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).

Provenance signature of a forearc basin modified by spreading ridge subduction: Detrital zircon geochronology and detrital modes from the Paleogene Arkose Ridge Formation, southern Alaska

Upper Paleocene–Eocene boulder conglomerate, cross-stratified sandstone, and laminated carbonaceous mudstone of the Arkose Ridge Formation exposed in the southern Talkeetna Mountains record fluvial-lacustrine deposition proximal to the volcanic arc in a forearc basin modified by Paleogene spreading ridge subduction beneath southern Alaska. U-Pb ages of detrital zircon grains and modal analyses were obtained from stratigraphic sections spanning the 2,000 m thick Arkose Ridge Formation in order to constrain the lithology, age, and location of sediment sources that provided detritus. Detrital modes from 24 conglomerate beds and 54 sandstone thin sections aredominated by plutonic and volcanic clasts and plagioclase feldspar with minor quartz, schist, hornblende, argillite, and metabasalt. Westernmost sandstone and conglomerate strata contain <5% volcanic clasts whereas easternmost sandstone and conglomerate strata contain 40 to >80% volcanic clasts. Temporally, eastern sandstones andconglomerates exhibit an upsection increase in volcanic detritus from <40 to >80% volcanic clasts. U-Pb ages from >1400 detrital zircons in 15 sandstone samples reveal three main populations: late Paleocene–Eocene (60-48 Ma; 16% of all grains), Late Cretaceous–early Paleocene (85–60 Ma; 62%) and Jurassic–Early Cretaceous (200–100 Ma; 12%). A plot of U/Th vs U-Pb ages shows that >97% of zircons are <200 Ma and>99% of zircons have <10 U/Th ratios, consistent with mainly igneous source terranes. Strata show increased enrichment in late Paleocene–Eocene detrital zircons from <2% in the west to >25% in the east. In eastern sections, this younger age population increases temporally from 0% in the lower 50 m of the section to >40% in samples collected >740 m above the base. Integration of the compositional and detrital geochronologic data suggests: (1) Detritus was eroded mainly from igneous sources exposed directly north of the Arkose Ridge Formation strata, mainly Jurassic–Paleocene plutons and Paleocene–Eocenevolcanic centers. Subordinate metamorphic detritus was eroded from western Mesozoic low-grade metamorphic sources. Subordinate sedimentary detritus was eroded from eastern Mesozoic sedimentary sources. (2) Eastern deposystems received higher proportions of juvenile volcanic detritus through time, consistent with construction of adjacent slab-window volcanic centers during Arkose Ridge Formation deposition. (3)Western deposystems transported detritus from Jurassic–Paleocene arc plutons that flank the northwestern basin margin. (4) Metasedimentary strata of the Chugach accretionaryprism, exposed 20-50 km south of the Arkose Ridge Formation, did not contribute abundant detritus. Conventional provenance models predict reduced input of volcanic detritus to forearc basins during exhumation of the volcanic edifice and increasing exposure ofsubvolcanic plutons (Dickinson, 1995; Ingersoll and Eastmond, 2007). In the forearc strata of these conventional models, sandstone modal analyses record progressive increases upsection in quartz and feldspar concomitant with decreases in lithic grains, mainly volcanic lithics. Additionally, as the arc massif denudes through time, theyoungest detrital U-Pb zircon age populations become significantly older than the age of forearc deposition as the arc migrates inboard or ceases magmatism. Westernmost strata of the Arkose Ridge Formation are consistent with this conventional model. However, easternmost strata of the Arkose Ridge Formation contain sandstone modes that record an upsection increase in lithic grains accompanied by a decrease in quartz and feldspar, and detrital zircon age populations that closely match the age of deposition. This deviation from the conventional model is due to the proximity of the easternmost strata to adjacent juvenile volcanic rocks emplaced by slab-window volcanic processes. Provenance data from the Arkose Ridge Formation show that forearc basins modified by spreading ridge subduction may record upsection increases in non-arc, syndepositional volcanic detritusdue to contemporaneous accumulation of thick volcanic sequences at slab-window volcanic centers. This change may occur locally at the same time that other regions of the forearc continue to receive increasing amounts of plutonic detritus as the remnant arc denudes, resulting in complex lateral variations in forearc basin petrofacies and chronofacies.

