Enhanced Degradation of Dissolved Benzene and Toluene Using a Solid Oxygen-Releasing Compound

A field lest to evaluate the applicability of an oxygon-releasing compound (ORC) to the rernediation of ground water contaminated with benzone and toluene was conducted in the Borden Aquifer in Ontario. Canada. Benzene and toluene were injected as organic substrates to represent BTEX compounds, bromide was used as a tracer, and nitrate was added to avoid nitrate-limited conditions.
The fate of the solutes was monitored along four lines of monitoring points and wells. Two lines studied the behavior of the solutes upgradient and downgradient of two large-diameter well screens filled with briquets containing ORC and briquets without ORC. One line was used to study the solute behavior upgradient and downgradient of columns of ORC powder placed directly in the saturated zone. The remaining line was a control.
The results indicate that ORC in both briquet and powder form can release significant amounts of oxygen to conlaminated ground water passing by it. In the formulation used in this work, oxygen release persisted for at least 10 weeks. Furthemiore, the study indicates that the enhancement of the available dissolved oxygen content of at least 4 mg/L each of the ground water by ORC can support biodegradation of benzene and toluene dissolved in ground water. Such concentrations are typical of those encountered at sites contaminated with petroleum hydrocarbons; therefore, these results suggest that there is promise for ORC to enhance in situ biodegradation of BTKX contaminants at such sites using passive (nonpumping) systems to contact the contaminated ground water with the oxygen source.     

Hydrogen Peroxide Treatment of Septic Systems and Its Negative Effects on Shallow Ground Water

Soil-solution samplers and shallow ground water monitoring wells were utilized to monitor nitrate movement to ground water following H₂O₂ application to a clogged soil absorption system. Nitrate-nitrogen concentrations in soil water and shallow ground water ranged from 29 to 67 mg/L and 9 to 22 mg/L, respectively, prior to H₂O₂ treatment. Mean nitrate-nitrogen concentrations in soil water and ground water increased and ranged from 67 to 115 mg/L and 23 to 37 mg/L, respectively, one week after H₂O₂ application. Elevated concentrations of nitrate-nitrogen above background persisted for several weeks following H₂O₂ treatment. The H₂O₂ treatment was unsuccessful in restoring the infiltrative capacity of a well-structured soil. Application of H₂O₂ to the soil absorption system poses a threat of nitrate contamination of ground water and its usefulness should be fully evaluated before rehabilitation is attempted.     

Permeable Asphalt: A New Tool to Reduce Road Salt Contamination of Groundwater in Urban Areas

Chloride contamination of groundwater in urban areas due to deicing is a well‐documented phenomenon in northern climates. The objective of this study was to evaluate the effects of permeable pavement on degraded urban groundwater. Although low impact development practices have been shown to improve stormwater quality, no infiltration practice has been found to prevent road salt chlorides from entering groundwater. The few studies that have investigated chlorides in permeable asphalt have involved sampling directly beneath the asphalt; no research has looked more broadly at surrounding groundwater conditions. Monitoring wells were installed upgradient and downgradient of an 860 m² permeable asphalt parking lot at the University of Connecticut (Storrs, Connecticut). Water level and specific conductance were measured continuously, and biweekly samples were analyzed for chloride. Samples were also analyzed for sodium (Na), calcium (Ca), and magnesium (Mg). Analysis of variance analysis indicated a significantly (p < 0.001) lower geometric mean Cl concentration downgradient (303.7 mg/L) as compared to upgradient (1280 mg/L). Concentrations of all alkali metals increased upgradient and downgradient during the winter months as compared to nonwinter months, indicating that cation exchange likely occurred. Despite the frequent high peaks of chloride in the winter months as well as the increases in alkali metals observed, monitoring revealed lower Cl concentrations downgradient than upgradient for the majority of the year. These results suggest that the use of permeable asphalt in impacted urban environments with high ambient chloride concentrations can be beneficial to shallow groundwater quality, although these results may not be generalizable to areas with low ambient chloride concentrations.     

