Crude Oil at the Bemidji Site: 25 Years of Monitoring,Modeling, and Understanding

The fate of hydrocarbons in the subsurface near Bemidji, Minnesota, has been investigated by a multidisciplinary group of scientists for over a quarter century. Research at Bemidji has involved extensive investigations of multiphase flow and transport, volatilization, dissolution, geochemical interactions, microbial populations, and biodegradation with the goal of providing an improved understanding of the natural processes limiting the extent of hydrocarbon contamination. A considerable volume of oil remains in the subsurface today despite 30 years of natural attenuation and 5 years of pump‐and‐skim remediation. Studies at Bemidji were among the first to document the importance of anaerobic biodegradation processes for hydrocarbon removal and remediation by natural attenuation. Spatial variability of hydraulic properties was observed to influence subsurface oil and water flow, vapor diffusion, and the progression of biodegradation. Pore‐scale capillary pressure‐saturation hysteresis and the presence of fine‐grained sediments impeded oil flow, causing entrapment and relatively large residual oil saturations. Hydrocarbon attenuation and plume extent was a function of groundwater flow, compound‐specific volatilization, dissolution and biodegradation rates, and availability of electron acceptors. Simulation of hydrocarbon fate and transport affirmed concepts developed from field observations, and provided estimates of field‐scale reaction rates and hydrocarbon mass balance. Long‐term field studies at Bemidji have illustrated that the fate of hydrocarbons evolves with time, and a snap‐shot study of a hydrocarbon plume may not provide information that is of relevance to the long‐term behavior of the plume during natural attenuation.     

Characteristics of distribution and transport of petroleum contaminants in fracture-karst water in Zibo Area, Shandong Province, China

Fracture-karst water is an important water resource for the water supply in North China. Petroleum contamination is one of the most problematic types of the groundwater pollution. The characteristics of distribution and transport of the petroleum contaminants in fracture-karst water are different from those in porous water. The flow velocity of fracture-karst water is much faster than the velocity of porous water on an average. Therefore, contaminant transport in fracture-karst water is an absolute advection-dominated problem. The plume of the petroleum contamination may extend to several kilometers from pollution sources. It was not caused by the oil pool floating on the water table but by the oil components dissolved and scattered in groundwater. The distribution of the petroleum contaminants over space are concentrated in the strong conductive zone on the plane. On the vertical section the highest concentration of the oil contaminants appeared in the strata where the contamination sources were located. The concentrations of the oil contaminants in wells changed greatly over time. Therefore, the curves of concentration versus time fluctuated greatly. The reasons are as follows. (a) Fracture-karst water has a very great velocity. (b) Local flow fields which were caused by pumping and stoppage in some wells changed frequently. (c) In fracture-karst aquifer the transport channels are complicated. (d) Residual oil in vadose zone was leached after rainfall. It is of great practical value for the control and remediation of petroleum contamination in fracture-karst aquifer to understand those characteristics.     

Free-product plume distribution and recovery modeling prediction in a diesel-contaminated volcanic aquifer

Light non-aqueous phase liquids (LNAPL) represent one of the most serious problems in aquifers contaminated with petroleum hydrocarbons liquids. To design an appropriate remediation strategy it is essential to understand the behavior of the plume. The aim of this paper is threefold: (1) to characterize the fluid distribution of an LNAPL plume detected in a volcanic low-conductivity aquifer (∼0.4 m/day from slug tests interpretation), (2) to simulate the recovery processes of the free-product contamination and (3) to evaluate the primary recovery efficiency of the following alternatives: skimming, dual-phase extraction, Bioslurping and multi-phase extraction wells. The API/Charbeneau analytical model was used to investigate the recovery feasibility based on the geological properties and hydrogeological conditions with a multi-phase (water, air, LNAPL) transport approach in the vadose zone. The modeling performed in this research, in terms of LNAPL distribution in the subsurface, show that oil saturation is 7% in the air–oil interface, with a maximum value of 70% in the capillary fringe. Equilibrium between water and LNAPL phases is reached at a depth of 1.80 m from the air–oil interface. On the other hand, the LNAPL recovery model results suggest a remarkable enhancement of the free-product recovery when simultaneous extra-phase extraction was simulated from wells, in addition to the LNAPL lens. Recovery efficiencies were 27%, 65%, 66% and 67% for skimming, dual-phase extraction, Bioslurping and multi-phase extraction, respectively. During a 3-year simulation, skimmer wells and multi-phase extraction showed the lowest and highest LNAPL recovery rates, with expected values from 207 to 163 and 2305 to 707 l-LNAPL/day, respectively. At a field level we are proposing a well distribution arrangement that alternates pairs of dual-phase well-Bioslurping well. This not only improves the recovery of the free-product plume, but also pumps the dissolve plume and enhances in situ biodegradation in the vadose zone. Thus, aquifer and soil remediation can be achieved at a shorter time. Rough calculations suggest that LNAPL can be recovered at an approximate cost of $6–$10/l.     

