Coprecipitation of Fe/Cr Hydroxides with Organics: Roles of Organic Properties in Composition and Stability of the Coprecipitates.

Iron hydroxides are important scavengers for dissolved chromium (Cr) via coprecipitation processes; however, the influences of organic matter (OM) on Cr sequestration in Fe/Cr-OM ternary systems and the stability of the coprecipitates are not well understood. Here, Fe/Cr-OM coprecipitation was conducted at pH 3, and Cr hydroxide was undersaturated. Acetic acid (HAc), poly(acrylic acid) (PAA), and Suwannee River natural organic matter (SRNOM) were selected as model OMs, which showed different complexation capabilities with Fe/Cr ions and Fe/Cr hydroxide particles. HAc had no significant effect on the coprecipitation, as the monodentate carboxyl ligand in HAc did not favor complexation with dissolved Fe/Cr ions or Fe/Cr hydroxide nanoparticles. Contrarily, PAA and SRNOM with polydentate carboxyl ligand had strong complexation with Fe/Cr ions and Fe/Cr hydroxide nanoparticles, leading to significant amounts of PAA/SRNOM sequestered in the coprecipitates, which caused the structural disorder and fast aggregation of the coprecipitates. In comparison with that of PAA, preferential complexation of Cr ions with SRNOM resulted in higher Cr/Fe ratios in the coprecipitates. This study advances the fundamental understanding of Fe/Cr-OM coprecipitation and mechanisms controlling the composition and stability of the coprecipitates, which is essential for successful Cr remediation and removal in both natural and engineered settings.

Increased fermentation activity and persistent methanogenesis in a model aquifer system following source removal of an ethanol blend release.

The increased probability of groundwater contamination by ethanol-blended fuel calls for improved understanding of how remediation efforts affect the fate and transport of constituents of concern, including the generation and fate of fermentation byproducts. A pilot-scale (8 m³) model aquifer was used to investigate changes in the concentrations of ethanol and its metabolites (methane and volatile fatty acids) after removal of the contamination source. Following the shut-off of a continuous release of a dissolved ethanol blend (10% v:v ethanol, 50 mg/L benzene, and 50 mg/L toluene), fermentation activity was surprisingly stimulated and the concentrations of ethanol metabolites increased. A microcosm experiment showed that this result was due to a decrease in the dissolved ethanol concentration below its toxicity threshold (∼2000 mg/L for this system). Methane generation (>1.5 mg/L of dissolved methane) persisted for more than 100 days after the disappearance of ethanol, despite clean air-saturated water flowing continuously through the tank at a relative high seepage velocity (0.76 m/day). Quantitative real-time PCR showed that functional genes associated with methane metabolism (mcrA for methanogenesis and pmoA for methanotrophy) also persisted in the aquifer material. Persistent methanogenesis was apparently due to the anaerobic degradation of soil-bound organic carbon (e.g., biomass grown on ethanol and other substrates). Overall, this study reflects the complex plume dynamics following source removal, and suggests that monitoring for increases in the concentration of ethanol metabolites that impact groundwater quality should be considered.

Numerical model investigation for potential methane explosion and benzene vapor intrusion associated with high-ethanol blend releases.

Ethanol-blended fuel releases usually stimulate methanogenesis in the subsurface, which could pose an explosion risk if methane accumulates in a confined space above the ground where ignitable conditions exist. Ethanol-derived methane may also increase the vapor intrusion potential of toxic fuel hydrocarbons by stimulating the depletion of oxygen by methanotrophs, and thus inhibiting aerobic biodegradation of hydrocarbon vapors. To assess these processes, a three-dimensional numerical vapor intrusion model was used to simulate the degradation, migration, and intrusion pathway of methane and benzene under different site conditions. Simulations show that methane is unlikely to build up to pose an explosion hazard (5% v/v) if diffusion is the only mass transport mechanism through the deeper vadose zone. However, if methanogenic activity near the source zone is sufficiently high to cause advective gas transport, then the methane indoor concentration may exceed the flammable threshold under simulated conditions. During subsurface migration, methane biodegradation could consume soil oxygen that would otherwise be available to support hydrocarbon degradation, and increase the vapor intrusion potential for benzene. Vapor intrusion would also be exacerbated if methanogenic activity results in sufficiently high pressure to cause advective gas transport in the unsaturated zone. Overall, our simulations show that current approaches to manage the vapor intrusion risk for conventional fuel released might need to be modified when dealing with some high ethanol blend fuel (i.e., E20 up to E95) releases.

Adaptive microbial population shifts in response to a continuous ethanol blend release increases biodegradation potential.

The fate of fuel releases largely depends on the poorly-understood response in microbial community structure and function. Here, we evaluate the impacts to the microbial community resulting from a pilot-scale continuous release (10 months) of a 10% v:v ethanol solution mixed with benzene and toluene (50 mg/L each). Microbial population shifts were characterized by pyrosequencing-based 16S rRNA analysis and by quantitative PCR targeting Bacteria, Archaea, and functional genes for methanogenesis (mcrA), acetogenesis (fhs) and aerobic degradation of aromatic hydrocarbons (PHE), which could occur in hypoxic micro-environments. The release stimulated microbial growth, increased species richness and diversity, and selected for genotypes involved in fermentative degradation (the relative abundance of mcrA and fhs increased 18- and 6-fold, respectively). The growth of putative hydrocarbon degraders and commensal anaerobes, and increases in microbial diversity and in degradation rates suggest an adaptive response that increases the potential for natural attenuation of ethanol blend releases.

Microbial processes influencing the transport, fate and groundwater impacts of fuel ethanol releases.