An Analysis of Nitrate-Nitrogen in Ground Water Beneath Unsewered Subdivisions

Water samples from private water supply wells in five unsewered subdivisions were tested for nitrate-nitrogen to determine the possible impact of septic systems on ground water quality. Three subdivisions are located in Eau Claire County and two in LaCrosse County, Wisconsin.
The nitrate-nitrogen concentrations in the wells were analyzed in relation to ground water flow direction, the location of septic systems within the subdivision, and the hydrogeologic and physical characteristics of the subdivisions. A comparison of three nitrogen mass balance models helped to identify the possible sources of nitrate-nitrogen in the wells.
The results indicate that nitrogen from septic systems and lawn fertilizer cause nitrate-nitrogen to increase in the ground water beneath the downgradient side of the subdivisions. In three of the five subdivisions the highest nitrate-nitrogen value exceeds the drinking water standard of 10 mg/L.     

Long-Term Ground Water Quality Impacts from the Use of Hexazinone for the Commercial Production of Lowbush Blueberries

Lowbush blueberries, native to eastern Canada and Maine, are an important economic crop in these areas. Herbicides containing the active ingredient hexazinone are commonly applied to blueberry fields, and there is a high frequency of detection of relatively low concentrations of hexazinone in domestic wells located close to areas of lowbush blueberry production. The objective of this study was to determine the long-term impacts from hexazinone-based herbicide use on ground water quality in the immediate growing areas.
Physical and chemical hydrogeologic data were collected for an outwash sand and gravel aquifer in southwestern New Brunswick, Canada. The majority of the land overlying the aquifer is devoted to lowbush blueberry production. Twenty-one nested monitoring wells were sampled for hexazinone and hexazinone metabolites over a four-year period. Hexazinone was consistently detected at values of 1 to 8 parts per billion (ppb) in all but two of these wells, one that is upgradient of herbicide applications, and one that is downgradient with anoxic conditions. Hexazinone metabolites B and A1 were also detected in all but two of the 21 wells at values ranging from 0.5 to 2.5 ppb. The hexazinone and metabolite data suggest both aerobic and anaerobic degradation of hexazinone. Complete degradation of hexazinone appears to occur only in the one downgradient well exhibiting anoxic ground water conditions. Concentrations of hexazinone and its metabolites in the ground water were essentially constant over the four-year period.     

Long-Term Confidence in Ground Water Monitoring Systems

State-of-the-art analytical techniques are capable of detecting contamination In the part per billion (ppb) range or lower. At these levels, a truly representative ground water sample Is essential to precisely evaluate ground water quality. The design specifications of a ground water monitoring system are critical in ensuring the collection of representative samples, particularly throughout the long-term monitoring period.
The potential interfaces from commonly used synthetic well casings require a thorough assessment of site, hydrogeology and the geochemical properties of ground water. Once designed, the monitoring system must be installed following guidelines that ensure adequate seals to prevent contaminant migration during the installation process or at some time in the future. Additionally, maintaining the system so the wells are in hydraulic connection with the monitored zone as well as periodically Inspecting the physical integrity of the system can prolong the usefulness of the wells for ground water quality. When ground water quality data become suspect due to potential interferences from existing monitoring wells, an appropriate abandonment technique must be employed to adequately remove or destroy the well while completely sealing the borehole.
The results of an inspection of a monitoring system comprised of six 4-inch diameter PVC monitoring wells at a hazardous well facility Indicated that the wells were improperly installed and in some cases provided a pathway for contamination. Subsequent down hole television inspections confirmed inaccuracies between construction logs and the existing system as well as identified defects in casing materials. An abandonment program was designed which destroyed the well casings in place while simultaneously providing a competent seal of the re-drilled borehole.     

Electrical Resistivity Studies to Delimit Zones of Acceptable Ground Water Quality

A total of four vertical electrical soundings were conducted in a layered andesitic rock aquifer known in places to yield ground water with total dissolved solids (TDS) in excess of 2,000 milligrams per liter (mg/L). The objective of the soundings was to locate zones of moderate to high permeability but with acceptable chemical quality.
The resistivity of a geologic unit is a function that includes the quantity of total dissolved solids in the interstitial water and the distribution of the water within the unit. Thus, the resistivity of most granular soils and rocks is controlled more by porosity, water content and water quality than by the conductivity of the matrix materials.
The electrical data delimited a drill site where it was believed that ground water of acceptable chemical quality could be expected. Completion and test pumping of two exploration wells confirmed the electrical sounding results.
The first test well drilled prior to the survey yielded only small amounts of ground water with total dissolved solids in excess of 2,000 mg/L. The second exploration well drilled at the site as a result of the electrical study yielded in excess of 100 gallons per minute of ground water with total dissolved solids of 830 mg/L.     

