Geology topics

C.S. Kirby

Publications and source records attributed to C.S. Kirby.

3 recordsLinked to original sources

USGS2011

Radium content of oil- and gas-field produced waters in the northern Appalachian Basin (USA): Summary and discussion of data

Radium activity data for waters co-produced with oil and gas in New York and Pennsylvania have been compiled from publicly available sources and are presented together with new data for six wells, including one time series. When available, total dissolved solids (TDS), and gross alpha and gross beta particle activities also were compiled. Data from the 1990s and earlier are from sandstone and limestone oil/gas reservoirs of Cambrian-Mississippian age; however, the recent data are almost exclusively from the Middle Devonian Marcellus Shale. The Marcellus Shale represents a vast resource of natural gas the size and significance of which have only recently been recognized. Exploitation of the Marcellus involves hydraulic fracturing of the shale to release tightly held gas. Analyses of the water produced with the gas commonly show elevated levels of salinity and radium. Similarities and differences in radium data from reservoirs of different ages and lithologies are discussed. The range of radium activities for samples from the Marcellus Shale (less than detection to 18,000 picocuries per liter (pCi/L)) overlaps the range for non-Marcellus reservoirs (less than detection to 6,700 pCi/L), and the median values are 2,460 pCi/L and 734 pCi/L, respectively. A positive correlation between the logs of TDS and radium activity can be demonstrated for the entire dataset, and controlling for this TDS dependence, Marcellus shale produced water samples contain statistically more radium than non-Marcellus samples. The radium isotopic ratio, Ra-228/Ra-226, in samples from the Marcellus Shale is generally less than 0.3, distinctly lower than the median values from other reservoirs. This ratio may serve as an indicator of the provenance or reservoir source of radium in samples of uncertain origin.

Pennsylvania;New York↗

USGS2005

Net alkalinity and net acidity 1: Theoretical considerations

Net acidity and net alkalinity are widely used, poorly defined, and commonly misunderstood parameters for the characterization of mine drainage. The authors explain theoretical expressions of 3 types of alkalinity (caustic, phenolphthalein, and total) and acidity (mineral, CO2, and total). Except for rarely-invoked negative alkalinity, theoretically defined total alkalinity is closely analogous to measured alkalinity and presents few practical interpretation problems. Theoretically defined "CO 2-acidity" is closely related to most standard titration methods with an endpoint pH of 8.3 used for determining acidity in mine drainage, but it is unfortunately named because CO2 is intentionally driven off during titration of mine-drainage samples. Using the proton condition/mass- action approach and employing graphs to illustrate speciation with changes in pH, the authors explore the concept of principal components and how to assign acidity contributions to aqueous species commonly present in mine drainage. Acidity is defined in mine drainage based on aqueous speciation at the sample pH and on the capacity of these species to undergo hydrolysis to pH 8.3. Application of this definition shows that the computed acidity in mg L -1 as CaCO3 (based on pH and analytical concentrations of dissolved FeII, FeIII, Mn, and Al in mg L -1):aciditycalculated=50{1000(10-pH)+[2(FeII)+3(FeIII)]/56+2(Mn)/ 55+3(Al)/27}underestimates contributions from HSO4- and H+, but overestimates the acidity due to Fe3+ and Al3+. However, these errors tend to approximately cancel each other. It is demonstrated that "net alkalinity" is a valid mathematical construction based on theoretical definitions of alkalinity and acidity. Further, it is shown that, for most mine-drainage solutions, a useful net alkalinity value can be derived from: (1) alkalinity and acidity values based on aqueous speciation, (2) measured alkalinity minus calculated acidity, or (3) taking the negative of the value obtained in a standard method "hot peroxide" acidity titration, provided that labs report negative values. The authors recommend the third approach; i.e., net alkalinity = -Hot Acidity. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2005

Net alkalinity and net acidity 2: Practical considerations

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples. A meaningful "net" acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinitymeasured - Hot Aciditymeasured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H+ acidity and is not recommended. The use of net alkalinity = -Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinitymeasured - Aciditycalculated) is recommended with some cautions. ?? 2005 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