Quantum-Mechanical Investigation of Large Water Clusters

The PM3 quantum-mechanical method has been used to study large water clusters ranging from 8 to 42 water molecules. These large clusters are built from smaller building blocks. The building blocks include cyclic tetramers, pentamers, octamers, and a pentagonal dodecahedron cage. The correlations between the strain energy resulting from bending of the hydrogen bonds formed by different cluster motifs and the number of waters involved in the cluster are discussed. The PM3 results are compared with TIP4P potential and ab initio results. The number of net hydrogen bonds per water increases with the cluster size. This places a limit on the size of clusters that would fit the Benson model of liquid water. Many of the 20-mer clusters fit the Benson model well. Calculations of the ion cluster (H20)4o(H30+)2 reveal that the m/e ratio obtainable by mass spectrometry experiments can uniquely indicate the conformation of the 20 water pentagonal dodecahedron cage present in the larger clusters.

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).