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Sampling strategies for volatile organic compounds at three karst springs in Tennessee

The influence of different sampling strategies on characterizing volatile organic compound (VOC) concentrations and estimating VOC loads was evaluated at three karst springs in Tennessee. During a 6-month period, water samples for VOC analyses were collected weekly at all three springs and as frequently as every 20 min during storms at the two springs with variable water quality conditions. Total 6-month loads for selected VOCs were calculated, and VOC data were systematically subsampled to simulate and evaluate several potential sampling strategies. Results from the study indicate that sampling strategies for karst springs need to be developed on a site-specific basis. The use of fixed sampling intervals (as infrequently as quarterly or semiannually) produced accurate concentration and load estimates at one of the springs; however, additional sampling was needed to detect storm-related changes at a second spring located in a similar hydrogeologic setting. Continuous discharge data and high-frequency or flow-controlled sampling were needed at the third spring, which had the most variable flow and water quality conditions. The lack of continuous discharge data at the third spring would substantially affect load calculations, and the use of fixed sampling intervals would affect load calculations and the ability to detect pulses of high contaminant concentrations that might exceed toxicity levels for aquatic organisms. ?? 2006 National Ground Water Association.

Ground Water Monitoring and Remediation

Low-temperature MTBE biodegradation in aquifer sediments with a history of low, seasonal ground water temperatures

Sediments from two shallow, methyl tert ‐butyl ether (MTBE)–contaminated aquifers, with mean ground water temperatures ∼10°C, demonstrated significant mineralization of [U‐ 14 C] MTBE to 14 CO 2 at incubation temperatures as low as 4°C. These results indicate that microbial degradation can continue to contribute to the attenuation of MTBE in ground water under wintertime, low‐temperature conditions.

Ground Water Monitoring and Remediation

The chemical quality of self-supplied domestic well water in the United States

Existing water quality data collected from domestic wells were summarized to develop the first national‐scale retrospective of self‐supplied drinking water sources. The contaminants evaluated represent a range of inorganic and organic compounds, and although the data set was not originally designed to be a statistical representation of national occurrence, it encompasses large parts of the United States including at least some wells sampled in every state and Puerto Rico. Inorganic contaminants were detected in many of the wells, and concentrations exceeded the U.S. EPA maximum contaminant levels (MCLs; federal drinking water standards used to regulate public drinking water quality) more often than organic contaminants. Of the inorganic constituents evaluated, arsenic concentrations exceeded the MCL (10 μg/L) in ∼11% of the 7580 wells evaluated, nitrate exceeded the MCL (10 mg/L) in ∼8% of the 3465 wells evaluated, uranium‐238 exceeded the MCL (30 μg/L) in ∼4% of the wells, and radon‐222 exceeded 300 and 4000 pCi/L (potential drinking water standards currently under review by the U.S. EPA) in ∼75% and 9% of the wells, respectively. The MCLs for total mercury and fluoride were each exceeded in <1% of the wells evaluated. The MCL was exceeded in <1% of all wells for all anthropogenically derived organic contaminants evaluated and was not exceeded for many contaminants. In addition, 10 contaminants evaluated do not currently have an MCL. Atrazine, however, was detected in 24% of the wells evaluated and was the most frequently detected organic contaminant of the 28 organic contaminants evaluated in this study. Simazine and metolachlor each were detected in ∼9% of all wells and tied for second in frequency of detection for organic contaminants. The third and fourth most frequently detected organic contaminants were methyl tert ‐butyl ether (MTBE) (6%) and chloroform (5%), respectively. Because the water quality of domestic wells is not federally regulated or nationally monitored, this study provides a unique, previously nonexistent, perspective on the quality of the self‐supplied drinking water resources used by ∼45 million Americans in the United States.

Ground Water Monitoring and Remediation

Effect of H2 and redox condition on biotic and abiotic MTBE transformation

Laboratory studies conducted with surface water sediment from a methyl tert-butyl ether (MTBE)-contaminated site in South Carolina demonstrated that, under methanogenic conditions, [U-14C] MTBE was transformed to 14C tert-butyl alcohol (TBA) with no measurable production of 14CO2. Production of TBA was not attributed to the activity of methanogenic microorganisms, however, because comparable transformation of [U-14C] MTBE to 14C-TBA also was observed in heat-sterilized controls with dissolved H2 concentrations > 5 nM. The results suggest that the transformation of MTBE to TBA may be an abiotic process that is driven by biologically produced H2 under in situ conditions. In contrast, mineralization of [U-14C] MTBE to 14CO2 was completely inhibited by heat sterilization and only observed in treatments characterized by dissolved H2 concentrations < 2 nM. These results suggest that the pathway of MTBE transformation is influenced by in situ H2 concentrations and that in situ H2 concentrations may be an useful indicator of MTBE transformation pathways in ground water systems.

