and remained always >11 Bq/L. The variability of radon activity measurements in wells affected by the pump‐and‐skim system was consistent with the measurements in wells that were not impacted by the system. The mean activities in wells in the source zone were, in general, significantly lower than in wells upgradient of the source zone, owing to partitioning of ²²²Rn into the oil phase. The lowest activities were found in zones with high non‐aqueous phase liquid (NAPL) recovery. LNAPL saturations around each recovery well were furthermore calculated during a period of high groundwater level, using a laboratory‐determined crude oil–water partitioning coefficient of 38.5 ± 2.9. This yielded an estimated volume of residual crude oil of 309 ± 93 m³ below the capillary fringe. We find that ²²²Rn is a useful and cheap groundwater tracer for finding zones of good LNAPL recovery in an aquifer treated by dual‐phase LNAPL removal, but that quantification of NAPL saturation using Rn is highly uncertain.     

Measurement of LNAPL Flux Using Single‐Well Intermittent Mixing Tracer Dilution Tests

The stability of subsurface Light Nonaqueous Phase Liquids (LNAPLs) is a key factor driving expectations for remedial measures at LNAPL sites. The conventional approach to resolving LNAPL stability has been to apply Darcy's Equation. This paper explores an alternative approach wherein single‐well tracer dilution tests with intermittent mixing are used to resolve LNAPL stability. As a first step, an implicit solution for single‐well intermittent mixing tracer dilution tests is derived. This includes key assumptions and limits on the allowable time between intermittent mixing events. Second, single‐well tracer dilution tests with intermittent mixing are conducted under conditions of known LNAPL flux. This includes a laboratory sand tank study and two field tests at active LNAPL recovery wells. Results from the sand tank studies indicate that LNAPL fluxes in wells can be transformed into formation fluxes using corrections for (1) LNAPL thicknesses in the well and formation and (2) convergence of flow to the well. Using the apparent convergence factor from the sand tank experiment, the average error between the known and measured LNAPL fluxes is 4%. Results from the field studies show nearly identical known and measured LNAPL fluxes at one well. At the second well the measured fluxes appear to exceed the known value by a factor of two. Agreement between the known and measured LNAPL fluxes, within a factor of two, indicates that single‐well tracer dilution tests with intermittent mixing can be a viable means of resolving LNAPL stability.     

Experimental and Economic Assessment of Two Surfactant Formulations for Source Zone Remediation at a Former Dry Cleaning Facility

Treatability tests and cost analyses were conducted to provide objective criteria for selection of a surfactant formulation to be used for surfactant enhanced aquifer remediation (SEAR) of a tetrachloroethene (PCE)-contaminated site in Oscoda, Michigan. Two surfactant formulations, 4% Tween 80 + 500 mg/L CaCl₂ and 8% Aerosol MA/IPA +15,000 mg/L NaCl + 1000 mg/L CaCl₂, were considered based on their capacity to solubilize PCE and prior use in SEAR applications. Results of a two-dimensional aquifer cell experiment indicated that 53% of the released PCE was recovered after flushing with approximately 8 pore volumes of 4% Tween 80. In contrast, only 3 pore volumes of 8% Aerosol MA/IPA solution were required to recover 78% of the PCE from the two-dimensional aquifer cell, although the greater recovery of PCE was attributed, in large part, to the higher concentration of Aerosol MA. However, mobilization of PCE as free product was observed during the 8% Aerosol MA/IPA flood, which was consistent with total trapping number (N_T) calculations. At the pilot-scale, SEAR treatment costs were estimated to be $222,000 and $244,000 for 4% Tween 80 and 8% Aerosol MA/IPA, respectively, which compared favorably to the estimated pump-and-treat cost of $316,000. Projected full-scale costs, based on a line-drive flushing system, were $382,000 for 4% Tween 80 and $443,000 for 8% Aerosol MA/IPA. In contrast, full-scale pump-and-treat costs were estimated to be $1,167,000. Surfactant recycling was shown to be logistically and economically infeasible at the pilot scale, and provided only a minimal cost benefit for 4% Tween 80 at the full scale. Based on the similarities in solubilization capacity and treatment cost, but substantially lower risk of PCE displacement, Tween 80 was recommended over Aerosol MA/IPA for pilot-scale testing of SEAR.     

