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Mark E Fuller

Publications and source records attributed to Mark E Fuller.

11 recordsLinked to original sources

Degradation of explosives-related compounds using nickel catalysts.

We report the ability of nickel-based catalysts to degrade explosives compounds in aqueous solution. Several nickel catalysts completely degraded the explosives, although rates varied. Nearly all of the organic explosive compounds tested, including 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), were rapidly degraded to below detection limits by a powdered nickel on an alumina-silicate support (Aldrich nickel catalyst). Perchlorate degradation was minimal (<25%). Degradation of TNT by Aldrich nickel catalyst resulted in apparent first-order kinetics. Significant gaseous 14C was released and collected in an alkaline solution (most likely carbon dioxide) from [14C]RDX and [14C]HMX, indicating heterocyclic ring cleavage. Significant gaseous 14C was not produced from [14C]TNT, but spectrophotometric evidence indicated loss of aromaticity. Degradation occurred in low ionic strength solutions, groundwater, and from pH 3 to pH 9. Degradation of TNT, RDX, and HMX was maintained in flow-through columns of Aldrich nickel catalyst mixed with sand down to a hydraulic retention time of 4h. These data indicate that nickel-based catalysts may be an effective means for remediation of energetics-contaminated groundwater.

Azocines↗

Microbiological changes during bioremediation of explosives-contaminated soils in laboratory and pilot-scale bioslurry reactors.

Changes in the microbial community during bioremediation of explosives-contaminated soil in a molasses-fed bioslurry process were examined. Upon addition of molasses to laboratory-scale reactors, total culturable heterotrophs increased rapidly by three to four orders of magnitude. However, heat-shocked heterotrophs and the percentage of gram-positive bacterial isolates did not increase until the soluble concentrations of 2,4,6-trinitrotoluene (TNT) and 2,4,6-trinitrobenzene (TNB) began to decrease. The number of identified phospholipid fatty acids (PLFA) and the total PLFA concentration also exhibited an immediate increase in response to molasses addition, while the concentration of branched PLFA, indicative of the gram-positive population, remained low until soluble TNT and TNB concentrations had significantly decreased. This same general relationship between explosives degradation and gram-positive-specific PLFA was observed during an experiment with a large field-scale bioslurry lagoon reactor. These results indicate that the gram-positive organisms, which have been shown to be severely impacted by even low concentrations of TNT and TNB [Current Microbiol. 35 (1997) 77; Environ. Toxicol. Chem. 17 (1998) 2185], are able to increase in concentrations after explosives compounds are reduced to non-inhibitory levels, and should therefore be able to reestablish themselves in remediated soils.

Biodegradation, Environmental↗

Application of a vital fluorescent staining method for simultaneous, near-real-time concentration monitoring of two bacterial strains in an Atlantic coastal plain aquifer in Oyster, Virginia.

Two differentially labeled bacterial strains were monitored in near-real time during two field-scale bacterial transport experiments in a shallow aquifer in July 2000 and July 2001. Comamonas sp. strain DA001 and Acidovorax sp. strain OY-107 were grown and labeled with the vital fluorescent stain TAMRA/SE (5 [and -6]-carboxytetramethylrhodamine, succinimidyl ester) or CFDA/SE (5 [and -6]-carboxyfluorescein diacetate, succinimidyl ester). Fluorescently labeled cells and a conservative bromide tracer were introduced into a suboxic superficial aquifer, followed by groundwater collection from down-gradient multilevel samplers. Cells were enumerated in the field by microplate spectrofluorometry, with confirmatory analyses for selected samples done in the laboratory by epifluorescence microscopy, flow cytometry, and ferrographic capture. There was general agreement in the results from all of the vital-stain-based enumeration methods, with differences ranging from <10% up to 40% for the analysis of identical samples between different tracking methods. Field analysis by microplate spectrofluorometry was robust and efficient, allowing thousands of samples to be analyzed in quadruplicate for both of the injected strains. The near-real-time data acquisition allowed adjustments to the predetermined sampling schedule to be made. The microplate spectrofluorometry data sets for the July 2000 and July 2001 experiments allowed the transport of the injected cells to be related to the site hydrogeology and injection conditions and enabled the assessment of differences in the transport of the two strains. This near-real-time method should prove effective for a number of microbial ecology applications.