Ground Water Monitoring and Remediation

Influence of dissolved oxygen convection on well sampling

Convective transport of dissolved oxygen (D.O.) from shallow to deeper parts of wells was observed as the shallow water in wells in South Carolina became cooler than the deeper water in the wells due to seasonal changes. Wells having a relatively small depth to water were more susceptible to thermally induced convection than wells where the depth to water was greater because the shallower water levels were more influenced by air temperature. The potential for convective transport of D.O. to maintain oxygenated conditions in a well screened in an anaerobic aquifer was diminished as ground water exchange through the well screen increased and as oxygen demand increased. Transport of D.O. to the screened interval can adversely affect the ability of passive samplers to produce accurate concentrations of oxygen-sensitive solutes such as iron, other redox indicators, and microbiological data. A comparison of passive sampling to low-flow sampling in a well undergoing convection, however, showed general agreement of volatile organic compound concentrations. During low-flow sampling, the pumped water may be a mixture of convecting water from within the well casing and aquifer water moving inward through the screen. This mixing of water during low-flow sampling can substantially increase equilibration times, can cause false stabilization of indicator parameters, can give false indications of the redox state, and can provide microbiological data that are not representative of the aquifer conditions. Data from this investigation show that simple in-well devices can effectively mitigate convective transport of oxygen. The devices can range from inflatable packers to simple, inexpensive baffle systems. ?? 2007 National Ground Water Association.

Ground Water Monitoring and Remediation

Effect of well disinfection on arsenic in ground water

Domestic water wells are routinely subjected to in situ chemical disinfection treatments to control nuisance or pathogenic bacteria. Most treatments are chlorine based and presumably cause strongly oxidizing conditions in the wellbore. Water resource managers in Wisconsin were concerned that such treatments might facilitate release of arsenic from sulfide minerals disseminated within a confined sandstone aquifer. To test this hypothesis, a well was subjected to four disinfection treatments over 9 months time. The first treatment consisted of routine pumping of the well without chemical disinfection; three subsequent treatments included chlorine disinfection and pumping. Pretreatment arsenic concentrations in well water ranged from 7.4 to 18 ??g/L. Elevated arsenic concentrations up to 57 ??g/L in the chemical treatment solutions purged from the well are attributed to the disintegration or dissolution of biofilms or scale. Following each of the four treatments, arsenic concentrations decreased to less than 10 ??g/L during a period of pumping. Arsenic concentrations generally returned to pretreatment levels under stagnant, nonpumping conditions imposed following each treatment. Populations of iron-oxidizing, heterotrophic, and sulfate-reducing bacteria decreased following chemical treatments but were never fully eradicated from the well. Strongly oxidizing conditions were induced by the chlorine-based disinfections, but the treatments did not result in sustained increases in well water arsenic. Results suggest that disruption of biofilm and mineral deposits in the well and the water distribution system in tandem with chlorine disinfection can improve water quality in this setting. ?? 2008 The Author(s).

Ground Water Monitoring and Remediation

Flowpath independent monitoring of reductive dechlorination potential in a fractured rock aquifer

The flowpath dependent approaches that are typically employed to assess biodegradation of chloroethene contaminants in unconsolidated aquifers are problematic in fractured rock settings, due to difficulties defining discrete groundwater flowpaths in such systems. In this study, the variation in the potential for chloroethene biodegradation with depth was evaluated in a fractured rock aquifer using two flowpath independent lines of field evidence: (1) the presence of the three biochemical prerequisites [electron donor(s), chloroethene electron acceptor(s), and chlororespiring microorganism(s)] for efficient chloroethene chlororespiration and (2) the in situ accumulation of chloroethene reductive dechlorination daughter products. The validity of this approach was assessed by comparing field results with the results of [1, 2‐ 14 C] cis ‐DCE microcosm experiments. Microcosms were prepared with depth‐specific core material, which was crushed and emplaced in discrete packer intervals for 1 year to allow colonization by the indigenous microbial community. Packer intervals characterized by significant electron donor concentrations, elevated numbers of chlororespiring microorganisms, and high reductive dechlorination product to parent contaminant ratios correlated well with the production of 14 C‐labeled reductive dechlorination products in the microcosm experiments. These results indicate that, in the absence of information on discrete groundwater flowpaths, a modified approach emphasizing flowpath independent lines of evidence can provide insight into the temporal and spatial variability of contaminant biodegradation in fractured rock systems.