Impacts of a Rural Subdivision on Groundwater Quality: Results of Long-Term Monitoring

A rural subdivision in south central Wisconsin was instrumented with monitoring wells and lysimeters before, during, and after its construction to examine the impacts of the unsewered subdivision on groundwater quality and quantity. Prior to construction, the 78-acre (32 ha) site was farmland. Sixteen homes were constructed beginning in 2003. Initial monitoring from 2002 to 2005 showed that groundwater beneath the site had been impacted by previous agricultural use, with nitrate-N values as high as 30 mg/L and some detections of the herbicide atrazine. Our 12-year study shows that the transition from agricultural to residential land use has changed groundwater quality in both negative and positive ways. Although groundwater elevations showed typical seasonal fluctuations each year, there were no measurable changes in groundwater levels or general flow directions during the 12-year study period. Chloride values increased in many wells, possibly as a result of road salting or water softener discharge. Nitrate concentrations varied spatially and temporally over the study period, with some initial concentrations substantially above the drinking water standard. In some wells, nitrate and atrazine levels have declined substantially since agriculture ceased. However, atrazine was still present at trace concentrations throughout the site in 2014. Wastewater tracers show there are small but detectable impacts from septic effluent on groundwater quality. Particle traces based on a groundwater flow model are consistent with the hypothesis that septic leachate has impacted groundwater quality.     

Effects of water use on arsenic release to well water in a confined aquifer

Field-based experiments were designed to investigate the release of naturally occurring, low to moderate (< 50 microg/L) arsenic concentrations to well water in a confined sandstone aquifer in northeastern Wisconsin. Geologic, geochemical, and hydrogeologic data collected from a 115 m2 site demonstrate that arsenic concentrations in ground water are heterogeneous at the scale of the field site, and that the distribution of arsenic in ground water correlates to solid-phase arsenic in aquifer materials. Arsenic concentrations in a test well varied from 1.8 to 22 microg/L during experiments conducted under no, low, and high pumping rates. The quality of ground water consumed from wells under typical domestic water use patterns differs from that of ground water in the aquifer because of reactions that occur within the well. Redox conditions in the well can change rapidly in response to ground water withdrawals. The well borehole is an environment conducive to microbiological growth, and biogeochemical reactions also affect borehole chemistry. While oxidation of sulfide minerals appears to release arsenic to ground water in zones within the aquifer, reduction of arsenic-bearing iron (hydr)oxides is a likely mechanism of arsenic release to water having a long residence time in the well borehole.     

Effects of River Stage and Waste Water Discharges on the Unconfined Aquifer, Hanford, Washington

This study examined the effects of river stage and waste water discharge on the unconfined aquifer near the N nuclear reactor on the U.S. Department of Energy-operated Hanford site in Washington State. River levels were statistically correlated with water-level data from 12 wells.
During the course of this study, water table elevations declined in the study area primarily as a result of a significant decrease in discharge to waste water disposal facilities, A minor contributing factor was the regional decline of the water table caused by decreasing waste water discharges upgradient of the study area.
High-frequency river-level fluctuations (e.g., short-term daily fluctuations) had good correlation with water-level variations in a well approximately 750 feet inland. Low-frequency river-level fluctuations (e.g., long-term seasonal fluctuations) had good correlation with water-level variations in a well approximately 1000 feet from the river shore. Time lags and attenuation generally increased with distance from the river as expected, with the exception of two northern wells. These two wells were relatively more responsive to river-level fluctuations at a greater distance inland from the river. This suggests that hydraulic properties (e.g., hydraulic conductivity) are a control on the aquifer reponses.
During peak river stage in June, the river level rose above water table elevations in several wells implying a temporary reversal in ground water flow direction near the river.     

