Kelvin B. Gregory

Transformations of Nanomaterials in the Environment

Increasing use of engineered nanomaterials with novel properties relative to their bulk counterparts has generated a need to define their behaviors and impacts in the environment. The high surface area to volume ratio of nanoparticles results in highly reactive and physiochemically dynamic materials in environmental media. Many transformations, e.g. reactions with biomacromolecules, redox reactions, aggregation, and dissolution, may occur in both environmental and biological systems. These transformations and others will alter the fate, transport, and toxicity of nanomaterials. The nature and extent of these transformations must be understood before significant progress can be made toward understanding the environmental risks posed by these materials.

Adsorbed polymer and NOM limits adhesion and toxicity of nano scale zerovalent iron to E. coli.

Nanoscale zerovalent iron (NZVI) is used for groundwater remediation. Freshly synthesized bare, i.e. uncoated NZVI is bactericidal at low mg/L concentration, but the impact of surface modifiers and aging (partial oxidation) on its bactericidal properties have not been determined. Here we assess the effect that adsorbed synthetic polymers and natural organic matter (NOM) and aging (partial oxidation) have on the bactericidal properties of NZVI to the gram-negative bacterium, Escherichia coli. Exposure to 100 mg/L of bare NZVI with 28% Fe(0) content resulted in a 2.2-log inactivation after 10 min and a 5.2-log inactivation after 60 min. Adsorbed poly(styrene sulfonate) (PSS), poly(aspartate) (PAP), or NOM on NZVI with the same Fe(0) content significantly decreased its toxicity, causing less than 0.2-log inactivation after 60 min. TEM images and heteroaggregation studies indicate that bare NZVI adheres significantly to cells and that the adsorbed polyelectrolyte or NOM prevents adhesion, thereby decreasing NZVI toxicity. The 1.8-log inactivation observed for bare NZVI with 7% Fe(0) content was lower than the 5.2-log inactivation using NZVI with 28% Fe(0) after 1 h; however, the minimum inhibitory concentration (MIC) after 24 h was 5 mg/L regardless of Fe(0) content. The MIC of PSS, PAP, and NOM coated NZVI were much higher: 500 mg/L, 100 mg/L, and 100 mg/L, respectively. But the MIC was much lower than the typical injection concentration used in remediation (10 g/L). Complete oxidation of Fe(0) in NZVI under aerobic conditions eliminated its bactericidal effects. This study indicates that polyelectrolyte coatings and NOM will mitigate the toxicity of NZVI for exposure concentrations below 0.1 to 0.5 g/L depending on the coating and that aged NZVI without Fe(0) is relatively benign to bacteria.

Sulfidation of Silver Nanoparticles Decreases Escherichia coli Growth Inhibition

Sulfidation of metallic nanoparticles such as silver nanoparticles (AgNPs) released to the environment may be an important detoxification mechanism. Two types of AgNPs-an engineered polydisperse and aggregated AgNP powder, and a laboratory-synthesized, relatively monodisperse AgNP aqueous dispersion-were studied. The particles were sulfidized to varying degrees and characterized to determine the effect of initial AgNP polydispersity and aggregation state on AgNP sulfidation, and then exposed to Escherichia coli to determine if the degree of sulfidation of pristine AgNPs affects growth inhibition of bacteria. The extent of sulfidation was found to depend on the HS(-)/Ag ratio. However, for the same reaction times, the more monodisperse particles were fully transformed to Ag(2)S, and the polydisperse, aggregated particles were not fully sulfidized, thus preserving the toxic potential of Ag(0) in the aggregates. A higher Ag(2)S:Ag(0) ratio in the sulfidized nanoparticles resulted in less growth inhibition of E. coli over 6 h of exposure. These results suggest that the initial properties of AgNPs can affect sulfidation products, which in turn affect microbial growth inhibition, and that these properties should be considered in assessing the environmental impact of AgNPs.

