A Model To Estimate Carbon Dioxide Injectivity and Storage Capacity for Geological Sequestration in Shale Gas Wells.

Recent studies suggest the possibility of CO2 sequestration in depleted shale gas formations, motivated by large storage capacity estimates in these formations. Questions remain regarding the dynamic response and practicality of injection of large amounts of CO2 into shale gas wells. A two-component (CO2 and CH4) model of gas flow in a shale gas formation including adsorption effects provides the basis to investigate the dynamics of CO2 injection. History-matching of gas production data allows for formation parameter estimation. Application to three shale gas-producing regions shows that CO2 can only be injected at low rates into individual wells and that individual well capacity is relatively small, despite significant capacity variation between shale plays. The estimated total capacity of an average Marcellus Shale well in Pennsylvania is 0.5 million metric tonnes (Mt) of CO2, compared with 0.15 Mt in an average Barnett Shale well. Applying the individual well estimates to the total number of existing and permitted planned wells (as of March, 2015) in each play yields a current estimated capacity of 7200-9600 Mt in the Marcellus Shale in Pennsylvania and 2100-3100 Mt in the Barnett Shale.

Direct measurements of methane emissions from abandoned oil and gas wells in Pennsylvania.

Abandoned oil and gas wells provide a potential pathway for subsurface migration and emissions of methane and other fluids to the atmosphere. Little is known about methane fluxes from the millions of abandoned wells that exist in the United States. Here, we report direct measurements of methane fluxes from abandoned oil and gas wells in Pennsylvania, using static flux chambers. A total of 42 and 52 direct measurements were made at wells and at locations near the wells ("controls") in forested, wetland, grassland, and river areas in July, August, October 2013 and January 2014, respectively. The mean methane flow rates at these well locations were 0.27 kg/d/well, and the mean methane flow rate at the control locations was 4.5 × 10(-6) kg/d/location. Three out of the 19 measured wells were high emitters that had methane flow rates that were three orders of magnitude larger than the median flow rate of 1.3 × 10(-3) kg/d/well. Assuming the mean flow rate found here is representative of all abandoned wells in Pennsylvania, we scaled the methane emissions to be 4-7% of estimated total anthropogenic methane emissions in Pennsylvania. The presence of ethane, propane, and n-butane, along with the methane isotopic composition, indicate that the emitted methane is predominantly of thermogenic origin. These measurements show that methane emissions from abandoned oil and gas wells can be significant. The research required to quantify these emissions nationally should be undertaken so they can be accurately described and included in greenhouse gas emissions inventories.

Novel apatite-based sorbent for defluoridation: synthesis and sorption characteristics of nano-micro-crystalline hydroxyapatite-coated-limestone.

Elevated levels of fluoride (F(-)) in groundwaters of granitic and basaltic terrains pose a major environmental problem and are affecting millions of people all over the world. Hydroxyapatite (HA) has been shown to be a strong sorbent for F(-); however, low permeability of synthetic HA results in poor sorption efficiency. Here we provide a novel method of synthesizing nano- to micrometer sized HA on the surfaces of granular limestone to improve the sorption efficiency of the HA-based filter. Our experiments with granular limestone (38-63, 125-500 µm) and dissolved PO4(3-) (0.5-5.3 mM) as a function of pH (6-8) and temperature (25-80 °C) indicated rapid formation of nano- to micrometer sized HA crystals on granular limestone with the maximum surface coverage at lower pH and in the presence of multiple additions of aqueous PO4(3-). The HA crystal morphology varied with the above variables. The sorption kinetics and magnitude of F(-) sorption by HA-coated-fine limestone are comparable to those of pure HA, and the F(-) levels dropped to below the World Health Organization's drinking water limit of 79 µM for F(-) concentrations commonly encountered in contaminated potable waters, suggesting that these materials could be used as effective filters. Fluorine XANES spectra of synthetic HA reacted with F(-) suggest that the mode of sorption is through the formation of fluoridated-HA or fluorapatite at low F(-) levels and fluorite at high F(-) loadings.