Comparison of bacterial and archaeal communities in depth-resolved zones in an LNAPL body.

Advances in our understanding of the microbial ecology at sites impacted by light non-aqueous phase liquids (LNAPLs) are needed to drive development of optimized bioremediation technologies, support longevity models, and develop culture-independent molecular tools. In this study, depth-resolved characterization of geochemical parameters and microbial communities was conducted for a shallow hydrocarbon-impacted aquifer. Four distinct zones were identified based on microbial community structure and geochemical data: (i) an aerobic, low-contaminant mass zone at the top of the vadose zone; (ii) a moderate to high-contaminant mass, low-oxygen to anaerobic transition zone in the middle of the vadose zone; (iii) an anaerobic, high-contaminant mass zone spanning the bottom of the vadose zone and saturated zone; and (iv) an anaerobic, low-contaminant mass zone below the LNAPL body. Evidence suggested that hydrocarbon degradation is mediated by syntrophic fermenters and methanogens in zone III. Upward flux of methane likely contributes to promoting anaerobic conditions in zone II by limiting downward flux of oxygen as methane and oxygen fronts converge at the top of this zone. Observed sulfate gradients and microbial communities suggested that sulfate reduction and methanogenesis both contribute to hydrocarbon degradation in zone IV. Pyrosequencing revealed that Syntrophus- and Methanosaeta-related species dominate bacterial and archaeal communities, respectively, in the LNAPL body below the water table. Observed phylotypes were linked with in situ anaerobic hydrocarbon degradation in LNAPL-impacted soils.

Measurement of Natural Losses of LNAPL Using CO2 Traps.

Efflux of CO2 above releases of petroleum light nonaqueous phase liquids (LNAPLs) has emerged as a critical parameter for resolving natural losses of LNAPLs and managing LNAPL sites. Current approaches for resolving CO2 efflux include gradient, flux chamber, and mass balance methods. Herein a new method for measuring CO2 efflux above LNAPL bodies, referred to as CO2 traps, is introduced. CO2 traps involve an upper and a lower solid phase sorbent elements that convert CO2 gas into solid phase carbonates. The sorbent is placed in an open vertical section of 10 cm ID polyvinyl chloride (PVC) pipe located at grade. The lower sorbent element captures CO2 released from the subsurface via diffusion and advection. The upper sorbent element prevents atmospheric CO2 from reaching the lower sorbent element. CO2 traps provide integral measurement of CO2 efflux based over the period of deployment, typically 2 to 4 weeks. Favorable attributes of CO2 traps include simplicity, generation of integral (time averaged) measurement, and a simple means of capturing CO2 for carbon isotope analysis. Results from open and closed laboratory experiments indicate that CO2 traps quantitatively capture CO2 . Results from the deployment of 23 CO2 traps at a former refinery indicate natural loss rates of LNAPL (measured in the fall, likely concurrent with high soil temperatures and consequently high degradation rates) ranging from 13,400 to 130,000 liters per hectare per year (L/Ha/year). A set of field triplicates indicates a coefficient of variation of 18% (resulting from local spatial variations and issues with measurement accuracy).

Continuous combined Fenton's oxidation and biodegradation for the treatment of pentachlorophenol-contaminated water.

Pentachlorophenol (PCP) was studied as a model recalcitrant compound for a sequential chemical oxidation and biodegradation treatment, in a continuous laboratory-scale system that combined a Fenton's chemical reactor and a packed-bed bioreactor. PCP degradation and dechlorination were observed in the Fenton's reactor at a residence time of 1.5 h, although no reduction of total organic carbon (TOC) was observed. Both PCP degradation and dechlorination were strongly dependent on the H(2)O(2) dose to the chemical reactor. The PCP degradation intermediates tetrachlorohydroquinone and dichloromaleic acid were identified in this reactor. Further treatment of the Fenton's reactor effluent with a packed-bed bioreactor (operating at a residence time of 5.5 h) resulted in partial biodegradation of PCP degradation intermediates and reduction in TOC, although no further reduction of PCP or dechlorination was achieved in the bioreactor. Increased residence time in the bioreactor had no significant impact on degradation of TOC. Recycle of the effluent from the bioreactor to the chemical reactor increased the TOC degradation, but not the extent of the PCP degradation or dechlorination. A mathematical model of the combined Fenton's oxidation and biodegradation system supported the experimental results. While the model over-predicted the PCP and TOC degradation in the combined system, it adequately predicted the sensitivity of these parameters to different H(2)O(2) doses and recycle rates. The model indicated that high recycle rates would improve TOC degradation.