Spatial and Temporal Correlation of Water Quality Parameters of Produced Waters from Devonian-Age Shale following Hydraulic Fracturing

The exponential increase in fossil energy production from Devonian-age shale in the Northeastern United States has highlighted the management challenges for produced waters from hydraulically fractured wells. Confounding these challenges is a scant availability of critical water quality parameters for this wastewater. Chemical analyses of 160 flowback and produced water samples collected from hydraulically fractured Marcellus Shale gas wells in Pennsylvania were correlated with spatial and temporal information to reveal underlying trends. Chloride was used as a reference for the comparison as its concentration varies with time of contact with the shale. Most major cations (i.e., Ca, Mg, Sr) were well-correlated with chloride concentration while barium exhibited strong influence of geographic location (i.e., higher levels in the northeast than in southwest). Comparisons against brines from adjacent formations provide insight into the origin of salinity in produced waters from Marcellus Shale. Major cations exhibited variations that cannot be explained by simple dilution of existing formation brine with the fracturing fluid, especially during the early flowback water production when the composition of the fracturing fluid and solid-liquid interactions influence the quality of the produced water. Water quality analysis in this study may help guide water management strategies for development of unconventional gas resources.

Growth with high planktonic biomass in Shewanella oneidensis fuel cells

Shewanella oneidensis MR-1 grew for over 50 days in microbial fuel cells, incompletely oxidizing lactate to acetate with high recovery of the electrons derived from this reaction as electricity. Electricity was produced with lactate or hydrogen and current was comparable to that of electricigens which completely oxidize organic substrates. However, unlike fuel cells with previously described electricigens, in which cells are primarily attached to the anode, at least as many of the S. oneidensis cells were planktonic as were attached to the anode. These results demonstrate that S. oneidensis may conserve energy for growth with an electrode serving as an electron acceptor and suggest that multiple strategies for electron transfer to fuel cell anodes exist.

Impact of nanoscale zero valent iron on geochemistry and microbial populations in trichloroethylene contaminated aquifer materials.

Nanoscale zerovalent iron (NZVI) particles are a promising technology for reducing trichloroethylene (TCE) contamination in the subsurface. Prior to injecting large quantities of nanoparticles into the groundwater it is important to understand what impact the particles will have on the geochemistry and indigenous microbial communities. Microbial populations are important not only for nutrient cycling, but also for contaminant remediation and heavy metal immobilization. Microcosms were used to determine the effects of NZVI addition on three different aquifer materials from TCE contaminated sites in Alameda Point, CA, Mancelona, MI, and Parris Island, SC. The oxidation and reduction potential of the microcosms consistently decreased by more than 400 mV when NZVI was added at 1.5 g/L concentrations. Sulfate concentrations decreased in the two coastal aquifer materials, and methane was observed in the presence of NZVI in Alameda Point microcosms, but not in the other two materials. Denaturing gradient gel electrophoresis (DGGE) showed significant shifts in Eubacterial diversity just after the Fe(0) was exhausted, and quantitative polymerase chain reaction (qPCR) analyses showed increases of the dissimilatory sulfite reductase gene (dsrA) and Archaeal 16s rRNA genes, indicating that reducing conditions and hydrogen created by NZVI stimulate both sulfate reducer and methanogen populations. Adding NZVI had no deleterious effect on total bacterial abundance in the microcosms. NZVI with a biodegradable polyaspartate coating increased bacterial populations by an order of magnitude relative to controls. The lack of broad bactericidal effect, combined with the stimulatory effect of polyaspartate coatings, has positive implications for NZVI field applications.

Regional variation in water-related impacts of shale gas development and implications for emerging international plays.

The unconventional fossil fuel industry is expected to expand dramatically in coming decades as conventional reserves wane. Minimizing the environmental impacts of this energy transition requires a contextualized understanding of the unique regional issues that shale gas development poses. This manuscript highlights the variation in regional water issues associated with shale gas development in the U.S. and the approaches of various states in mitigating these impacts. The manuscript also explores opportunities for emerging international shale plays to leverage the diverse experiences of U.S. states in formulating development strategies that minimize water-related impacts within their environmental, cultural, and political ecosystem.