Influence of Ambient Temperature,Precipitation, and Groundwater Level on Natural Source Zone Depletion Rates at a Large Semiarid LNAPL Site

Natural source zone depletion (NSZD) is increasingly being integrated into management strategies for petroleum release sites. Measurements of NSZD rates can be used to evaluate naturally occurring hydrocarbon (HC) mass losses, and provide a baseline for evaluating engineered recovery systems. Here, nominal saturated and unsaturated zone HC losses were quantified by groundwater sampling and ground surface CO₂ effluxes approximately monthly over a 1-year period. In addition, subsurface gas profiles and temperature, precipitation, and groundwater elevation were evaluated to elucidate dominant environmental factors controlling NSZD rates. Results showed that NSZD rates estimated by surface CO₂ effluxes were, on average, more than a factor of 3 greater than those estimated by uptake of electron acceptors (primarily sulfate) in extracted groundwater. This may indicate that vadose zone mass loss mechanisms (e.g., volatilization and subsequent biodegradation) were dominant in this system, but possible transfer of gases from the saturated zone to the vadose zone confounds this interpretation. Results for this semiarid site revealed that increasing NSZD rates tended to occur with increasing ambient monthly precipitation and temperature when accounting for time lags associated with subsurface transport. However, groundwater elevation was not found to be significantly related to NSZD rates. This result is counter to an expectation that increased smear zone exposure increases HC mass losses, and suggests that the pump-and-treat system did not greatly influence total NSZD rates directly through smear zone flushing or indirectly by lowering the regional water table.     

Collected Rain Water as Cost-Efficient Source for Aquifer Tracer Testing

Locally collected precipitation water can be actively used as a groundwater tracer solution based on four inherent tracer signals: electrical conductivity, stable isotopic signatures of deuterium [δ²H], oxygen-18 [δ¹⁸O], and heat, which all may strongly differ from the corresponding background values in the tested groundwater. In hydrogeological practice, a tracer test is one of the most important methods for determining subsurface connections or field parameters, such as porosity, dispersivity, diffusion coefficient, groundwater flow velocity, or flow direction. A common problem is the choice of tracer and the corresponding permission by the appropriate authorities. This problem intensifies where tracer tests are conducted in vulnerable conservation or water protection areas (e.g., around drinking water wells). The use of (if required treated) precipitation as an elemental groundwater tracer is a practical solution for this problem, as it does not introduce foreign matters into the aquifer system, which may contribute positively to the permission delivery. Before tracer application, the natural variations of the participating end members' tracer signals have to be evaluated locally. To obtain a sufficient volume of tracer solution, precipitation can be collected as rain using a detached, large-scale rain collector, which will be independent from possibly existing surfaces like roofs or drained areas. The collected precipitation is then stored prior to a tracer experiment.     

抚顺活断层探测震源计算模型的建立及优化

本文通过对断层震源模型的讨论,明确了建立有限震源模型的方法。在考虑抚顺活断层的空间展布、错动方式、凹凸体的数量等多种参数的综合影响的基础上,建立了抚顺目标断层的震源计算模型,为同类工作的开展提供了参考。     

Field Demonstration of Permeable Wall Flushing for Biostimulation of a Shallow Sandy Aquifer

A pilot-scale nutrient injection will (NIW) (4 m by 4 m by 1 m) was installed in the Borden Aquifer lo serve as a pulsed injection source of a potassium acetate solution for the stimulation of anaerobic microbial activity. The success of the flushing procedure was evaluated by monitoring the breakthrough of the acetate solution at several multilevel piezometers installed in the wall. Although some variation in the ground water velocity was observed with depth, the wall was flushed with reasonable uniformity after about six hours of injection and withdrawal, representing about one pore volume, Calculations bused on head level data collected during the flush, and on the solute breakthrough curves, indicated that about 90% of the flow induced by the pumping and injecting was confined to the permeable wall. These results show that a permeable wall injection system is a viable method of introducing solutes uniformly to a cross section of aquifer, with minimal perturbation of the natural flow system. In addition lo its importance for the biostimulation system tested in this project the flushing of permeable walls may have applications in other semi-passive remedial systems, such as the rejuvenation of reactive barriers.     