Monitoring strategies at phreatic wellfields: a 3D travel time approach

Ground water quality networks for monitoring phreatic drinking water wellfields are generally established for two main purposes: (1) the short-term safeguarding of public water supply and (2) signaling and predicting future quality changes in the extracted ground water. Six monitoring configurations with different well locations and different screen depths and lengths were evaluated using a numerical model of the 3D ground water flow toward a partially penetrating pumping well in a phreatic aquifer. Travel times and breakthrough curves for observation and pumping wells were used to judge the effectiveness of different design configurations for three monitoring objectives: (1) early warning; (2) prediction of future quality changes; and (3) evaluation of protection measures inside a protection zone. Effectiveness was tested for scenarios with advective transport, first-order degradation, and linear sorption. It is shown that the location and especially the depth of the observation wells should be carefully chosen, taking into account the residence time from the surface to the observation well, the residual transit times to the extraction well, and the transformation and retardation rates. Shallow monitoring was most functional for a variety of objectives and conditions. The larger the degradation rates or retardation, the shallower should the monitoring be for effective early warning and prediction of future ground water quality. The general approach followed in the current study is applicable for many geohydrological situations, tuning specific monitoring objectives with residence times and residual transit times obtained from a site-specific ground water flow model.     

Modeling a Ground Water Circulation Well Alternative

Ground water circulation wells (GCWs) provide an appealing alternative to typical pump-and-treat ground water remediation systems because of the inherent resource-conservative nature of the GCW systems. GCW performance prediction is challenging because the consideration of extraction and recharge in a single well is unusual for most practitioners, the technology is relatively new, and a meaningful body of literature has not been published. A three-part evaluation process using state-of-the-practice numerical ground water flow and mass transport models was developed for application during GCW pilot studies at the former Nebraska Ordnance Plant site. A small-scale ground water flow model was developed during the pilot study planning process to predict the system performance and to locate performance-measuring monitoring wells. Key predictions included the capture zone predicted to develop upgradient of the GCW, the downgradierit GCW recharge zone, and the circulation zone centered on the GCW. The flow model was subsequently verified using ground water elevation data and contaminant concentration data collected during pilot study operation. Aquifer parameters were reestimated as a result of the verification process. Those parameter values were used as input to a larger scale model, which was used to develop a remedial alternative consisting of multiple GCW systems.     

The Effect of Latex Gloves and Nylon Cord on Ground Water Sample Quality

Eighteen sites in South Carolina under investigation by the Superfund program were sampled to determine ambient ground water quality. Samples from 11 of 15 monitoring wells sampled with a bailer contained either caprolactam or Santowhite® (a registered trademark of the Monsanto Co.) or both organic compounds. A maximum of 540 μg/L of caprolactam and 780 μg/L of Santowhite was observed in the samples from the monitoring wells. None of the samples collected using dedicated submersible pumps at 28 other wells contained either compound.
Caprolactam is used in the manufacturing of nylon cord, and Santowhite is used as an antioxidant in latex gloves. Therefore, it was suspected that the nylon cord used to raise and lower the bailer and the latex gloves that were worn during sampling may have contributed the caprolactam and Santowhite to the sample.
An experiment using pH-adjusted distilled water and private well water revealed that the nylon cord and the latex gloves may contribute contaminants to ground water samples. Research is needed into the potential for caprolactam and Santowhite to interfere with laboratory analyses in addition to the potential for absorption of contaminants by nylon cord. Until additional information is available, alternative materials or sampling techniques should be considered to minimize the potential impact of nylon cord and latex gloves on the quality of bailed samples.     

Heat, chloride, and specific conductance as ground water tracers near streams

Commonly measured water quality parameters were compared to heat as tracers of stream water exchange with ground water. Temperature, specific conductance, and chloride were sampled at various frequencies in the stream and adjacent wells over a 2-year period. Strong seasonal variations in stream water were observed for temperature and specific conductance. In observation wells where the temperature response correlated to stream water, chloride and specific conductance values were similar to stream water values as well, indicating significant stream water exchange with ground water. At sites where ground water temperature fluctuations were negligible, chloride and/or specific conductance values did not correlate to stream water values, indicating that ground water was not significantly influenced by exchange with stream water. Best-fit simulation modeling was performed at two sites to derive temperature-based estimates of hydraulic conductivities of the alluvial sediments between the stream and wells. These estimates were used in solute transport simulations for a comparison of measured and simulated values for chloride and specific conductance. Simulation results showed that hydraulic conductivities vary seasonally and annually. This variability was a result of seasonal changes in temperature-dependent hydraulic conductivity and scouring or clogging of the streambed. Specific conductance fits were good, while chloride data were difficult to fit due to the infrequent (quarterly) stream water chloride measurements during the study period. Combined analyses of temperature, chloride, and specific conductance led to improved quantification of the spatial and temporal variability of stream water exchange with shallow ground water in an alluvial system.     

