Dustin L. McIntyre

Alterations of Fractures in Carbonate Rocks by CO2-Acidified Brines

Fractures in geological formations may enable migration of environmentally relevant fluids, as in leakage of CO2 through caprocks in geologic carbon sequestration. We investigated geochemically induced alterations of fracture geometry in Indiana Limestone specimens. Experiments were the first of their kind, with periodic high-resolution imaging using X-ray computed tomography (xCT) scanning while maintaining high pore pressure (100 bar). We studied two CO2-acidified brines having the same pH (3.3) and comparable thermodynamic disequilibrium but different equilibrated pressures of CO2 (PCO2 values of 12 and 77 bar). High-PCO2 brine has a faster calcite dissolution kinetic rate because of the accelerating effect of carbonic acid. Contrary to expectations, dissolution extents were comparable in the two experiments. However, progressive xCT images revealed extensive channelization for high PCO2, explained by strong positive feedback between ongoing flow and reaction. The pronounced channel increasingly directed flow to a small region of the fracture, which explains why the overall dissolution was lower than expected. Despite this, flow simulations revealed large increases in permeability in the high-PCO2 experiment. This study shows that the permeability evolution of dissolving fractures will be larger for faster-reacting fluids. The overall mechanism is not because more rock dissolves, as would be commonly assumed, but because of accelerated fracture channelization.

Application of laser-induced breakdown spectroscopy for total carbon quantification in soil samples

The increase of greenhouse gas (i.e., CO(2)) levels in the atmosphere has caused noticeable climate change. Many nations are currently looking into methods of permanent underground storage for CO(2) in an attempt to mitigate this problem. The goal of this work is to develop a process for studying the total carbon content in soils before, during, and after CO(2) injection to ensure that no leakage is occurring or to determine how much is leaking if it is occurring and what effect it will have on the ecosystem between the injection formation and the atmosphere. In this study, we quantitatively determine the total carbon concentration in soil using laser-induced breakdown spectroscopy (LIBS). A soil sample from Starkville, Mississippi, USA was mixed with different amounts of carbon powder, which was used as a calibration for additional carbon in soil. Test samples were prepared by adding different but known amounts of carbon powder to a soil sample and then mixing with polyvinyl alcohol binder before being pressed into pellets. LIBS spectra of the test samples were collected and analyzed to obtain optimized conditions for the measurement of total carbon in soil with LIBS. The total carbon content in the samples was also measured by a carbon analyzer, and the data (average of triplicates) were used as a reference in developing calibration curves for a modified version of the single linear regression model and the multiple linear regression model. The calibration data were then used to determine the total carbon concentration of an unknown sample. This work is intended to be used in the initial development of a miniaturized, field-portable LIBS analyzer for CO(2) leak detection.

Lean-Burn Stationary Natural Gas Reciprocating Engine Operation with a Prototype Miniature Diode Side Pumped Passively Q-switched Laser Spark Plug

To meet the ignition system needs of large bore lean burn stationary natural gas engines a laser diode side pumped passively Q-switched laser igniter was developed and used to ignite lean mixtures in a single cylinder research engine. The laser design was produced from previous work. The in-cylinder conditions and exhaust emissions produced by the miniaturized laser were compared to that produced by a laboratory scale commercial laser system used in prior engine testing. The miniaturized laser design as well as the combustion and emissions data for both laser systems was compared and discussed. It was determined that the two laser systems produced virtually identical combustion and emissions data.

Laser Spark Ignition: Laser Development and Engine Testing

Evermore demanding market and legislative pressures require stationary lean-burn natural gas engines to operate at higher efficiencies and reduced levels of emissions. Higher in-cylinder pressures and leaner air/fuel ratios are required in order to meet these demands. Contemporary ignition systems, more specifically spark plug performance and durability, suffer as a result of the increase in spark energy required to maintain suitable engine operation under these conditions. This paper presents a discussion of the need for an improved ignition source for advanced stationary natural gas engines and introduces laser spark ignition as a potential solution to that need. Recent laser spark ignition engine testing with natural gas fuel including NOx mapping is discussed. A prototype laser system in constructed and tested and the results are discussed and solutions provided for improving the laser system output pulse energy and pulse characteristics.Copyright

Lean-Burn Stationary Natural Gas Engine Operation With a Prototype Laser Spark Plug

An end pumped passively Q-switched laser igniter was developed to meet the ignition system needs of large bore lean burn stationary natural gas engines. The laser spark plug used an optical fiber coupled diode pump source to axially pump a passively Q-switched Nd:YAG laser and transmit the laser pulse through a custom designed lens. The optical fiber coupled pump source permits the excitation energy to be transmitted to the spark plug at relatively low optical power, less than 250 W. The Q-switched laser then generates as much as 8 mJ of light in 2.5 ns, which is focused through an asymmetric biconvex lens to create a laser spark from a focused intensity of approximately 225 GW/cm 2 . A single cylinder engine fueled with either natural gas only or hydrogen augmented natural gas was operated with the laser spark plug for approximately 10 h in tests spanning 4 days. The tests were conducted with fixed engine speed, fixed boost pressure, no exhaust gas recirculation, and laser spark timing advance set at maximum brake torque timing. Engine operational and emissions data were collected and analyzed.