澄江5.2级地震的震源机制、震源应力场和震源断层

利用地震波资料对澄江5．2级地震序列的震源机制、震源应力场和震源断层作了分析研究。结果表明，整个序列发展中，震源区及附近、构造应力场以南东东方向、水平作用为主的压应力场为主。其次还有南南东向、水平作用为主的压应力场的作用。由序列震源机制解分析，主震发震断层是走向北北东、倾角较陡的断层面，在南南东－南东向，接近水平的压应力场作用下，该断层面具有以左旋走滑为主的错动性质。该断层面是序列的主破裂面。在序列发展过程中，北西西－北西向断层也参与了活动。有的余震，虽然发生在与主破裂面一致或接近的断层面上，但破裂错动的旋性发生了变化，出现了相对主破裂事件的反向错动。极少数余震破裂错动性质呈现以倾向滑动为主的特征。在序列发展过程中，破裂面及其错动性质显地复杂。由于强震的发生，主破裂的错动，使得震源区局部应力场状态错综复杂。     

Source Parameters for 1999 North Anatolian Fault Zone Aftershocks

We develop a data set of aftershock recordings of the 1999, M = 7.4 Izmit and M = 7.2 Duzce (Turkey) earthquakes to study their source parameters. We combined seismograms from 44 stations maintained by several sources (organizations) to obtain a unified data set of events (2.1 ≤ M_w ≤ 5.5). We calculate source parameters of these small earthquakes by two methods that use different techniques to address the difficulty in obtaining source spectra for small earthquakes subject to interference from site response. One method (program NetMoment (NM), Hutchings, 2004) uses spectra of direct S waves in a simultaneous inversion of local high-frequency network data to estimate seismic moment, source corner frequency (f_c), site attenuation (k) and whole-path Q. This approach takes advantage of the source commonality in all recordings for a particular earthquake by fitting a common Brune source spectrum to the data with a and individual k. The second approach (Mayeda et al., 2003) uses the coda method (CM) to obtain “nonmodel-based” source spectra and moment estimates from selected broadband recording sites. We found that both methods do well for events that allow the comparison with seismic moment estimates derived from waveform modeling. Also, source spectra obtained from the two methods are very closely matched for most of the events they have in common. We use an F test to examine the trade-off between k and f_c picks identified by the direct S-wave method. About half of the events could be constrained to have less than a 50% average uncertainty in f_c and k. We used these source spectra solutions to calculate energy and apparent stress and compare these to estimates from the selected “good quality” source spectra from CM. Both studies have values mutually consistent and show a similar increase in apparent stress with increasing moment. This result has added merit due to the independent approaches to calculate apparent stress. We conclude that both methods are at least partially validated by our study, and they both have usefulness for different circumstances of recording local small earthquakes. CM would work well in studies for which there is a broad magnitude range of events and NM works well for local events recorded by band-limited recorders.     

A Tracer Test for Detecting Cross Contamination Along a Monitoring Well Column

A tracer test was used to evaluate whether cross contamination exists along a monitoring well completed through a shallow ground water system in fractured clay and screened in a sand and gravel aquifer. The fractured clay is separated from the sand and gravel deposit by a layer of highly plastic unfractured clay. A natural vertical downward hydraulic gradient of approximately 0.5 exists between the shallow system and the sand and gravel aquifer. Ground water contamination was detected in an adjacent monitoring well screened in the fractured clay and in the monitoring well screened in the sand and gravel deposit. No ground water contamination was apparent in an intermediate well screened in the unfractured clay layer. A tracer of sodium bromide was injected into a shallow boring near the monitoring wells. The tracer was detected in the monitoring well in the sand and gravel aquifer after three to seven days. The bromide concentration continued to increase in this well with time while the concentration in the shallow boring declined. This trend of tracer concentration indicates the tracer has in fact migrated downward and possibly traveled along the well column.     

Source of Ash Zone 1 in the North Atlantic

Geochemical evidence shows that the silicic component of the widespread Ash Zone 1 in the North Atlantic is derived from a major ignimbrite-forming eruption which occurred at the Katla caldera in southern Iceland during the transition from glacial to interglacial conditions in Younger Dryas time. Both trace and major element evidence of the rhyolitic products excludes the Öræfajökull volcano as a source. The high-Ti basaltic component in the marine ash zone can also be attributed to contemporaneous eruption in the Katla volcanic complex. Dispersal of tephra from this event is primarily attributed to the generation of co-ignimbrite ash columns in the atmosphere, with ash fallout on both sea ice and on the ocean floor north and east of Iceland. Owing to the changing ocean circulation characteristics of the glacial regime, including suppression of the Irminger Current and a stronger North Atlantic Current, tephra was rafted on sea ice south into the central North Atlantic and deposited as dispersed Ash Zone 1. Sediments south of Iceland also show evidence of the formation of ash turbidites, generated either by the entrance of pyroclastic flows into the sea, or during discharge of jökulhlaups or glacier bursts from this subglacial eruption.