Accounting for Temporal Variations in Large-Scale Retrospective Studies of Agricultural Chemicals in Ground Water

Ground water studies that require long data collection periods may be affected by temporal changes in ground water chemistry. Seasonal fluctuations in ground water chemistry are particularly apparent in shallow aquifers. Of specific interest is the inclusion of temporal variability in the design of statistical surveys of agricultural chemicals in well water. Statistical treatment of temporal variability involves selecting a probability sample from temporal units. The selection strategy may include repeating the same spatial units in each temporal stratum or choosing an independent sample of spatial units for each temporal stratum. The appropriate strategy depends on the specific study objectives. Failure to account for temporal variability may compromise the validity of study conclusions. An example of a large-scale retrospective survey designed to estimate temporal averages of water quality across all wells is presented.     

The Effect of Three Drilling Fluids on Ground Water Sample Chemistry

Three monitoring wells were installed in borings that were constructed using water-based drilling fluids containing either (1) guar bean, (2) guar bean with breakdown additive, or (3) bentonite. These fluids were selected to observe their effect on the chemistry of subsequent water samples collected from the wells. The wells were installed to depths of 66 feet, 100.5 feet and 103 feet, respectively, in fine-to-medium sand and gravel outwash deposits near Antigo, Wisconsin. Drilling fluids were necessary to maintain an open borehole during well construction through strata containing cobbles and boulders.
The bentonite and guar drilling fluids caused temporarily elevated concentrations of chemical oxygen demand (COD) in ground water samples collected from the monitoring wells. Using standard development, purging and sampling procedures, elevated COD concentrations persisted for about 50 days for the well bored with the guar-with-additive fluid, 140 days for the bentonite well and 320 days for the guar well. Unfiltered ground water samples for all wells had greater concentrations of COD than samples filtered through a 0.45 micron filter. Sulfate concentrations also decreased with time in the guar-with-additive well and bentonite well, but not in the guar well.
The elevated COD concentrations are attributed to the large concentrations of oxidizable carbon present in the guar bean drilling fluid and in the organic polymers present in the bentonite drilling fluid. Well development and purging procedures, including borehole flushing, surging, bailing and/or chemically induced viscosity breakdown of the guar mud decreased the time before background conditions were achieved. Future research should evaluate the physical and geochemical interaction of different drilling fluid compositions with a variety of geologic matrices and drilling, well development and well purging techniques.     

Long-term performance of permeable reactive barriers using zero-valent iron: geochemical and microbiological effects

Geochemical and microbiological factors that control long-term performance of subsurface permeable reactive barriers were evaluated at the Elizabeth City, North Carolina, and the Denver Federal Center, Colorado, sites. These ground water treatment systems use zero-valent iron filings (Peerless Metal Powders Inc.) to intercept and remediate chlorinated hydrocarbon compounds at the Denver Federal Center (funnel-and-gate system) and overlapping plumes of hexavalent chromium and chlorinated hydrocarbons at Elizabeth City (continuous wall system). Zero-valent iron at both sites is a long-term sink for carbon, sulfur, calcium, silicon, nitrogen, and magnesium. After about four years of operation, the average rates of inorganic carbon (IC) and sulfur (S) accumulation are 0.09 and 0.02 kg/m2/year, respectively, at Elizabeth City where upgradient waters contain <400 mg/L of total dissolved solids (TDS). At the Denver Federal Center site, upgradient ground water contains 1000 to 1200 mg/L TDS and rates of IC and S accumulation are as high as 2.16 and 0.80 kg/m2/year, respectively. At both sites, consistent patterns of spatially variable mineral precipitation and microbial activity are observed. Mineral precipitates and microbial biomass accumulate the fastest near the upgradient aquifer-Fe0 interface. Maximum net reductions in porosity due to the accumulation of sulfur and inorganic carbon precipitates range from 0.032 at Elizabeth City to 0.062 at the Denver Federal Center (gate 2) after about four years. Although pore space has been lost due the accumulation of authigenic components, neither site shows evidence of pervasive pore clogging after four years of operation.     