Fenton's oxidation of pentachlorophenol.

The combination of H(2)O(2) and Fe(II) (Fenton's reaction) has been demonstrated to rapidly degrade many organics via hydroxyl radicals. However, few studies have related hydroxyl radical generation rates with measured organic chemical degradation data. The goals of this work were to investigate the kinetics, stoichiometry, and intermediates of pentachlorophenol (PCP) degradation in the Fenton's reaction and to develop a mathematical model of this reaction system. Batch reaction experiments were performed to assess both initial transients and steady states, and special attention was given to the analysis of intermediates. Solutions of PCP (55 microM) and Fe(II) (200 microM) were treated with variable levels of H(2)O(2) (<850 microM), and the concentrations of these reactants and their products were measured. Partial PCP degradation and near stoichiometric dechlorination were observed at low initial H(2)O(2) concentrations. Higher H(2)O(2) doses achieved at most 70% dechlorination even though nearly all of the PCP was degraded. The reaction intermediates tetrachlorohydroquinone and dichloromaleic acid accounted for up to 5% of the PCP degraded. Organic carbon mineralization (transformation to CO(2)) was not observed. The ()OH scavenging effects of the PCP-by-products mixture were characterized as a lumped parameter in the reaction kinetics model, which provided reasonable predictions of experimental results at different oxidant concentrations and reaction time.

Effects of reduced contaminant loading on downgradient water quality in an idealized two-layer granular porous media.

The following explores the issue of how reductions in contaminant loading to plumes will effect downgradient water quality. An idealized scenario of two adjacent layers of uniform geologic media, one transmissive and the other low permeability, is considered. A high concentration source, similar to a thin DNAPL pool, is introduced in the transmissive layer immediately above the low permeability layer. While the source is active, dissolved constituents are driven along the contact by advection and into the low permeability layer by transverse diffusion. Removing the source reverses the concentration gradient between the layers, driving back diffusion of contaminants from the low permeability layer. Laboratory studies involving four contaminants demonstrate that 15 to 44% of the introduced contaminant moves into the low permeability zone (along a distance of 87 cm in a sand tank) over a period of 25 days. The greatest movement of contaminants into the low permeability zone is seen with the contaminants with the greatest sorption coefficients. A unique two-dimensional analytical solution is developed for the two-layer scenario. Processes addressed include advection; transverse dispersion; adsorption and degradation in the transmissive zones; and diffusion, adsorption, and degradation in the low permeability layer. Laboratory data agree favorably with the analytical solutions. Collectively, the laboratory results and analytical solutions provide a basis for testing other modeling approaches that can be applied to more complex problems. A set of field-scale scenarios are considered using the analytical solutions. Results indicate that improvement in water quality associated with source removal diminish with distance downgradient of the source. Furthermore, contaminant degradation and contaminant adsorption in the stagnant zone are shown to be critical factors governing the timing and magnitude of downgradient improvements in water quality. For five of six scenarios considered, observed improvements in water quality 100 m downgradient of the source fall in the range of 1 to 2 orders of magnitude 15 years after complete source removal. The sixth scenario, involving a contaminant half-life of three years and no adsorption, shows greater than three order of magnitude improvements in downgradient water quality within one year of source removal.

Hydroxyl free radical reactivity toward aqueous chlorinated phenols.

Second-order kinetic constants (k(OH,S)) for the hydroxyl free radical attack on a series of nine chlorophenols (2-chlorophenol, 2,4-dichlorophenol, 2,5-dichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,3,5,6-tetrachlorophenol, 2,3,4,5-tetrachlorophenol, 2,3,4,6-tetrachlorophenol, and pentachlorophenol) in aqueous solution were determined by means of the competitive kinetics method. Experimental values ranged from 3.5 x 10(09)M(-1)s(-1) for pentachlorophenol to 8.2 x 10(09)M(-1)s(-1) for 2-chlorophenol. A general trend of lower kinetic constant values with higher degree of chlorination was observed and tested with four different correlations using Hammett's sigma values, the number of chlorine substituents on the aromatic ring, and estimated diffusion coefficients. These correlations were statistically significant (alpha=0.01), although the regression coefficients were moderate (R(2)<0.6). Statistical analysis indicated that all correlations were equally valid. This report includes second-order kinetic constants not previously reported for six chlorophenols, and also provides the means to estimate constants for other chlorophenols for which no experimental data are available.