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Francis H. Chapelle

Publications and source records attributed to Francis H. Chapelle.

48 records · Page 3Linked to original sources

Monitored natural attenuation of chlorinated solvents: Moving beyond reductive dechlorination

Monitored natural attenuation (MNA), while a remedy of choice for many sites, can be challenging when the contaminants are chlorinated solvents. Even with many high-quality technical guidance references available, there continue to be challenges implementing MNA at some chlorinated solvent sites. The U.S. Department of Energy, as one organization facing such challenges, is leading a project that will incorporate developing concepts and tools into the existing toolbox for selecting and implementing MNA as a remediation option at sites with chlorinated solvent contamination. The structure and goals of this project were introduced in an article in the Winter 2004 issue of Remediation (Sink et al., 2004). This article is a summary of the three technical areas being developed through the project: mass balance, enhanced attenuation, and characterization and monitoring supporting the first two areas.

Remediation Journal

Stable Carbon Isotopes of HCO3 in the Aquia Aquifer, Maryland: Evidence for an Isotopically Heavy Source of CO2

Concentrations of HCO 3 and δ 13 C values of dissolved inorganic carbon change along the hydrologic gradient of the Aquia aquifer. In the outcrop area, meteoric recharge rapidly dissolves carbonate shell material (δ 13 C ∼ 0.0 per mil) in the presence of soil-gas CO 2 (δ 13 C∼–26 per mil). HCO 3 concentrations in this area range from 150-200 mg/1 and δ 13 C values of dissolved HCO 3 are approximately –13.0 per mil. Concentrations of HCO 3 decrease gradually (to about 130 mg/1) and δ 13 C values become slightly heavier (to about –11.4 per mil) as water flows away from the outcrop area. These trends reflect progressive dissolution of metastable carbonate shell material and subsequent precipitation of secondary calcite cement. At about 40 miles downgradient in the flow system, HCO 3 concentrations increase sharply (to about 400 mg/1), and δ 13 C values become significantly heavier (δ 13 C ∼–6.2 per mil). The observed 1:1 molar ratio of Na + to HCO - 3 in this downgradient water shows that dissolution of isotopically heavy carbonate shell material cannot by itself explain the observed δ 13 C trend. Rather, the Na:HCO - 3 ratio demonstrates that shell material dissolution must take place in the presence of CO 2 . Because the aquifer in this area is closed to both soil-gas and atmospheric CC>2, an aquifer-generated source of isotopically heavy (δ 13 C ∼–5.3 per mil) CO 2 is implied. Possible sources of aquifer-generated CO 2 include bacterially-mediated fermentation of lignitic aquifer materials and bacterially-mediated methanogenesis.

Ground Water

Biodegradation of N-nitrosodimethylamine in soil from a water reclamation facility

The potential introduction of N -nitrosodimethylamine (NDMA) into groundwater during water reclamation activities poses a significant risk to groundwater drinking supplies. Greater than 54% biodegradation of N -[methyl- 14 C]NDMA to 14 CO 2 or to 14 CO 2 and 14 CH 4 was observed in soil from a water reclamation facility under oxic or anoxic conditions, respectively. Likewise, biodegradation was significant in microcosms containing soil with no history of NDMA contamination. These results indicate that aerobic and anaerobic biodegradation of NDMA may be an effective component of NDMA attenuation in water reclamation facility soils.

Bioremediation Journal

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

Ground-water microbiology and geochemistry

Up-to-date coverage and a unique, multidisciplinary approach The ongoing effort to protect our valuable ground-water resources necessarily involves scientists and engineers from many disciplines. Ground-Water Microbiology and Geochemistry, Second Edition is designed to bridge the historical lack of communication among these disciplines by detailing-in language that cuts across specialties-the impact of microorganisms and microbial processes on ground-water systems. Carefully revised to reflect the many recent discoveries that have been made in the field, the Second Edition begins with an overview of microbiology, ideal for hydrologists and others who may lack formal training in the field. These initial chapters systematically cover the kinds of microorganisms found in subsurface environments, focusing on their growth, metabolism, genetics, and ecology. The second part of the book offers a hydrologic perspective on how microbial processes affect ground-water geochemistry in pristine systems. It also introduces the different classes of ground-water systems, and gives an overview of techniques for sampling subsurface environments. Readers gain an understanding of biogeochemical cycling in ground-water systems-in coverage unique to this book-and how ground-water chemistry can be used to study microbial processes in aquifer systems. The final section of the book deals with the biodegradation of human-introduced contaminants in ground-water systems, with an up-to-date review of the physiology, biochemistry, and redox conditions that favor biodegradation processes. Ground-Water Microbiology and Geochemistry, Second Edition is important reading for geoscientists, hydrologists, and environmental engineers, as well as for water planners and lawyers involved in environmental issues. It also serves as a compelling text for upper-level undergraduate and graduate courses in ground-water chemistry.