Cone Penetrometer Tests and HydroPunch® Sampling: A Screening Technique for Plume Definition

Cone penetrometer tests and HydroPunch® sampling were used to define the extent of volatile organic compounds in ground water. The investigation indicated that the combination of these techniques is effective for obtaining ground water samples for preliminary plume definition. HydroPunch samples can be collected in unconsolidated sediments and the analytical results obtained from these samples are comparable to those obtained from adjacent monitoring wells. This sampling method is a rapid and cost-effective screening technique for characterizing the extent of contaminant plumes in soft sediment environments. Use of this screening technique allowed monitoring wells to be located at the plume boundary, thereby reducing the number of wells installed and the overall cost of the plume definition program.     

Migration of Petroleum Products Through Sandy Hydrogeologic Systems

Laboratory column experiments were carried out to study the migration of petroleum products through a sandy porous medium. It was found that the oil pressure needed to displace water from the pores of the sand medium increased with depth below the top of the column. While oil under negative pressure displaced water through the variably unsaturated zone, a significant vertical column of oil was needed to displace water from the pores at the water table. These results indicate that oil penetration to and below the water table will occur only if the porous medium is highly conductive and the rate of oil leak is high. For small to moderate leak rates and hydraulic conductivities, oil would preferentially spread laterally through the zones above the water table. This process of spreading could serve as a natural barrier to severe aquifer contamination by petroleum products.
A simplified procedure was developed to give an order-of-magnitude estimate of the preferred subsurface migration pathways of leaked petroleum products. This procedure utilizes the main drainage and wetting curves for oil and water and the interfacial pressure between these two fluids. This approach could be useful in guiding exploratory investigations, reducing both the risk for further spreading of the contaminants and the investigative cost.     

Thermal DNAPL Source Zone Treatment Impact on a CVOC Plume

The tetrachloroethene (PCE) source zone at a site in Endicott, New York had caused a dissolved PCE plume. This plume was commingled with a petroleum hydrocarbon plume from an upgradient source of fuel oil. The plume required a system for hydraulic containment, using extraction wells located about 360 m downgradient of the source. The source area was remediated using in situ thermal desorption (ISTD). Approximately 1406 kilograms (kg) of PCE was removed in addition to 4082 kg of commingled petroleum‐related compounds. The ISTD treatment reduced the PCE mass discharge into the plume from an estimated 57 kg/year to 0.07 kg/year, essentially removing the source term. In the 5 years following the completion of the thermal treatment in early 2010, the PCE plume has collapsed, and the concentration of degradation products in the PCE‐series plume area has declined by two to three orders of magnitude. Anaerobic dechlorination is the suspected dominant mechanism, assisted by the presence of a fuel oil smear zone and a petroleum hydrocarbon plume from a separate source area upgradient of the PCE source. Based on the post‐thermal treatment groundwater monitoring data, the hydraulic containment system was reduced in 2014 and discontinued in early 2015.     

Effects of a Dual‐Pump Crude‐Oil Recovery System,Bemidji, Minnesota,USA

A crude‐oil spill occurred in 1979 when a pipeline burst near Bemidji, MN. In 1998, the pipeline company installed a dual‐pump recovery system designed to remove crude oil remaining in the subsurface at the site. The remediation from 1999 to 2003 resulted in removal of about 115,000 L of crude oil, representing between 36% and 41% of the volume of oil (280,000 to 316,000 L) estimated to be present in 1998. Effects of the 1999 to 2003 remediation on the dissolved plume were evaluated using measurements of oil thicknesses in wells plus measurements of dissolved oxygen in groundwater. Although the recovery system decreased oil thicknesses in the immediate vicinity of the remediation wells, average oil thicknesses measured in wells were largely unaffected. Dissolved‐oxygen measurements indicate that a secondary plume was caused by disposal of the pumped water in an upgradient infiltration gallery; this plume expanded rapidly immediately following the start of the remediation in 1999. The result was expansion of the anoxic zone of groundwater upgradient and beneath the existing natural attenuation plume. Oil‐phase recovery at this site was shown to be challenging, and considerable volumes of mobile and entrapped oil remain in the subsurface despite remediation efforts.     