Ground Water Monitoring and Remediation

Paleosols in central Illinois as potential sources of ammonium in groundwater

Glacially buried paleosols of pre-Holocene age were evaluated as potential sources for anomalously large concentrations of ammonium in groundwater in East Central Illinois. Ammonium has been detected at concentrations that are problematic to water treatment facilities (greater than 2.0 mg/L) in this region. Paleosols characterized for this study were of Quaternary age, specifically Robein Silt samples. Paleosol samples displayed significant capacity to both store and release ammonium through experiments measuring processes of sorption, ion exchange, and weathering. Bacteria and fungi within paleosols may significantly facilitate the leaching of ammonium into groundwater by the processes of assimilation and mineralization. Bacterial genetic material (DNA) was successfully extracted from the Robein Silt, purified, and amplified by polymerase chain reaction to produce 16S rRNA terminal restriction fragment length polymorphism (TRFLP) community analyses. The Robein Silt was found to have established diverse and viable bacterial communities. 16S rRNA TRFLP comparisons to well-known bacterial species yielded possible matches with facultative chemolithotrophs, cellulose consumers, nitrate reducers, and actinomycetes. It was concluded that the Robein Silt is both a source and reservoir for groundwater ammonium. Therefore, the occurrence of relatively large concentrations of ammonium in groundwater monitoring data may not necessarily be an indication of only anthropogenic contamination. The results of this study, however, need to be placed in a hydrological context to better understand whether paleosols can be a significant source of ammonium to drinking water supplies. ?? 2009 National Ground Water Association.

Ground Water Monitoring and Remediation

Relative vulnerability of public supply wells to VOC contamination in hydrologically distinct regional aquifers

A process-based methodology was used to compare the vulnerability of public supply wells tapping seven study areas in four hydrologically distinct regional aquifers to volatile organic compound (VOC) contamination. This method considers (1) contributing areas and travel times of groundwater flowpaths converging at individual supply wells, (2) the oxic and/or anoxic conditions encountered along each flowpath, and (3) the combined effects of hydrodynamic dispersion and contaminant- and oxic/anoxic-specific biodegradation. Contributing areas and travel times were assessed using particle tracks generated from calibrated regional groundwater flow models. These results were then used to estimate VOC concentrations relative to an unspecified initial concentration (C/C0) at individual public supply wells. The results show that the vulnerability of public supply wells to VOC contamination varies widely between different regional aquifers. Low-recharge rates, long travel times, and the predominantly oxic conditions characteristic of Basin and Range aquifers in the western United States leads to lower vulnerability to VOCs, particularly to petroleum hydrocarbons such as benzene and toluene. On the other hand, high recharge rates and short residence times characteristic of the glacial aquifers of the eastern United States leads to greater vulnerability to VOCs. These differences lead to distinct patterns of C/C0 values estimated for public supply wells characteristic of each aquifer, information that can be used by resource managers to develop monitoring plans based on relative vulnerability, to locate new public supply wells, or to make land-use management decisions.

Ground Water Monitoring and Remediation

Accuracy of flowmeters measuring horizontal groundwater flow in an unconsolidated aquifer simulator.

Borehole flowmeters that measure horizontal flow velocity and direction of groundwater flow are being increasingly applied to a wide variety of environmental problems. This study was carried out to evaluate the measurement accuracy of several types of flowmeters in an unconsolidated aquifer simulator. Flowmeter response to hydraulic gradient, aquifer properties, and well-screen construction was measured during 2003 and 2005 at the U.S. Geological Survey Hydrologic Instrumentation Facility in Bay St. Louis, Mississippi. The flowmeters tested included a commercially available heat-pulse flowmeter, an acoustic Doppler flowmeter, a scanning colloidal borescope flowmeter, and a fluid-conductivity logging system. Results of the study indicated that at least one flowmeter was capable of measuring borehole flow velocity and direction in most simulated conditions. The mean error in direction measurements ranged from 15.1 degrees to 23.5 degrees and the directional accuracy of all tested flowmeters improved with increasing hydraulic gradient. The range of Darcy velocities examined in this study ranged 4.3 to 155 ft/d. For many plots comparing the simulated and measured Darcy velocity, the squared correlation coefficient (r 2 ) exceeded 0.92. The accuracy of velocity measurements varied with well construction and velocity magnitude. The use of horizontal flowmeters in environmental studies appears promising but applications may require more than one type of flowmeter to span the range of conditions encountered in the field. Interpreting flowmeter data from field settings may be complicated by geologic heterogeneity, preferential flow, vertical flow, constricted screen openings, and nonoptimal screen orientation.