Biodegradation, Environmental↗

Enhancing the attenuation of explosives in surface soils at military facilities: sorption-desorption isotherms.

The primary objective of the present study was to develop inexpensive soil amendments that can be applied to enhance the adsorption of energetic compounds on military training ranges, thus limiting the potential for these compounds to migrate to groundwater. Adsorption and desorption isotherms were determined for 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine with a wide variety of natural and man-made adsorbents, including wheat straw, sawdust, peat moss, ground rubber tires, and clays. Among the various adsorbents tested, peat moss proved to be the most effective sorbent for the three explosives. The adsorption coefficients (Kd(s)) for TNT and RDX with peat (310 and 87 L/kg, respectively) were at least two orders of magnitude higher than that determined for adsorption of these energetics with two surface soils. The adsorption-desorption isotherms for the explosives showed considerable hysteresis (Kd(s) < Kd(d)) with some of the solid adsorbents, suggesting that the sorption process is not readily reversible but, rather, that some fraction of the adsorbed contaminant is either irreversibly bound or present as a slowly desorbed fraction. The data indicate that the application of specific adsorbents to soils at military impact ranges may significantly improve the protection of local groundwater resources.

Adsorption↗

Enhancing the attenuation of explosives in surface soils at military facilities: combined sorption and biodegradation.

This research evaluated soil amendments designed to enhance the adsorption and biodegradation of explosives at military training facilities, thus minimizing their potential for transport to subsurface environments. Several carbon cosubstrates were tested in soil slurries for their ability to stimulate the biodegradation of 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (royal demolition exposive [RDX]), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (high-melting explosive [HMX]) by indigenous soil microorganisms. Crude soybean oil and molasses stimulated mineralization of RDX (30-40%) and HMX (approximately 10%). The TNT was not significantly mineralized in any of the treatments, but high-performance liquid chromatography (HPLC) analysis indicated extensive transformation of TNT to amino-containing compounds. The biodegradation of explosives was then examined in unsaturated soil microcosms amended with crude soybean oil and molasses combined with sphagnum peat moss and sawdust. Minimal TNT mineralization was observed, and HMX mineralization was only observed with molasses addition. In contrast, RDX mineralization was extensive in microcosms amended with soybean oil or molasses. The presence of peat moss decreased soybean oil-stimulated RDX mineralization by approximately 5%, but resulted in about 5% greater RDX mineralization compared with molasses only. Sawdust markedly decreased mineralization regardless of cosubstrate type. Mass balance results indicated that the formation of bound residues likely was occurring, especially for TNT. These results indicate that the application of inexpensive adsorbents and cosubstrates to soils may significantly improve the protection of groundwater resources underlying live fire ranges.

Adsorption↗

Bioslurry treatment for soils contaminated with very high concentrations of 2,4,6-trinitrophenylmethylnitramine (tetryl).

Past and current DoD activities have resulted in the contamination of soil, sediment and groundwater with various explosive compounds. This research was undertaken to determine the effectiveness of a soil bioslurry process for remediation of soil with very high concentrations of 2,4,6-trinitrophenylmethylnitramine (tetryl). A 99.9% reduction in tetryl concentrations (from 100,000 to below 100 mg/kg) was achieved in 180 to 200 days. A variety of process modifications (i.e. addition of fertilizer, microbial biomass, purging with nitrogen, etc.) that were performed during the course of the experiment did not increase the tetryl biodegradation rate beyond the rates of degradation without modifications. Subsequent batches of soil added as a 25% (v/v) replacement of the slurry were also degraded. These results indicate the potential for this process to remediate highly contaminated soils at many former and current ammunition manufacturing sites.

