Richard Hammack

Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ~375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (ε(Sr)(SW) = +13.8 to +41.6, where ε(Sr) (SW) is the deviation of the (87)Sr/(86)Sr ratio from that of seawater in parts per 10(4)); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

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.

Geochemical and isotopic evolution of water produced from Middle Devonian Marcellus shale gas wells, Appalachian basin, Pennsylvania

The number of Marcellus Shale gas wells drilled in the Appalachian basin has increased rapidly over the past decade, leading to increased interest in the highly saline water produced with the natural gas which must be recycled, treated, or injected into deep disposal wells. New geochemical and isotopic analyses of produced water for 3 time-series and 13 grab samples from Marcellus Shale gas wells in southwest and north central Pennsylvania (PA) are used to address the origin of the water and solutes produced over the long term (>12 months). The question of whether the produced water originated within the Marcellus Shale, or whether it may have been drawn from adjacent reservoirs via fractures is addressed using measurements of and activity. These parameters indicate that the water originated in the Marcellus Shale, and can be more broadly used to trace water of Marcellus Shale origin. During the first 1–2 weeks of production, rapid increases in salinity and positive shifts in values were observed in the produced water, followed by more gradual changes until a compositional plateau was reached within approximately 1 yr. The values and relationships between Na, Cl, and Br provide evidence that the water produced after compositional stabilization is natural formation water, the salinity for which originated primarily from evaporatively concentrated paleoseawater. The rapid transition from injected water to chemically and isotopically distinct water while of the injected water volume had been recovered, supports the hypothesis that significant volumes of injected water were removed from circulation by imbibition.

The functional potential of microbial communities in hydraulic fracturing source water and produced water from natural gas extraction characterized by metagenomic sequencing

Microbial activity in produced water from hydraulic fracturing operations can lead to undesired environmental impacts and increase gas production costs. However, the metabolic profile of these microbial communities is not well understood. Here, for the first time, we present results from a shotgun metagenome of microbial communities in both hydraulic fracturing source water and wastewater produced by hydraulic fracturing. Taxonomic analyses showed an increase in anaerobic/facultative anaerobic classes related to Clostridia, Gammaproteobacteria, Bacteroidia and Epsilonproteobacteria in produced water as compared to predominantly aerobic Alphaproteobacteria in the fracturing source water. The metabolic profile revealed a relative increase in genes responsible for carbohydrate metabolism, respiration, sporulation and dormancy, iron acquisition and metabolism, stress response and sulfur metabolism in the produced water samples. These results suggest that microbial communities in produced water have an increased genetic ability to handle stress, which has significant implications for produced water management, such as disinfection.

Isotope Approach to Assess Hydrologic Connections During Marcellus Shale Drilling

Water and gas samples were collected from (1) nine shallow groundwater aquifers overlying Marcellus Shale in north-central West Virginia before active shale gas drilling, (2) wells producing gas from Upper Devonian sands and Middle Devonian Marcellus Shale in southwestern Pennsylvania, (3) coal-mine water discharges in southwestern Pennsylvania, and (4) streams in southwestern Pennsylvania and north-central West Virginia. Our preliminary results demonstrate that the oxygen and hydrogen isotope composition of water, carbon isotope composition of dissolved inorganic carbon, and carbon and hydrogen isotope compositions of methane in Upper Devonian sands and Marcellus Shale are very different compared with shallow groundwater aquifers, coal-mine waters, and stream waters of the region. Therefore, spatiotemporal stable isotope monitoring of the different sources of water before, during, and after hydraulic fracturing can be used to identify migrations of fluids and gas from deep formations that are coincident with shale gas drilling.

Strontium Isotopes Test Long-Term Zonal Isolation of Injected and Marcellus Formation Water after Hydraulic Fracturing

One concern regarding unconventional hydrocarbon production from organic-rich shale is that hydraulic fracture stimulation could create pathways that allow injected fluids and deep brines from the target formation or adjacent units to migrate upward into shallow drinking water aquifers. This study presents Sr isotope and geochemical data from a well-constrained site in Greene County, Pennsylvania, in which samples were collected before and after hydraulic fracturing of the Middle Devonian Marcellus Shale. Results spanning a 15-month period indicated no significant migration of Marcellus-derived fluids into Upper Devonian/Lower Mississippian units located 900-1200 m above the lateral Marcellus boreholes or into groundwater sampled at a spring near the site. Monitoring the Sr isotope ratio of water from legacy oil and gas wells or drinking water wells can provide a sensitive early warning of upward brine migration for many years after well stimulation.