Rapid Cleanup of a Perchlorate Plume from Fireworks

Perchlorate was detected in a municipal wellfield in Evart, Michigan in April 2015. Perchlorate concentrations were detected initially in six of the City's wells at concentrations ranging up to 20 μg/L. An investigation to identify the source determined that the perchlorate was from fireworks launched during the annual 4th of July show held at the fairgrounds located upgradient from the wellfield. The use of approximately 600 kg of fireworks during the annual display resulted in an annual loading of approximately 4 kg of perchlorate to groundwater. An aggressive groundwater extraction system began operation in June 2016 to restore water quality in the affected aquifer, and the 2016 fireworks display was relocated to a location outside the capture zone of the water supply wells. Within 18 months average perchlorate concentrations in the water supply wells had been reduced to about 0.6 μg/L. The extraction system continued to operate through the end of 2019, by which time the average perchlorate concentrations in the water supply wells were reduced to 0.2 μg/L. In 2019, approximately 0.4 kg of perchlorate were removed from the aquifer, about one-half of the amount removed in 2018, reflecting the slow leaching of perchlorate of fireworks residuals from vadose zone soils.     

Estimating background and threshold nitrate concentrations using probability graphs

Because of the ubiquitous nature of anthropogenic nitrate (NO3(-)) in many parts of the world, determining background concentrations of NO3(-) in shallow ground water from natural sources is probably impossible in most environments. Present-day background must now include diffuse sources of NO3(-) such as disruption of soils and oxidation of organic matter, and atmospheric inputs from products of combustion and evaporation of ammonia from fertilizer and livestock waste. Anomalies can be defined as NO3(-) derived from nitrogen (N) inputs to the environment from anthropogenic activities, including synthetic fertilizers, livestock waste, and septic effluent. Cumulative probability graphs were used to identify threshold concentrations separating background and anomalous NO(3)-N concentrations and to assist in the determination of sources of N contamination for 232 spring water samples and 200 well water samples from karst aquifers. Thresholds were 0.4, 2.5, and 6.7 mg/L for spring water samples, and 0.1, 2.1, and 17 mg/L for well water samples. The 0.4 and 0.1 mg/L values are assumed to represent thresholds for present-day precipitation. Thresholds at 2.5 and 2.1 mg/L are interpreted to represent present-day background concentrations of NO(3)-N. The population of spring water samples with concentrations between 2.5 and 6.7 mg/L represents an amalgam of all sources of NO3(-) in the ground water basins that feed each spring; concentrations > 6.7 mg/L were typically samples collected soon after springtime application of synthetic fertilizer. The 17 mg/L threshold (adjusted to 15 mg/L) for well water samples is interpreted as the level above which livestock wastes dominate the N sources.     

Long-term trends in chloride concentrations in shallow aquifers near Chicago

The rapid expansion of major cities throughout the world is resulting in the degradation of water quality in local aquifers. Increased use of road deicers since the middle of the 20th century in cities in the northern United States, Canada, and Europe has been linked to degraded ground water quality. In this article, Chicago, Illinois, and its outlying suburban areas are used as an example of the effects of urbanization in a historical context. A statistical study of historical water quality data was undertaken to determine how urbanization activities have affected shallow (<60 m) ground water quality. Chloride (Cl⁻) concentrations have been increasing, particularly in counties west and south of Chicago. In the majority of shallow public supply wells in the western and southern counties, Cl⁻ concentrations have been increasing since the 1960s. About 43% of the wells in these counties have rate increases greater than 1 mg/L/year, and 15% have increases greater than 4 mg/L/year. Approximately 24% of the samples collected from public supply wells in the Chicago area in the 1990s had Cl⁻ concentrations greater than 100 mg/L (35% in the western and southern counties); median values were less than 10 mg/L before 1960. The greater increase in Cl⁻ concentrations in the outer counties is most likely due to both natural and anthropogenic factors, including the presence of more significant and shallower sand and gravel deposits, less curbing of major highways and streets, and less development in some parts of these counties.