Fuel releases that impact groundwater are a common occurrence, and the growing use of ethanol as a transportation biofuel is increasing the likelihood of encountering ethanol in such releases. Microorganisms play a critical role in the fate of ethanol-blended fuel releases, often determining their region of influence and potential impacts. This review summarizes current understanding on the biogeochemical footprint of such releases and the factors that influence their natural attenuation. Implications for site investigation, risk assessment and remediation strategies are also addressed along with research priorities.

Methane bioattenuation and implications for explosion risk reduction along the groundwater to soil surface pathway above a plume of dissolved ethanol.

Fuel ethanol releases can stimulate methanogenesis in impacted aquifers, which could pose an explosion risk if methane migrates into enclosed spaces where ignitable conditions exist. To assess this potential risk, a flux chamber was emplaced on a pilot-scale aquifer exposed to continuous release (21 months) of an ethanol solution (10% v:v) that was introduced 22.5 cm below the water table. Despite methane concentrations within the ethanol plume reaching saturated levels (20-23 mg/L), the maximum methane concentration reaching the chamber (21 ppm(v)) was far below the lower explosion limit in air (50,000 ppm(v)). The low concentrations of methane observed in the chamber are attributed to methanotrophic activity, which was highest in the capillary fringe. This was indicated by methane degradation assays in microcosms prepared with soil samples from different depths, as well as by PCR measurements of pmoA, which is a widely used functional gene biomarker for methanotrophs. Simulations with the analytical vapor intrusion model "Biovapor" corroborated the low explosion risk associated with ethanol fuel releases under more generic conditions. Model simulations also indicated that depending on site-specific conditions, methane oxidation in the unsaturated zone could deplete the available oxygen and hinder aerobic benzene biodegradation, thus increasing benzene vapor intrusion potential. Overall, this study shows the importance of methanotrophic activity near the water table to attenuate methane generated from dissolved ethanol plumes and reduce its potential to migrate and accumulate at the surface.

Microbial community response to a release of neat ethanol onto residual hydrocarbons in a pilot-scale aquifer tank.

The microbial community response to a neat ethanol release (E100, 76 l) onto residual hydrocarbons in sandy soil was evaluated in a continuous-flow 8 m(3) pilot-scale aquifer tank, simulating a release at a bulk fuel terminal. Microbial genotypic shifts were assessed using quantitative real-time PCR analysis. High ethanol concentrations in the capillary fringe at potentially toxic levels, exceeding 100,000 mg l(-1), were tolerated by the microbial community. The high biochemical oxygen demand exerted by ethanol rapidly induced anaerobic conditions, and both methane production (up to 1.2 mg l(-1)) and growth of putative methanogenic Archaea (up to 10(6) gene copies per g of soil) were observed in shallow groundwater and soil samples 75 cm down gradient from the source. Aerobic conditions returned after ethanol was flushed out of the system, approximately 45 days after the spill (less than 7.5 pore volumes flushed). Total Bacteria growth coincided with ethanol migration and availability, which was restricted to a relatively thin layer at the capillary fringe and water table interface. The concentrations of bacteria harbouring the aerobic catabolic genes dmpN (coding for phenol hydroxylase) and to dC1 (coding for toluene dioxygenase) increased (up to 100x) down gradient from the source, likely as a result of both fortuitous growth on ethanol and on aromatic hydrocarbons mobilized by ethanol. Growth of hydrocarbon degraders was corroborated by denaturing gradient gel electrophoresis analysis showing proliferation of Azospirillum and Brevundimonas spp., which are bacteria commonly associated with microaerophilic hydrocarbon degradation. Nevertheless, the relative abundance of hydrocarbon-specific degraders (as a fraction of total Bacteria) decreased as other bacteria grew to a higher extent. Overall, the observed growth of hydrocarbon degraders suggests a potential enhancement in aerobic natural attenuation in shallow aquifers after ethanol and its degradation by-products are degraded or flushed from sites impacted by ethanol-blended fuels.

Fuel-grade ethanol transport and impacts to groundwater in a pilot-scale aquifer tank.

Fuel-grade ethanol (76L of E95, 95%v/v ethanol, 5%v/v hydrocarbon mixture as a denaturant) was released at the water table in an 8150-L continuous-flow tank packed with fine-grain masonry sand. Ethanol, which is buoyant and hygroscopic, quickly migrated upwards and spread laterally in the capillary zone. Horizontal migration of ethanol occurred through a shallow thin layer with minimal vertical dispersion, and was one order of magnitude slower than the preceding bromide tracer. Dyes, one hydrophobic (Sudan-IV) and one hydrophilic (Fluorescein) provided evidence that the fuel hydrocarbons phase separated from the E95 mixture as ethanol was diluted by pore water and its cosolvent effect was diminished. Most of the added ethanol (98%) was recovered in the effluent wells that captured the flow through the high water content regions above the water table. Complementary bench-scale 2-D visualization experiments with E95 confirmed hydrocarbon phase separation, residual NAPL formation and migration within the capillary fringe. These results corroborate previous bench-scale studies showing that ethanol has high affinity for vadose-zone pore water and can migrate through the capillary zone. The pilot-scale tank experiment provides the first hydrocarbon and ethanol concentration measurements (and thus, quantification of impacts to groundwater quality) from a subsurface spill of E95 in a well-characterized system with a well-defined source. It also provides the first quantitative near-field-scale evidence that capillarity can significantly retard the vertical dispersion and horizontal advection of ethanol. Such effects could be important determinants of the extent of ethanol migration and longevity as well as groundwater impacts.