A Practical Approach to Evaluating Natural Attenuation of Contaminants in Ground Water

The extent of natural attenuation is an important consideration in determining the most appropriate corrective action at sites where ground water quality has been impacted by releases of petroleum hydrocarbons or other chemicals. The objective of this study was to develop a practical approach that would evaluate natural attenuation based on easily obtained field data and field tested indicators of natural attenuation. The primary indicators that can he used to evaluate natural attenuation include plume characteristics and dissolved oxygen levels in ground water. Case studies of actual field sites show that plumes migrate more slowly than expected, reach a steady state, and decrease in extent and concentration when natural attenuation is occurring. Background dissolved oxygen levels greater than 1 to 2 mg/L and an inverse correlation between dissolved oxygen and contaminant levels have been identified through laboratory and field studies as key indicators of aerobic biodegradation. an important attenuation mechanism. Secondary indicators such as geochemical data, and more intensive methods such as contaminant mass balances, laboratory microcosm studies, and detailed ground water modeling can demonstrate natural attenuation as well. The recommended approach for evaluating natural attenuation is to design site assessment activities so that required data such as dissolved oxygen levels and historical plume flow path concentrations are obtained. With the necessary data, the primary indicators should be applied to evaluate natural attenuation. II the initial evaluation suggests that natural attenuation is a viable corrective action alternative, then a monitoring plan should be implemented to verify the extent of natural attenuation.     

Laboratory Study of Air Sparging: Air Flow Visualization

Laboratory flow visualization experiments, using glass beads as the porous medium, were conducted to study air sparging, an innovative technology for subsurface contaminant remediation. The purpose of these experiments was to observe how air flows through saturated porous media and to obtain a basic understanding of air plume formation and medium heterogeneity effects. The experiments indicate that air flow occurring in discrete, stable channels is the most probable flow behavior in medium to fine grained water saturated porous media and that medium heterogeneity plays an important role in the development of air channels. Several simulated scales of heterogeneities, from pore to field, have been studied. The results suggest that air channel formation is sensitive to the various scales of heterogeneities. Site-specific hydrogeologic settings have to be carefully reviewed before air sparging is applied to remediate sites contaminated by volatile organic compounds.     

Elements in Cottonwood Trees as an Indicator of Ground Water Contaminated by Landfill Leachate

Ground water at the Norman Landfill Research Site is contaminated by a leachate plume emanating from a closed, unlined landfill formerly operated by the city of Norman, Oklahoma, Ground water contaminated by the leachate plume is known to be elevated in the concentration of many, organic and inorganic constituents. Specific conductance, alkalinity, chloride, dissolved organic carbon, boron, sodium, strontium, and deuterium in ground water are considered to be indicators of the leachate plume at this site.
Leaf samples of broad-leafed cottonwood, Populus deltoides , were collected from 57 sites around the closed landfill. Cottonwood, a phreatophyte or "well plant," functions as a & surrogate well and serves as a ground water quality sampler. The leaf samples were combusted to ash and analyzed by instrumental neutron activation for 35 elements and by prompt-gamma instrumental neutron activation, for boron. A monitoring well was located within a few meters of a sampled cottonwood tree at 15 of the 57 sites, and ground water samples were collected from these monitoring wells simultaneously with a leaf sample. The chemical analyses of the ground water and leaf samples from these 15 sites indicated that boron, bromine, sodium, and strontium concentrations in leaves were significantly correlated with leachate indicator constituents in ground water. A point-plot map of selected percentiles indicated high concentrations of boron, bromine, and sodium in leaf ash from sites downgradient of the most recent landfill and from older landfills nearby.
Data from leaf analysis greatly extended the known areal extent of the leachate plume previously determined from a network of monitoring wells and geophysical surveys. This phytosgeochemical study provided a cost-effective method for assessing the extent of a leachate plume from an old landfill. Such a method may be useful as a preliminary sampling tool to guide the design of hydrogeochemical and geophysical studies.     