Ground Water Monitoring and Remediation

Application of a new vertical profiling tool (ESASS) for sampling groundwater quality during hollow-stem auger drilling

A new tool called ESASS (Enhanced Screen Auger Sampling System) was developed by the U.S. Geological Survey. The use of ESASS, because of its unique U.S. patent design (U.S. patent no. 7,631,705 B1), allows for the collection of representative, depth-specific groundwater samples (vertical profiling) in a quick and efficient manner using a 0.305-m long screen auger during hollow-stem auger drilling. With ESASS, the water column in the flights above the screen auger is separated from the water in the screen auger by a specially designed removable plug and collar. The tool fits inside an auger of standard inner diameter (82.55 mm). The novel design of the system constituted by the plug, collar, and A-rod allows the plug to be retrieved using conventional drilling A-rods. After retrieval, standard-diameter (50.8 mm) observation wells can be installed within the hollow-stem augers. Testing of ESASS was conducted at one waste-disposal site with tetrachloroethylene (PCE) contamination and at two reference sites with no known waste-disposal history. All three sites have similar geology and are underlain by glacial, stratified-drift deposits. For the applications tested, ESASS proved to be a useful tool in vertical profiling of groundwater quality. At the waste site, PCE concentrations measured with ESASS profiling at several depths were comparable (relative percent difference <25%) to PCE concentrations sampled from wells. Vertical profiling with ESASS at the reference sites illustrated the vertical resolution achievable in the profile system; shallow groundwater quality varied by a factor of five in concentration of some constituents (nitrate and nitrite) over short (0.61 m) distances.

Ground Water Monitoring and Remediation

Microbial mineralization of dichloroethene and vinyl chloride under hypoxic conditions

Mineralization of 14C-radiolabled vinyl chloride ([1,2-14C] VC) and cis-dichloroethene ([1,2-14C] cis-DCE) under hypoxic (initial dissolved oxygen (DO) concentrations about 0.1 mg/L) and nominally anoxic (DO minimum detection limit = 0.01 mg/L) was examined in chloroethene-exposed sediments from two groundwater and two surface water sites. The results show significant VC and dichloroethene (DCE) mineralization under hypoxic conditions. All the sample treatments exhibited pseudo-first-order kinetics for DCE and VC mineralization over an extended range of substrate concentrations. First-order rates for VC mineralization were approximately 1 to 2 orders of magnitude higher in hypoxic groundwater sediment treatments and at least three times higher in hypoxic surface water sediment treatments than in the respective anoxic treatments. For VC, oxygen-linked processes accounted for 65 to 85% of mineralization at DO concentrations below 0.1 mg/L, and 14CO2 was the only degradation product observed in VC treatments under hypoxic conditions. Because the lower detection limit for DO concentrations measured in the field is typically 0.1 to 0.5 mg/L, these results indicate that oxygen-linked VC and DCE biodegradation can be significant under field conditions that appear anoxic. Furthermore, because rates of VC mineralization exceeded rates of DCE mineralization under hypoxic conditions, DCE accumulation without concomitant accumulation of VC may not be evidence of a DCE degradative “stall” in chloroethene plumes. Significantly, mineralization of VC above the level that could reasonably be attributed to residual DO contamination was also observed in several nominally anoxic (DO minimum detection limit = 0.01 mg/L) microcosm treatments.

Georgia

Sewers as a source and sink of chlorinated-solvent groundwater contamination, Marine Corps Recruit Depot, Parris Island, South Carolina

Groundwater contamination by tetrachloroethene and its dechlorination products is present in two partially intermingled plumes in the surficial aquifer near a former dry‐cleaning facility at Site 45, Marine Corps Recruit Depot, Parris Island, South Carolina. The northern plume originates from the vicinity of former above‐ground storage tanks. Free‐phase tetrachloroethene from activities in this area entered the groundwater. The southern plume originates at a nearby, new dry‐cleaning facility, but probably was the result of contamination released to the aquifer from a leaking sanitary sewer line from the former dry‐cleaning facility. Discharge of dissolved groundwater contamination is primarily to leaking storm sewers below the water table. The strong influence of sanitary sewers on source distribution and of storm sewers on plume orientation and discharge at this site indicates that groundwater‐contamination investigators should consider the potential influence of sewer systems at their sites.

