Geochemical Modeling and Analysis of the Frac Water Used in the Hydraulic Fracturing of the Marcellus Formation, Pennsylvania

The hydraulic fracturing of the Marcellus Formation creates a byproduct known as frac water. Five frac water samples were collected in Bradford County, PA. Inorganic chemical analysis, field parameters analysis, alkalinity titrations, total dissolved solids(TDS), total suspended solids (TSS), biological oxygen demand (BOD), and chemical oxygen demand (COD) were conducted on each sample to characterize frac water. A database of frac water chemistry results from across the state of Pennsylvania from multiple sources was compiled in order to provide the public and research communitywith an accurate characterization of frac water. Four geochemical models were created to model the reactions between frac water and the Marcellus Formation, Purcell Limestone, and the oil field brines presumed present in the formations. The average concentrations of chloride and TDS in the five frac water samples were 1.1 �± 0.5 x 105 mg/L (5.5X average seawater) and 140,000 mg/L (4X average seawater). BOD values for frac water immediately upon flow back were over 10X greater than the BOD of typical wastewater, but decreased into the range of typical wastewater after a short period of time. The COD of frac water decreases dramatically with an increase in elapsed time from flow back, but remain considerably higher than typicalwastewater. Different alkalinity calculation methods produced a range of alkalinity values for frac water: this result is most likely due to high concentrations of aliphatic acid anions present in the samples. Laboratory analyses indicate that the frac watercomposition is quite variable depending on the companies from which the water was collected, the geology of the local area, and number of fracturing jobs in which the frac water was used, but will require more treatment than typical wastewater regardless of theprecise composition of each sample. The geochemical models created suggest that the presence of organic complexes in an oil field brine and Marcellus Formation aid in the dissolution of ions such as bariumand strontium into the solution. Although equilibration reactions between the Marcellus Formation and the slickwater account for some of the final frac water composition, the predominant control of frac water composition appears to be the ratio of the mixture between the oil field brine and slickwater. The high concentration of barium in the frac water is likely due to the abundance of barite nodules in the Purcell Limestone, and the lack of sulfate in the frac water samples is due to the reducing, anoxic conditions in the earth's subsurface that allow for the degassing of H2S(g).

OPTIMIZING A SHORT-END ELECTROPHORETICALLY MEDIATED MICRO-ANALYSIS (EMMA) ASSAY FOR CREATININE

In this work electrophoretically mediated micro-analysis (EMMA) is used in conjunction with short end injection to improve the in-capillary Jaffé assay for creatinine. Key advances over prior work include (i) using simulation to ensure intimate overlap of reagent plugs, (ii) using OH- to drive the reaction, (iii) using short-end injection to minimize analysis time and in-line product degradation. The potential-driven overlapping time with the EMMA approach, as well as the borate buffer background electrolyte (BGE) concentration and pH are optimized with the short end approach. The best conditions for short-end analyses would not have been predicted by the prior long end work, owing to a complex interplay of separation time and product degradation rates. Raw peak areas and flow-adjusted peak areas for the Jaffé reaction product (at 505 nm) are used to assess the sensitivity of the short-end EMMA approach. Optimal overlap conditions depend heavily on local conductivity differences within the reagent zone(s), as these differences cause dramatic voltage field differences, which effect reagent overlap dynamics. Simul 5.0, a dynamic simulation program for capillary electrophoresis (CE) systems, is used to understand the ionic boundaries and profiles that give rise to the experimentally obtained data for EMMA analysis. Overall, fast migration of hydroxide ions from the picrate zone makes difficult reagent overlap. In addition, the challenges associated with the simultaneous overlapping of three reagent zones are considered, and experimental results validate the predictions made by the simulation. With one set of “optimized” conditions including OH- (253 mM) as the third reagent zone the response was linear with creatinine concentration (R2 = 0.998) and reproducible over the clinically relevant range (0.08 to 0.1 mM) of standard creatinine concentrations. An LOD (S/N = 3) of 0.02 mM and LOQ (S/N=10) of 0.08 mM were determined. A significant improvement (43%) in assay sensitivity was obtained compared to prior work that considered only two reagents in the overlap.

Measurement Properties of the Short Multi-Dimensional Observation Scale for Elderly Subjects (MOSES)

This study evaluated the five-factor measurement model of the abbreviated Multidimensional Observation Scale for Elderly Subjects (MOSES), originally proposed by Pruchno, Kleban, and Resch in 1988. Modifications of the five-factor model were examined and evaluated with regard to their practical significance. A confirmatory second-order factor analysis was performed to examine whether the correlations among the first-order factors were adequately accounted for by a global dysfunction factor. Findings indicated that the proposed measurement model was replicated adequately. Although post hoc modifications resulted in significant improvements in overall model fit, the minor parameters had only a trivial influence on the major parameters of the baseline model. Results from the second-order factor analysis showed that a global dysfunc tion factor accounted adequately for the intercorrelations among the first-order factors.