Laser Spark Ignition of a Blended Hydrogen-Natural Gas Fueled Single Cylinder Engine

Charge dilution, due to the reduced combustion temperatures that it brings about, has long been proven as effective means of reducing Nitrogen Oxides (NOx ) emissions in reciprocating engines. The extent of this dilution is practically bounded on the lean side of stoichiometric conditions by engine misfire or the point at which the combustion process is no longer sufficiently reliable to sustain engine operation within some specified limit. Extending this misfire limit of an engine becomes a worth while goal as it brings about further reductions in NOx emissions. Much work has been dedicated to reaching this end and several techniques have proven viable in natural gas fueled engines. This work explores potential synergies between two proven techniques for NOx reductions in lean-burn natural gas fueled engines, hydrogen enrichment of the natural gas fuel and application of laser spark ignition. Independently both techniques have been shown to provide significant NOx emissions reductions through lean limit extension in spark ignited gaseous fueled reciprocating engines [1–11, 13–15]. Here hydrogen is blended with natural gas at five different levels ranging from 0% to 40% by volume in a single cylinder engine. The mixtures are fired using a conventional spark plug based ignition system and then again with an open beam path laser induced breakdown spark ignition system. NOx emissions measurements were made at different levels including misfire conditions for each level of hydrogen enrichment with both ignition systems. Data are presented and the emissions and engine performance of two configurations are compared to determine realizable benefits that arise from combining the two techniques.Copyright

Effect of sodium chloride concentration on elemental analysis of brines by laser-induced breakdown spectroscopy (LIBS).

Leakage of injected carbon dioxide (CO2) or resident fluids, such as brine, is a major concern associated with the injection of large volumes of CO2 into deep saline formations. Migration of brine could contaminate drinking water resources by increasing their salinity or endanger vegetation and animal life as well as human health. The main objective of this study was to investigate the effect of sodium chloride (NaCl) concentration on the detection of calcium and potassium in brine samples using laser-induced breakdown spectroscopy (LIBS). The ultimate goals were to determine the suitability of the LIBS technique for in situ measurements of metal ion concentrations in NaCl-rich solution and to develop a chemical sensor that can provide the early detection of brine intrusion into formations used for domestic or agricultural water production. Several brine samples of NaCl–CaCl2 and NaCl–KCl were prepared at NaCl concentrations between 0.0 and 3.0 M. The effect of NaCl concentration on the signal-to-background ratio (SBR) and signal-to-noise ratio (SNR) for calcium (422.67 nm) and potassium (769.49 nm) emission lines was evaluated. Results show that, for a delay time of 300 ns and a gate width of 3 μs, the presence of and changes in NaCl concentration significantly affect the SBR and SNR for both emission lines. An increase in NaCl concentration from 0.0 to 3.0 M produced an increase in the SNR, whereas the SBR dropped continuously. The detection limits obtained for both elements were in the milligrams per liter range, suggesting that a NaCl-rich solution does not severely limit the ability of LIBS to detect trace amount of metal ions.

Laser-Induced Breakdown Spectroscopy (LIBS) of a High-Pressure CO2–Water Mixture: Application to Carbon Sequestration

Geologic carbon storage in deep saline aquifers is considered a feasible and possible approach of mitigating the problem of increasing greenhouse gas emissions. However, there are latent risks in which carbon dioxide (CO2) could migrate from the deep saline formations to shallower aquifers. In the event of a significant CO2 leakage to an underground source of drinking water, CO2 will dissolve in the water, thereby increasing its acidity, which could potentially enhance the solubility of various aquifer constituents, including hazardous compounds, subsequently compromising groundwater quality due to increased concentration of aqueous metals. In this paper we explore the possibility of detecting such leakage by the use of laser-induced breakdown spectroscopy (LIBS). The experiments were conducted in calcium chloride solution at three pressures of 10, 50, and 120 bar. To evaluate the direct effect of elevated CO2 on the intensity of calcium emission lines (422.67 and 393.37 nm), we also performed experiments with pure nitrogen (N2) gas, offering large water solubility contrast. We found that when performed in presence of CO2, LIBS showed only a modest decrease in Ca emission intensity from 10 to 120 bar compared to N2. These results indicate that LIBS is a viable tool for measuring brine/water contents in high-pressure CO2 environment and can be applied for monitoring CO2 leakage and displaced brine migration.

Determination of elemental impurities in plastic calibration standards using laser-induced breakdown spectroscopy

Dual-energy computed tomography (CT) scanning is a rapidly emerging imaging technique employed in nondestructive evaluation of various materials. CT has been used for characterizing rocks and visualizing multiphase flow through rocks for over 25 years. The most common technique for dual-energy CT scanning relies on homogeneous calibration standards to produce the most accurate decoupled data. However, the use of calibration standards with impurities increases the probability of error in the reconstructed data and results in poor rock characterization. Laser-induced breakdown spectroscopy was used to determine impurity concentration in a set of commercially purchased calibration standards used in dual-energy scanning for material identification with coal samples. Two calibration models were developed by using univariate calibration with the internal ratio method and multiple linear regression. Seven elements (Al, Fe, Mg, Na, Ni, Sr, and Ti) were examined in five different samples containing varying amounts of each ion to compare calibration from univariate data analysis and from multivariate data analysis. The contaminant concentrations were also measured by a commercially available inductively coupled plasma optical emission spectroscopy instrument, and the data were used as a reference in developing calibration curves for a modified version of the single linear regression model and the multiple linear regression model.

Determination of Rare Earth Elements in Geological Samples Using Laser-Induced Breakdown Spectroscopy (LIBS):

Laser-induced breakdown spectroscopy (LIBS) was used to detect rare earth elements (REEs) in natural geological samples. Low and high intensity emission lines of Ce, La, Nd, Y, Pr, Sm, Eu, Gd, and Dy were identified in the spectra recorded from the samples to claim the presence of these REEs. Multivariate analysis was executed by developing partial least squares regression (PLS-R) models for the quantification of Ce, La, and Nd. Analysis of unknown samples indicated that the prediction results of these samples were found comparable to those obtained by inductively coupled plasma mass spectrometry analysis. Data support that LIBS has potential to quantify REEs in geological minerals/ores.