South Carolina

Potentially bioavailable natural organic carbon and hydrolyzable amino acids in aquifer sediments

This study evaluated the relationship between concentrations of operationally defined potentially bioavailable organic -carbon (PBOC) and hydrolyzable amino acids (HAAs) in sediments collected from a diverse range of chloroethene--contaminated sites. Concentrations of PBOC and HAA were measured using aquifer sediment samples collected at six selected study sites. Average concentrations of total HAA and PBOC ranged from 1.96 ± 1.53 to 20.1 ± 25.6 mg/kg and 4.72 ± 0.72 to 443 ± 65.4 mg/kg, respectively. Results demonstrated a statistically significant positive relationship between concentrations of PBOC and total HAA present in the aquifer sediment (p < 0.05). Higher levels of HAA were consistently observed at sites with greater levels of PBOC and first-order decay rates. Because amino acids are known to be readily biodegradable carbon compounds, this relationship suggests that the sequential chemical extraction procedure used to measure PBOC is a useful indicator of bioavailable carbon in aquifer sediments. This, in turn, is consistent with the interpretation that PBOC measurements can be used for estimating the amount of natural organic carbon available for driving the reductive dechlorination of chloroethenes in groundwater systems.

Ground Water Monitoring and Remediation

Site characterization in densely fractured dolomite: Comparison of methods

One of the challenges in characterizing fractured-rock aquifers is determining whether the equivalent porous medium approximation is valid at the problem scale. Detailed hydrogeologic characterization completed at a small study site in a densely fractured dolomite has yielded an extensive data set that was used to evaluate the utility of the continuum and discrete-fracture approaches to aquifer characterization. There are two near-vertical sets of fractures at the site; near-horizontal bedding-plane partings constitute a third fracture set. Eighteen boreholes, including five coreholes, were drilled to a depth of ???10.6 m. Borehole geophysical logs revealed several laterally extensive horizontal fractures and dissolution zones. Flowmeter and short-interval packer testing identified which of these features were hydraulically important. A monitoring system, consisting of short-interval piezometers and multilevel samplers, was designed to monitor four horizontal fractures and two dissolution zones. The resulting network consisted of >70 sampling points and allowed detailed monitoring of head distributions in three dimensions. Comparison of distributions of hydraulic head - and hydraulic conductivity determined by these two approaches suggests that even in a densely fractured-carbonate aquifer, a characterization approach using traditional long-interval monitoring wells is inadequate to characterize ground water movement for the purposes of regulatory monitoring or site remediation. In addition, traditional multiwell pumping tests yield an average or bulk hydraulic conductivity that is not adequate for predicting rapid ground water travel times through the fracture network, and the pumping test response does not appear to be an adequate tool for assessing whether the porous medium approximation is valid. Copyright ?? 2005 National Ground Water Association.

Ground Water

Progression of natural attenuation processes at a crude-oil spill site . I. Geochemical evolution of the plume

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho -xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe 2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.

Journal of Contaminant Hydrology

Monitoring the natural attenuation of petroleum in ground water at the former naval complex, Operable Unit A, Adak Island, Alaska, May and June 2003

During May and June 2003, the U.S. Geological Survey installed monitoring wells and collected data to characterize the effectiveness of natural attenuation processes for remediating petroleum-contaminated ground water at Operable Unit A of the former Naval complex on Adak Island, Alaska. In addition, the evidence for petroleum biodegradation in ground water was evaluated at selected petroleum sites, plans for future natural attenuation monitoring were suggested for the selected petroleum sites, and the natural attenuation monitoring strategy for the Downtown area of Adak Island was reviewed and refinements were suggested. U.S. Geological Survey personnel measured water levels and collected ground-water samples from about 100 temporary boreholes and 50 monitoring wells. Most samples were analyzed on-site for concentrations of selected petroleum compounds and natural attenuation parameters such as dissolved oxygen, ferrous iron, and carbon dioxide. The U.S. Geological Survey evaluated the data on-site, selected new monitoring well locations, and installed, developed, and sampled 10 monitoring wells. The review and suggestions for the natural attenuation monitoring strategy focused on how to better achieve monitoring objectives specified in the Record of Decision for Adak Island petroleum sites. To achieve the monitoring objective of verifying that natural attenuation is occurring, the monitoring plans for each monitored natural attenuation site need to include sampling of at least one strategically placed well at the downgradient margin of the contaminant plume margin, preferably where contaminant concentrations are detectable but less than the cleanup level. Collection of natural attenuation parameter data and sampling background wells is no longer needed to achieve the monitoring objective of demonstrating the occurrence of natural attenuation. To achieve the objective of monitoring locations where chemical concentrations exceed specified cleanup levels, at least one natural attenuation well within or immediately downgradient from the contaminant source area at each site needs to be monitored. Achieving the Record of Decision-specified final monitoring objective of estimating the rate of natural attenuation to demonstrate achievement of cleanup levels within 75 years will be problematic. Demonstrating (predicting) achievement of cleanup levels within any timeframe in a technically defensible manner will be difficult to achieve using any type of short-term monitoring and evaluation, and will be particularly difficult to achieve through monitoring and evaluation of dissolved-phase petroleum only. Overall, natural attenuation processes appear to have greatly limited the extent of ground-water contamination at most sites investigated and have limited the risk that petroleum contaminants pose to downgradient receptors. Clarification or refinement of the monitoring objective to demonstrate cleanup within 75 years would be a reasonable prelude to developing a monitoring and data evaluation strategy to meet the objective.