Aniline Compounds↗

Determination of in situ bacterial growth rates in aquifers and aquifer sediments.

Laboratory and field-scale studies with stained cells were performed to monitor cell growth in groundwater systems. During cell division, the fluorescence intensity of the protein stain 5-(and 6-)-carboxyfluorescein diacetate succinimidyl ester (CFDA/SE) for each cell is halved, and the intensity can be tracked with a flow cytometer. Two strains of bacteria, Comamonas sp. strain DA001 and Acidovorax sp. strain OY-107, both isolated from a shallow aquifer, were utilized in this study. The change in the average generation or the average fluorescence intensity of the CFDA/SE-stained cells could be used to obtain estimates of doubling times. In microcosm experiments, the CFDA/SE-based doubling times were similar to the values calculated by total cell counting and were independent of cell concentration. Intact and repacked sediment core experiments with the same bacteria indicated that changes in groundwater chemistry were just as important as growth rates in determining planktonic cell concentrations. The growth rates within the sediment cores were similar to those calculated in microcosm experiments, and preferential transport of the daughter cells was not observed. The experiments indicated that the growth rates could be determined in systems with cell losses due to other phenomena, such as attachment to sediment or predation. Application of this growth rate estimation method to data from a field-scale bacterial transport experiment indicated that the doubling time was approximately 15 days, which is the first known direct determination of an in situ growth rate for bacteria in an aquifer.

Aeromonas↗

Relative dominance of physical versus chemical effects on the transport of adhesion-deficient bacteria in intact cores from South Oyster, Virginia.

Bacterial transport experiments were conducted using intact sediment cores collected from sites on the Delmarva Peninsula near South Oyster, VA, to delineate the relative importance of physical and chemical heterogeneity in controlling transport of an adhesion-deficient bacterial strain. Electron microscopy revealed that the sediments consisted of quartz and feldspar with a variable amount of clay and iron and aluminum hydroxide coatings on the grains. A nonmotile, gram-negative indigenous groundwater strain, designated as Comamonas sp. DA001, was injected into the cores along with a conservative tracer bromide (Br). DA001 cells were 1.2 x 0.6 microm in size with a hydrophilic surface and a slightly negative surface charge. Bacterial breakthrough preceded that of Br. This differential advection phenomenon can be accounted for by reduction of the effective porosity for the bacteria relative to Br. The distribution of cells remaining in the core as determined by scintillation counting and phosphor imaging techniques was variable, ranging from nearly uniform concentrations throughout the core to exponentially decreasing concentrations with distance from the point of injection. The fraction of bacterial retention in the core was positively correlated with the abundance of the metal hydroxides and negatively correlated with grain size. Because grain size was inversely correlated with the abundance of the metal hydroxide coatings, it was necessary to separate the effects of grain size and mineralogy. The fraction of the bacterial retention accounting for the effect of grain size, the collision efficiency, exhibited no correlation with the abundance of the metal hydroxides, indicating that the bacterial retention was primarily controlled by grain size. Reasons for the lack of influence of mineralogy on bacterial transport include (i) the slightly negatively charged bacterial surfaces; (ii) an insufficient heterogeneity of sediment surface properties; and (iii) the masking of the positive charge of the metal hydroxide surfaces by adsorbed organic carbon (up to 1180 ppm). This study demonstrates that the laboratory-based bacterial transport experiments are effective in delineating physical versus chemical controlling factors and provide an important link to field-based bacterial transport studies.

Bacteria↗

Simultaneous transport of two bacterial strains in intact cores from Oyster, Virginia: biological effects and numerical modeling.