Hydration of the Sulfuric Acid−Methylamine Complex and Implications for Aerosol Formation

The binary H2SO4−H2O nucleation is one of the most important pathways by which aerosols form in the atmosphere, and the presence of ternary species like amines increases aerosol formation rates. In this study, we focus on the hydration of a ternary system of sulfuric acid (H2SO4), methylamine (NH2CH3), and up to six waters to evaluate its implications for aerosol formation. By combining molecular dynamics (MD) sampling with high-level ab initio calculations, we determine the thermodynamics of forming H2SO4(NH2CH3)(H2O)n, where n = 0−6. Because it is a strong acid−base system, H2SO4−NH2CH3 quickly forms a tightly bound HSO4−−NH3CH3+ complex that condenses water more readily than H2SO4 alone. The electronic binding energy of H2SO4−NH2CH3 is −21.8 kcal mol−1 compared with −16.8 kcal mol−1 for H2SO4−NH3 and −12.8 kcal mol−1 for H2SO4−H2O. Adding one to two water molecules to the H2SO4−NH2CH3 complex is more favorable than adding to H2SO4 alone, yet there is no systematic difference for n ≥ 3. However, the average number of water molecules around H2SO4−NH2CH3 is consistently higher than that of H2SO4, and it is fairly independent of temperature and relative humidity.

Hydration of the Sulfuric Acid-Methylamine Complex and Implications for Aerosol Formation

The binary H2SO4-H2O nucleation is one of the most important pathways by which aerosols form in the atmosphere, and the presence of ternary species like amines increases aerosol formation rates. In this study, we focus on the hydration of a ternary system of sulfuric acid (H2SO4), methylamine (NH2CH3), and up to six waters to evaluate its implications for aerosol formation. By combining molecular dynamics (MD) sampling with high-level ab initio calculations, we determine the thermodynamics of forming H2SO4(NH2CH3)(H2O)n, where n = 0-6. Because it is a strong acid-base system, H2SO4-NH2CH3 quickly forms a tightly bound HSO4(-)-NH3CH3(+) complex that condenses water more readily than H2SO4 alone. The electronic binding energy of H2SO4-NH2CH3 is -21.8 kcal mol(-1) compared with -16.8 kcal mol(-1) for H2SO4-NH3 and -12.8 kcal mol(-1) for H2SO4-H2O. Adding one to two water molecules to the H2SO4-NH2CH3 complex is more favorable than adding to H2SO4 alone, yet there is no systematic difference for n ≥ 3. However, the average number of water molecules around H2SO4-NH2CH3 is consistently higher than that of H2SO4, and it is fairly independent of temperature and relative humidity.

Paleoenvironment and Paleoecology of a Late Paleocene High-Latitude Terrestrial Succession, Arkose Ridge Formation at Box Canyon, Southern Talkeetna Mountains, Alaska

Paleogene sedimentary rocks of the Arkose Ridge Formation (Talkeetna Mountains, Alaska) preserve a record of a fluvial-lacustrine depositional environment and its forested ecosystem in an active basin among the convergent margin tectonic processes that shaped southern Alaska. An -800 m measured succession at Box Canyon indicates braid-plain deposition with predominantly gravelly deposits low in the exposure to sandy and muddy facies associations below an overlying lava flow sequence. U-Pb geochronology on zircons from a tuff and a sandstone within the measured section, as well as an Ar/Ar date from the overlying lava constrain the age of the sedimentary succession to between similar to 59 Ma and 48 Ma Fossil plant remains occur throughout the Arkose Ridge Formation as poorly-preserved coalified woody debris and fragmentary leaf impressions. At Box Canyon, however, a thin la-custrine depositional lens of rhythmically laminated mudrocks yielded fish fossils and a well-preserved floral assemblage including foliage and reproductive organs representing conifers, sphenopsids, monocots, and dicots. Leaf physiognomic methods to estimate paleoclimate were applied to the dicot leaf collection and indicate warm temperate paleotemperatures (-11-15 +/- -4 degrees C MAT) and elevated paleoprecipitation (-120 cm/yr MAP) estimates as compared to modem conditions; results that are parallel with previously published estimates from the partly coeval Chickaloon Formation deposited in more distal depositional environments in the same basin. The low abundance of leaf herbivory in the Box Canyon dicot assemblage (-9% of leaves damaged) is also similar to the results from assemblages in the meander-plain depositional systems of the Chickaloon. This new suite of data informs models of the tectonostratigraphic evolution of southern Alaska and the developing understanding of terrestrial paleoecology and paleoclimate at high latitudes during the Late Paleocene-Early Eocene greenhouse climate phase. (c) 2014 Elsevier B.V. All rights reserved.