Scientific Investigations Report

Methodology for estimating times of remediation associated with monitored natural attenuation

Natural attenuation processes combine to disperse, immobilize, and biologically transform anthropogenic contaminants, such as petroleum hydrocarbons and chlorinated ethenes, in ground-water systems. The time required for these processes to lower contaminant concentrations to levels protective of human health and the environment, however, varies widely between different hydrologic systems, different chemical contaminants, and varying amounts of contaminants. This report outlines a method for estimating timeframes required for natural attenuation processes, such as dispersion, sorption, and biodegradation, to lower contaminant concentrations and mass to predetermined regulatory goals in groundwater systems. The time-of-remediation (TOR) problem described in this report is formulated as three interactive components: (1) estimating the length of a contaminant plume once it has achieved a steady-state configuration from a source area of constant contaminant concentration, (2) estimating the time required for a plume to shrink to a smaller, regulatoryacceptable configuration when source-area contaminant concentrations are lowered by engineered methods, and (3) estimating the time needed for nonaqueous phase liquid (NAPL) contaminants to dissolve, disperse, and biodegrade below predetermined levels in contaminant source areas. This conceptualization was used to develop Natural Attenuation Software (NAS), an interactive computer aquifers. NAS was designed as a screening tool and requires the input of detailed site information about hydrogeology, redox conditions, and the distribution of contaminants. Because NAS is based on numerous simplifications of hydrologic, microbial, and geochemical processes, the program may introduce unacceptable errors for highly heterogeneous hydrologic systems. In such cases, application of the TOR framework outlined in this report may require more detailed, site-specific digital modeling. The NAS software may be downloaded from the Web site http://www.cee.vt.edu/NAS/ Application of NAS illustrates several general characteristics shared by all TOR problems. First, the distance of stabilization of a contaminant plume is strongly dependent on the natural attenuation capacity of particular ground-water systems. The time that it takes a plume to reach a steady-state configuration, however, is independent of natural attenuation capacity. Rather, the time of stabilization is most strongly affected by the sorptive capacity of the aquifer, which is dependent on the organic matter content of the aquifer sediments, as well as the sorptive properties of individual contaminants. As a general rule, a high sorptive capacity retards a plume.s growth or shrinkage, and increases the time of stabilization. Finally, the time of NAPL dissolution depends largely on NAPL mass, composition, geometry, and hydrologic factors, such as ground-water flow rates. An example TOR analysis for petroleum hydrocarbon NAPL was performed for the Laurel Bay site in South Carolina. About 500 to 1,000 pounds of gasoline leaked into the aquifer at this site in 1991, and the NAS simulations suggested that TOR would be on the order of 10 years for soluble and poorly sorbed compounds, such as benzene and methyl tertiary-butyl ether (MTBE). Conversely, TOR would be on the order of 40 years for less soluble, more strongly sorbed compounds, such as toluene, ethylbenzene, and xylenes (TEX). These TOR estimates are roughly consistent with contaminant concentrations observed over 10 years of monitoring at this site where benzene and MTBE concentrations were observed to decrease rapidly and are approaching regulatory maximum concentration limits, whereas toluene, ethylbenzene, and xylene concentrations decreased at a slower rate and have remained relatively high. An example TOR analysis for petroleum hydrocarbon NAPL was performed for the Laurel Bay site in South Carolina.

South Carolina