Book

Role for acetotrophic methanogens in methanogenic biodegradation of vinyl chloride

Under methanogenic conditions, stream-bed sediment microorganisms rapidly degraded [1,2-14C]vinyl chloride to 14CH4 and 14CO2. Amendment with 2-bromoethanesulfonic acid eliminated 14CH4 production and decreased 14CO2 recovery by an equal molar amount. Results obtained with [14C]ethene, [14C]acetate, or 14CO2 as substrates indicated that acetotrophic methanogens were responsible for the production of 14CH4 during biodegradation of [1,2-14C]VC.Under methanogenic conditions, stream-bed sediment microorganisms rapidly degraded [1,2-14C]vinyl chloride to 14CH4 and 14CO2. Amendment with 2-bromoethanesulfonic acid eliminated 14CH4 production and decreased 14CO2 recovery by an equal molar amount. Results obtained with [14C]-ethene, [14C]acetate, or 14CO2 as substrates indicated that acetotrophic methanogens were responsible for the production of 14CH4, during biodegradation of [1,2-14C]VC.

Environmental Science & Technology

Evidence against hydrogen-based microbial ecosystems in basalt aquifers

It has been proposed that hydrogen produced from basalt-ground-water interactions may serve as an energy source that supports the existence of microorganisms in the deep subsurface on Earth and possibly on other planets. However, experiments demonstrated that hydrogen is not produced from basalt at an environmentally relevant, alkaline pH. Small amounts of hydrogen were produced at a lower pH in laboratory incubations, but even this hydrogen production was transitory. Furthermore, geochemical considerations suggest that previously reported rates of hydrogen production cannot be sustained over geologically significant time frames. These findings indicate that hydrogen production from basalt-ground-water interactions may not support microbial metabolism in the subsurface.

Idaho

Technical protocol for evaluating natural attenuation of chlorinated solvents in ground water

This Protocol is designed to evaluate the fate in ground water of chlorinated aliphatic hydrocarbons and/or fuel hydrocarbons. Documentation of natural attenuation requires detailed site characterization. The data collected under this protocol can be used to compare the relative effectiveness of other remedial options. and natural attenuation. This protocol should be used to evaluate whether monitored natural attenuation by itself or in conjunction with other remedial technologies is sufficient to achieve site-specific remedial objectives. Understanding the contaminant flow field in the subsurface is essential for a technically justified evaluation of a monitored natural attenuation remedial option; therefore, use of this protocol is not appropriate for evaluating monitored natural attenuation at sites where the contaminant flow field cannot be determined with an acceptable degree of certainty (e.g., complex fractured bedrock, karst, aquifers.)

Report

Comparison of Eh and H2 measurements for delineating redox processes in a contaminated aquifer

Measurements of oxidation-reduction potential ( E h ) and concentrations of dissolved hydrogen (H 2 ) were made in a shallow groundwater system contaminated with solvents and jet fuel to delineate the zonation of redox processes. E h measurements ranged from +69 to -158 mV in a cross section of the contaminated plume and accurately delineated oxic from anoxic groundwater. Plotting measured E h and pH values on an equilibrium stability diagram indicated that Fe(III) reduction was the predominant redox process in the anoxic zone and did not indicate the presence of methanogenesis and sulfate reduction. In contrast, measurements of H 2 concentrations indicated that methanogenesis predominated in heavily contaminated sediments near the water table surface (H 2 ∼ 7.0 nM) and that the methanogenic zone was surrounded by distinct sulfate-reducing (H 2 ∼ 1-4 nM) and Fe(III)-reducing (H 2 ∼ 0.1-0.8 nM) zones. The presence of methanogenesis, sulfate reduction, and Fe(III) reduction was confirmed by the distribution of dissolved oxygen, sulfate, Fe(II), and methane in groundwater. These results show that H 2 concentrations were more useful for identifying anoxic redox processes than E h measurements in this groundwater system. However, H 2 -based redox zone delineations are more reliable when H 2 concentrations are interpreted in the context of electron-acceptor (oxygen, nitrate, sulfate) availability and the presence of final products [Fe(II), sulfide, methane] of microbial metabolism.