Microbial Community Changes in Hydraulic Fracturing Fluids and Produced Water from Shale Gas Extraction

Microbial communities associated with produced water from hydraulic fracturing are not well understood, and their deleterious activity can lead to significant increases in production costs and adverse environmental impacts. In this study, we compared the microbial ecology in prefracturing fluids (fracturing source water and fracturing fluid) and produced water at multiple time points from a natural gas well in southwestern Pennsylvania using 16S rRNA gene-based clone libraries, pyrosequencing, and quantitative PCR. The majority of the bacterial community in prefracturing fluids constituted aerobic species affiliated with the class Alphaproteobacteria. However, their relative abundance decreased in produced water with an increase in halotolerant, anaerobic/facultative anaerobic species affiliated with the classes Clostridia, Bacilli, Gammaproteobacteria, Epsilonproteobacteria, Bacteroidia, and Fusobacteria. Produced water collected at the last time point (day 187) consisted almost entirely of sequences similar to Clostridia and showed a decrease in bacterial abundance by 3 orders of magnitude compared to the prefracturing fluids and produced water samplesfrom earlier time points. Geochemical analysis showed that produced water contained higher concentrations of salts and total radioactivity compared to prefracturing fluids. This study provides evidence of long-term subsurface selection of the microbial community introduced through hydraulic fracturing, which may include significant implications for disinfection as well as reuse of produced water in future fracturing operations.

Microbial communities in flowback water impoundments from hydraulic fracturing for recovery of shale gas

Hydraulic fracturing for natural gas extraction from shale produces waste brine known as flowback that is impounded at the surface prior to reuse and/or disposal. During impoundment, microbial activity can alter the fate of metals including radionuclides, give rise to odorous compounds, and result in biocorrosion that complicates water and waste management and increases production costs. Here, we describe the microbial ecology at multiple depths of three flowback impoundments from the Marcellus shale that were managed differently. 16S rRNA gene clone libraries revealed that bacterial communities in the untreated and biocide-amended impoundments were depth dependent, diverse, and most similar to species within the taxa γ-proteobacteria, α-proteobacteria, δ-proteobacteria, Clostridia, Synergistetes, Thermotogae, Spirochetes, and Bacteroidetes. The bacterial community in the pretreated and aerated impoundment was uniform with depth, less diverse, and most similar to known iodide-oxidizing bacteria in the α-proteobacteria. Archaea were identified only in the untreated and biocide-amended impoundments and were affiliated to the Methanomicrobia class. This is the first study of microbial communities in flowback water impoundments from hydraulic fracturing. The findings expand our knowledge of microbial diversity of an emergent and unexplored environment and may guide the management of flowback impoundments.

Effect of bare and coated nanoscale zerovalent iron on tceA and vcrA gene expression in Dehalococcoides spp.

Nanoscale zerovalent iron (NZVI) can be used to dechlorinate trichloroethylene (TCE) in contaminated aquifers. Dehalococcoides spp. is the only microbial genus known to dechlorinate TCE to ethene as a respiratory process. However, little is known about how NZVI affects the expression of genes coding for reductive dechlorination. We examined a high-rate TCE-dechlorinating mixed culture which contains organisms similar to known Dehalococcoides to study the effects of NZVI on the expression of two model genes coding for reductive dehalogenases (tceA and vcrA). A novel pretreatment approach, relying on magnetic separation of NZVI prior to reverse transcription qPCR (to avoid RNA adsorption by NZVI), was developed and used with relative quantification (relative to 16S rRNA as endogenous housekeeping gene) to quantify reductive dehalogenase gene expression. Both tceA and vcrA were significantly down-regulated (97- and 137-fold, respectively) relative to baseline (time 0) conditions after 72-h exposure to chlorinated ethenes (0.12 ± 0.03 mg/L cis-DCE, 0.69 ± 0.11 mg/L t-DCE, and 0.54 ± 0.16 mg/L VC) and bare-NZVI (1 g-NZVI/L). However, coating NZVI with an olefin maleic acid copolymer (a common approach to enhance its mobility in aquifers) overcame this significant inhibitory effect, and both tceA and vcrA were up-regulated (3.0- and 3.5-fold, respectively) after 48-h exposure. Thus, NZVI coating might enhance the expression of dechlorinating genes and the concurrent or sequential participation of Dehalococcoides spp. in the remediation process.