Fate of Radium in Marcellus Shale Flowback Water Impoundments and Assessment of Associated Health Risks

Natural gas extraction from Marcellus Shale generates large quantities of flowback water that contain high levels of salinity, heavy metals, and naturally occurring radioactive material (NORM). This water is typically stored in centralized storage impoundments or tanks prior to reuse, treatment or disposal. The fate of Ra-226, which is the dominant NORM component in flowback water, in three centralized storage impoundments in southwestern Pennsylvania was investigated during a 2.5-year period. Field sampling revealed that Ra-226 concentration in these storage facilities depends on the management strategy but is generally increasing during the reuse of flowback water for hydraulic fracturing. In addition, Ra-226 is enriched in the bottom solids (e.g., impoundment sludge), where it increased from less than 10 pCi/g for fresh sludge to several hundred pCi/g for aged sludge. A combination of sequential extraction procedure (SEP) and chemical composition analysis of impoundment sludge revealed that Barite is the main carrier of Ra-226 in the sludge. Toxicity characteristic leaching procedure (TCLP) (EPA Method 1311) was used to assess the leaching behavior of Ra-226 in the impoundment sludge and its implications for waste management strategies for this low-level radioactive solid waste. Radiation exposure for on-site workers calculated using the RESRAD model showed that the radiation dose equivalent for the baseline conditions was well below the NRC limit for the general public.

Analysis of Radium-226 in High Salinity Wastewater from Unconventional Gas Extraction by Inductively Coupled Plasma-Mass Spectrometry

Elevated concentration of naturally occurring radioactive material (NORM) in wastewater generated from Marcellus Shale gas extraction is of great concern due to potential environmental and public health impacts. Development of a rapid and robust method for analysis of Ra-226, which is the major NORM component in this water, is critical for the selection of appropriate management approaches to properly address regulatory and public concerns. Traditional methods for Ra-226 determination require long sample holding time or long detection time. A novel method combining Inductively Coupled Mass Spectrometry (ICP-MS) with solid-phase extraction (SPE) to separate and purify radium isotopes from the matrix elements in high salinity solutions is developed in this study. This method reduces analysis time while maintaining requisite precision and detection limit. Radium separation is accomplished using a combination of a strong-acid cation exchange resin to separate barium and radium from other ions in the solution and a strontium-specific resin to isolate radium from barium and obtain a sample suitable for analysis by ICP-MS. Method optimization achieved high radium recovery (101 ± 6% for standard mode and 97 ± 7% for collision mode) for synthetic Marcellus Shale wastewater (MSW) samples with total dissolved solids as high as 171,000 mg/L. Ra-226 concentration in actual MSW samples with TDS as high as 415,000 mg/L measured using ICP-MS matched very well with the results from gamma spectrometry. The Ra-226 analysis method developed in this study requires several hours for sample preparation and several minutes for analysis with the detection limit of 100 pCi/L with RSD of 45% (standard mode) and 67% (collision mode). The RSD decreased to below 15% when Ra-226 concentration increased over 500 pCi/L.

The removal of sulfate and metals from mine waters using bacterial sulfate reduction: Pilot plant results

A treatment process that bacterially converts sulfate into elemental sulfur via a hydrogen sulfide intermediate was demonstrated at pilot scale for the treatment of three mine waters that contained metals and sulfate. Ethanol served as the bacterial carbon and energy source. The mine waters were treated at rates that ranged from 50–150 L day−1. Contaminant concentrations up to 13 mg L−1 copper, 0.1 mg L−1 mercury, 0.04 mg L−1 cadmium, 3.5 mg L−1 zinc, 0.68 mg L−1 cobalt, 1.3 mg L−1 nickel, 49 mg L−1 iron, and 63 mg L−1 aluminum were removed to meet water quality effluent limits. Manganese removal was about 80% under normal operating conditions but increased to 96% when the process was optimized for manganese removal. The process was shown to be capable of decreasing sulfate concentrations from 1800 mg L−1 to less than 250 mg L−1, nitrate from 100 mg L−1 to less than 1 mg L−1, arsenic from 8 mg L−1 to less than 0.03 mg L−1, and calcium from 310 mg L−1 to less than 100 mg L−1. Acid mine waters were neutralized using bacterially-generated alkalinity; no external alkalinity source was needed.