Environmental Science & Technology

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO 2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO 2 to respiration CO 2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO 2 to respiration CO 2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.

South Carolina

Hydrogeology, digital solute-transport simulation, and geochemistry of the Lower Cretaceous aquifer system near Baltimore, Maryland

This study was made to develop information on the hydrogeology and ground-water geochemistry of the Patuxent and Patapsco aquifers (Lower Cretaceous) near Baltimore, Maryland. This information is needed to evaluate the availability and chemical quality of water from these aquifers. The Patuxent aquifer unconformably overlies Lower Paleozoic and Precambrian basement rocks and consists primarily of medium- to coarse-grained quartz sand. Discontinuous lenses of gravel and silty clay are commonly interbedded with the sand-sized material. The Patuxent aquifer in this area attains a thickness of 250 feet and transmissivities range from 2,000 to 8,000 feet squared per day. The Patuxent is the most productive source of ground water in the Baltimore area. In 1982, approximately 11 million gallons of water per day was produced from this unit. Several cones of depression, ranging from 30 to 50 feet below sea level, have developed in response to this pumping stress. The Arundel Formation conformably overlies the Patuxent aquifer. The Arundel is composed predominantly of clay and ranges from 0 to 150 feet thick. The Arundel exhibits very low vertical hydraulic conductivities that are on the order of 10 -9 to 10 -11 feet per second. This unit acts as the upper confining bed of the Patuxent aquifer in much of the project area. The Patapsco aquifer unconformably overlies the Arundel Formation and is a medium- to fine-grained quartz sand. The Patapsco functions as a water-table aquifer in much of the project area. Although the Patapsco has been heavily pumped in the past, pumpage from that aquifer in Baltimore was negligible in 1982. Brackish-water contamination of the Patuxent and Patapsco aquifers has been a major water-quality problem since the early 1900's. The Patuxent aquifer presently (1982) contains a circular plume of brackish-water contamination about 5 miles in diameter. This plume is centered on the Harbor district and has enlarged measurably since 1945. The Patapsco aquifer has a smaller zone of brackish-water contamination that has decreased in size since 1945. Borehole data demonstrate that the Arundel Formation has been breached by Pleistocene river channels near the Harbor district. These erosional channels provide a conduit for brackish water to intrude into the Patuxent aquifer. A two-dimensional areal solute-transport model of the Patuxent aquifer was constructed. This model was designed to estimate the future movement of the brackish-water plume based on alternative scenarios of aquifer use. Model simulations suggest that the plume will remain relatively immobile if 1982 pumping patterns continue into the foreseeable future. However, increased pumpage in the Marley Neck peninsula could draw the plume to the southeast and increase contamination of the Fairfield area. The water quality of the Patuxent aquifer is extremely variable. Because of this variability, it is useful to divide the aquifer into three water-quality zones: Zone 1 -- This zone corresponds to the plume of brackish-water contamination. Zone 2 -- This zone exhibits evidence of urbanization-related contamination such as measurable concentrations of organic chemicals and elevated concentrations of trace elements and total organic carbon. Zone 3 -- Water composition in this zone is controlled exclusively by naturally occurring chemical processes. These processes are dominated by reactions involving dissolved iron. Near the outcrop area, oxidation of pyrite and lignite consumes dissolved oxygen and produces ledges of iron hydroxide-cemented sandstones and conglomerates. The predominant dissolved iron species in oxic water is Fe(OH) 2 + . Downgradient, the water becomes anoxic and sulfate reduction becomes an important process. The predominant dissolved iron species in anoxic water is Fe 2+ .

Maryland