The transport characteristics of two adhesion-deficient, indigenous groundwater strains, Comamonas sp. strain DA001 and Erwinia herbicola OYS2-A, were studied by using intact sediment cores (7 by 50 cm) from Oyster, Va. Both strains are gram-negative rods (1.10 by 0.56 and 1.56 by 0.46 microm, respectively) with strongly hydrophilic membranes and a slightly negative surface charge. The two strains exhibited markedly different behaviors when they were transported through granular porous sediment. To eliminate any effects of physical and chemical heterogeneity on bacterial transport and thus isolate the biological effect, the two strains were simultaneously injected into the same core. DA001 cells were metabolically labeled with (35)S and tagged with a vital fluorescent stain, while OYS2-A cells were metabolically labeled with (14)C. The fast decay of (35)S allowed deconvolution of the two isotopes (and therefore the two strains). Dramatic differences in the transport behaviors were observed. The breakthrough of DA001 and the breakthrough of OYS2-A both occurred before the breakthrough of a conservative tracer (termed differential advection), with effluent recoveries of 55 and 30%, respectively. The retained bacterial concentration of OYS2-A in the sediment was twofold higher than that of DA001. Among the cell properties analyzed, the statistically significant differences between the two strains were cell length and diameter. The shorter, larger-diameter DA001 cells displayed a higher effluent recovery than the longer, smaller-diameter OYS2-A cells. CXTFIT modeling results indicated that compared to the DA001 cells, the OYS2-A cells experienced lower pore velocity, higher porosity, a higher attachment rate, and a lower detachment rate. All these factors may contribute to the observed differences in transport.

Biological Transport↗

A modular injection system, multilevel sampler, and manifold for tracer tests.

Ground water injection and sampling systems were developed for bacterial transport experiments in both homogenous and heterogeneous unconsolidated, surficial aquifers. Two types of injection systems, a large single tank and a dynamic mixing tank, were designed to deliver more than 800 L of amended ground water to the aquifer over 12 hours, without altering the ground water temperature, pH, Eh, or dissolved gas composition. Two types of multilevel samplers (MLSs) were designed and installed. Permanent MLSs performed well for the homogenous surficial aquifer, but their installation procedure promoted vertical mixing, which could obfuscate experimental data obtained from vertically stratified, heterogeneous aquifers. A novel, removable MLS was designed to fit in 2- and 4-inch wells. Expandable O-rings between each sampling port hydraulically isolated each port for sample collection when a nut was tightened at the land surface. A low-cost vacuum manifold system designed to work with both MLS designs used 50 mL centrifuge tubes to efficiently sample 12 MLS ports with one peristaltic pump head. The integrated system was developed and used during four field campaigns over a period of three years. During each campaign, more than 3000 ground water samples were collected in less than one week. This system should prove particularly useful for ground water tracer, injection, and push-pull experiments that require high-frequency and/or high-density sampling.

Bacteria↗

Change of collision efficiency with distance in bacterial transport experiments.

Understanding the mechanisms of bacterial transport in aquifers is important in developing bioremediation strategies. Collision efficiency (alpha) is one important parameter used in modeling bacterial transport. This study was undertaken to measure change in alpha with distance by performing a bacterial transport experiment in Oyster, Virginia. Following injection of a bacterium, Comamonas sp., into a well, water samples were collected at various distances along the flowpath and injected into columns packed with homogenized South Oyster focus area sediment. Zeta potentials of the bacteria in the samples were measured. Values of alpha were determined at various locations in the field in two ways: based on field breakthrough concentrations at the sampling points and based on column breakthrough concentrations. The alpha values estimated from field breakthrough decreased with distance, whereas those estimated from column breakthrough increased with distance. Bacterial cell surface charge became progressively more negative with distance in the field. We hypothesize that the apparent contradiction between field and column alpha values was caused by differences in the flow of the two systems. Flow in the columns was forced to occur through fine-grained zones of iron and aluminum hydroxide coatings that selectively removed the most negatively charged bacteria. In contrast, in the field, the injected cells did not come into contact with the positively charged coatings because the bulk solution bypassed them due to heterogeneous hydraulic properties. These results suggest that laboratory-based models may underestimate bacterial transport distance in the field. A more realistic approach may be necessary to capture the degree of heterogeneity.

Colony Count, Microbial↗