In Situ Chemical Oxidation of RDX-Contaminated Groundwater with Permanganate at the Nebraska Ordnance Plant

Groundwater beneath the former Nebraska Ordnance Plant (NOP) is contaminated with the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The current pump and treat facility is preventing offsite migration but does not offer a short-term solution. Our objective was to quantify the effectiveness of permanganate to degrade RDX in situ. This was accomplished by performing laboratory treatability experiments, aquifer characterization, and a pilot-scale in situ chemical oxidation (ISCO) demonstration. Treatability experiments confirmed that permanganate could mineralize RDX in the presence of NOP aquifer solids. The pilot-scale ISCO demonstration was performed using an extraction-injection well configuration to create a curtain of permanganate between two injection wells. RDX destruction was then quantified as the RDX-permanganate plume migrated downgradient through a monitoring well field. Electrical resistivity imaging (ERI) was used to identify the subsurface distribution of permanganate after injection. Results showed that RDX concentrations temporally decreased in wells closest to the injection wells by 70% to 80%. Observed degradation rates (0.12 and 0.087/d) were lower than those observed under laboratory batch conditions at 11.5 °C (0.20/d) and resulted from lower than projected permanganate concentrations. Both ERI and spatial electrical conductivity measurements verified that permanganate distribution was not uniform throughout the 6.1-m (20 feet) well screens and that groundwater sampling captured both treated and nontreated groundwater during pumping. Although heterogeneous flow paths precluded a uniform permanganate distribution, pilot-scale results provided proof-of-concept that permanganate can degrade RDX in situ and support permanganate as a possible remedial treatment for RDX-contaminated groundwater.     

Persistence of a Groundwater Contaminant Plume after Hydraulic Source Containment at a Chlorinated‐Solvent Contaminated Site

The objective of this study was to characterize the behavior of a groundwater contaminant (trichloroethene, TCE) plume after implementation of a source‐containment operation at a site in Arizona. The plume resides in a quasi‐three‐layer system comprising a sand/gravel unit bounded on the top and bottom by relatively thick silty clayey layers. The system was monitored for 60 months beginning at start‐up in 2007 to measure the change in contaminant concentrations within the plume, the change in plume area, the mass of the contaminant removed, and the integrated contaminant mass discharge (CMD). The concentrations of TCE in groundwater pumped from the plume extraction wells have declined significantly over the course of operation, as have concentrations for groundwater sampled from 40 monitoring wells located within the plume. The total CMD associated with operation of the plume extraction wells peaked at 0.23 kg/d, decreased significantly within 1 year, and thereafter began an asymptotic decline to a current value of approximately 0.03 kg/d. Despite an 87% reduction in contaminant mass and a comparable 87% reduction in CMD for the plume, the spatial area encompassed by the plume has decreased by only approximately 50%. This is much less than would be anticipated based on ideal flushing and mass‐removal behavior. Simulations produced with a simplified three‐dimensional (3D) numerical model matched reasonably well to the measured data. The results of the study suggest that permeability heterogeneity, back diffusion, hydraulic factors associated with the specific well field system, and residual discharge from the source zone are all contributing to the observed persistence of the plume, as well as the asymptotic behavior currently observed for mass removal and for the reduction in CMD.     

Screened Auger Sampling: The Technique and Two Case Studies

The screened auger is a laser-slotted, hollow-stem auger through which a representative sample of ground water is pumped from an aquifer and tested for water-quality parameters by appropriate field-screening methods. Screened auger sampling can be applied to ground water quality remedial investigations, providing:(1) a mechanism for determining a monitoring well's optimal screen placement in a contaminant plume; and (2) data to define the three-dimensional configuration of the contaminant plume.
Screened auger sampling has provided an efficient method for investigating hexavalent chromium and volatile organic compound contamination in two sandy aquifers in Cadillac, Michigan. The aquifers approach 200 feet in thickness and more than 1 square mile in area. A series of screened auger borings and monitoring wells was installed, and ground water was collected at 10-foot intervals as the boreholes were advanced to define the horizontal and vertical distribution of the contaminant plumes. The ability of the screened auger to obtain representative ground water samples was supported by the statistical comparison of field screening results and subsequent laboratory analysis of ground water from installed monitoring wells.     

The Hydraulic Effects of Lost Circulation and the Implications for Contaminant Migration During Drilling

The impact of lost circulation during rotary drilling near an existing monitoring well cluster was evaluated by periodic measurements of water levels and contaminant concentrations at the well cluster. Due to regulatory concerns, changes in water levels or VOC concentration in the well cluster during drilling would trigger monitoring well redevelopment. The borehole was drilled approximately 30 feet northeast of four nested monitoring wells that screen Devonian and Silurian carbonate bedrock at depths of 15, 60, 130, and 190 feet. Following complete circulation loss at depths of 177 and 1 S3 feet in the borehole, a rapid decrease in water levels was observed in the upper three monitoring wells. The water level in the well that was screened through the lost circulation zones increased slightly.
Decreasing water levels in formations located above the point of circulation loss appear to occur in response to a sudden decrease in borehole fluid pressure caused by the flow of drilling fluid into the formation. The relative contribution of contaminated formation water lo the borehole can be estimated by using the time-drawdown relationship and estimates of transmissivity. At the point of circulation loss, significant dilution of contaminant concentrations occurs from the loss of drilling fluid into the contaminated zone. Contaminated formation water entering the borehole during periods of complete lost circulation may mobilize contaminants from upper lo lower formations. Lost circulation into a formation would be signaled by a water level increase in monitoring wells. The wells would subsequently require development to remove the volume of fluid lost to the formation, including both drilling fluid and contaminated formation water. Monitoring wells exhibiting declining water levels following lost circulation would not require development since drilling water has not entered the zones screened by these wells.     

Optimization of groundwater-monitoring networks for identification of the distribution of a contaminant plume

A new methodology is proposed to optimize monitoring networks for identification of the extent of contaminant plumes. The optimal locations for monitoring wells are determined as the points where maximal decreases are expected in the quantified uncertainty about contaminant existence after well installation. In this study, hydraulic conductivity is considered to be the factor that causes uncertainty. The successive random addition (SRA) method is used to generate random fields of hydraulic conductivity. The expected value of information criterion for the existence of a contaminant plume is evaluated based on how much the uncertainty of plume distribution reduces with increases in the size of the monitoring network. The minimum array of monitoring wells that yields the maximum information is selected as the optimal monitoring network. In order to quantify the uncertainty of the plume distribution, the probability map of contaminant existence is made for all generated contaminant plume realizations on the domain field. The uncertainty is defined as the sum of the areas where the probability of contaminant existence or nonexistence is uncertain. Results of numerical experiments for determination of optimal monitoring networks in heterogeneous conductivity fields are presented.     

Techniques and Equipment Used in Contaminant Detection at Hoe Creek Underground Coal Gasification Experimental Site

Data from an existing network of ground water monitoring wells at the U.S. Department of Energy (DOE) Hoe Creek Underground Coal Gasification (UCG) Experimental Site indicated that organic contaminants, particularly phenols produced during gasification experiments, were threatening neighboring ground water resources. The existing monitoring well network was sparse and further definition of the extent and direction of contaminant migration was needed. Additionally, water level data, important in determining flow directions, was incomplete. A field program was designed and implemented to locate and define the organic contamination and expand the existing ground water monitoring program. The program utilized field analysis of phenol for contaminant detection and well location, followed by completion using gas-drive ground water samplers/piezometers. Geophysical logging was used to permit optimum placement of the samplers. The geologic aspects of the site posed some interesting problems to the installation of the samplers. The contaminant plume edge was defined in the east, west and south directions during the field program. Further work is needed in the north direction.     

Effects of Improper Characterization of Aquifer Thickness on Estimates of Hydraulic Conductivity from Pumping Tests

Pumping test data for surficial aquifers are commonly analyzed under the assumption that the base of the aquifer corresponds to the bottom of the test wells (i.e., the aquifer is truncated). This practice can lead to inaccurate hydraulic conductivity estimates, resulting from the use of low saturated thickness values with transmissivity estimates, and not accounting for the effects of partially penetrating wells. Theoretical time-drawdown data were generated at an observation well in a hypothetical unconfined aquifer for various values of saturated thickness and were analyzed by standard curve-matching techniques. The base of the aquifer was assumed to be the bottom of the pumping and observation wells. The overestimation of horizontal hydraulic conductivity was found to be directly proportional to the error in assumed saturated thickness, and to the (actual) ratio of vertical to horizontal hydraulic conductivity (K_v/K_h). Inaccurately high estimates of hydraulic conductivity obtained by aquifer truncation can lead to overestimates of ground water velocity and contaminant plume spreading, narrow capture zone configuration estimates, and overestimates of available ground water resources.     

Transport and fate of nonaqueous phase liquid (NAPL) in variably saturated porous media with evolving scales of heterogeneity

 A stochastic simulation is performed to study multiphase flow and contaminant transport in fractal porous media with evolving scales of heterogeneity. Numerical simulations of residual NAPL mass transfer and subsequent transport of dissolved and/or volatilized NAPL mass in variably saturated media are carried out in conjunction with Monte Carlo techniques. The impact of fractal dimension, plume scale and anisotropy (stratification) of fractal media on relative dispersivities is investigated and discussed. The results indicate the significance of evolving scale of porous media heterogeneity to the NAPL transport in the subsurface. In general, the fractal porous media enhance the dispersivities of NAPL mass plume transport in both the water phase and the gas phase while the influence on the water phase is more significant. The porous media with larger fractal dimension have larger relative dispersivities. The aqueous horizontal dispersivity exhibits a most significant increase against the plume scale.     

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.