Geology topics

Nicholas J. Geboy

Publications and source records attributed to Nicholas J. Geboy.

13 recordsLinked to original sources

USGS2018

Cadmium isotope fractionation during coal combustion: Insights from two U.S. coal-fired power plants

Coal combustion, one of the principal energy sources of electricity in the United States, produces over 100 million tons of coal combustion products (CCPs) per year in the U.S. The reuse and disposal of CCPs has the potential to release toxic trace elements, including cadmium (Cd), into the environment. In this study, we investigated CCPs, including bottom ash (BA), economizer fly ash (EFA), and fly ash (FA), as well as feed coal (FC) and pulverized coal (PC) collected from two U.S. coal-fired power plants in New Mexico and Ohio with different coal supplies. The New Mexico plant uses high volatile C bituminous, low-sulfur coals mined from the San Juan Basin (Cretaceous Fruitland Formation) and the Ohio plant uses high volatile A bituminous, high-sulfur central Appalachian Basin coals (Upper Pennsylvanian Monongahela Formation). Mineralogical and elemental analysis showed that these CCP samples consist of ∼70% amorphous Al-Si-rich glasses and ∼30% mineral phases of quartz (SiO 2 ) and mullite (Ai 6 Si 2 O 13 ). The Cd isotope compositions (δ 114 Cd, normalized to NIST Cd standard 3108) of FA and EFA samples (ranging from −0.51 to +0.47‰) are distinctively heavier than those of BA samples (−0.75 to −0.52‰) in both power plants. We interpret this Cd isotope difference as a result of Cd condensation from the gas phase during flue gas cooling, instead of evaporation of Cd phase during coal combustion. Cd condensation is the main process to generate the isotopically heavy Cd signatures that preferentially partition on the fine FA particles. We also investigated Cd isotope compositions in different leachate products from a series of batch-leaching experiments with these CCPs, using diluted acetic acid, hydroxyl ammonium chloride, hydrogen peroxide followed by ammonium acetate, and 5% nitric acid, as a possible means to identify CCP-released Cd in the environment. Unusually and significantly heavier Cd isotope compositions were observed in each leachate of FA samples (+1.10 to +7.09‰), which fall far outside from the range of Cd isotope ratios observed in natural soils and rocks, but less so for the EFA samples (−0.43 to +1.18‰). Such an observation is consistent with the interpretation that isotopically heavy Cd preferentially partitions on the fine FA particles after coal combustion and is readily to be released during these leaching experiments. This study demonstrates that high-temperature coal combustion can lead to a very large degree of fractionation of Cd isotopes that can be used as a unique tracer for identifying anthropogenic metal inputs in the environment. The major Cd isotope fractionation process occurs as the Cd gas phase condenses on fine FA particles during the flue gas cooling stage after coal combustion.

New Mexico, Ohio↗

USGS2018

Gas emissions, tars, and secondary minerals at the Ruth Mullins and Tiptop coal mine fires

Both the Tiptop and Ruth Mullins coal fires, Kentucky, were reinvestigated in 2009 and 2010. The Tiptop fire was not as active in 2009 and may have been on the path to burning out at the time of the 2009 visit. The Ruth Mullins coal mine fire, Perry County, Kentucky, has been the subject of several field investigations, including November 2009–February 2010 investigations in which we measured gas emissions, collected minerals and tars, and characterized the nature of the fire. Vents exhibiting the greatest gas flux (>100,000 mg/s/m 2 ) are those with the largest amount of condensate minerals and tars. Vents with moderate gas flux (10,000–100,000 mg/s/m 2 ) are less likely to contain condensate minerals, but are collocated with tars, and vents with the lowest flux (<10,000 mg/s/m 2 ) generally lack both minerals and tars. Aliphatic hydrocarbons present in the gases include C1-C9 compounds, and aromatics include BTEX compounds. Diffuse-CO 2 emissions are concentrated along the fracture zones overlying abandoned mine works. The area of peak diffuse flux corresponds to the trend of the collapsed portal that forms vent 5. The greatest vent emissions were also recorded at vent 5. The snow-melt zone mapped in January 2010 overlies the areas of peak diffuse-CO 2 emissions measured in November; together they delineate the zone of active combustion. Comparison of greenhouse gas emissions from the two sources shows that vent emissions exceed diffuse emissions. The highly fractured, quartz-cemented roof rock funnels the majority of emissions toward the vents. Significant decreases are seen in estimates of yearly greenhouse emissions based on data gathered from November 2009 to February 2010, with estimates from November significantly exceeding any previously published estimates. For example, September 2009 estimates from vent 3 alone indicated that 19 ± 7.5 T CO 2 /yr were emitted while the November 2009 estimates were 1800 ± 690 T/yr. Barometric pressure was lower in November than September. This implies that there are many factors influencing the seasonal variations in fire emissions and that more frequent monitoring will be necessary to derive accurate estimates of coal fires' contribution to the carbon budget.

Kentucky↗

USGS2017

Mercury and trace element distribution in density separates of a South African Highveld (#4) coal: Implications for mercury reduction and preparation of export coal

Eight density separates of Permian Highveld (#4) coal were investigated for partitioning of Hg and trace elements. The separates include float fractions obtained in heavy media having densities of 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 g/cm 3 , and the sink fraction for 2.0 g/cm 3 . Bulk analysis of the separates shows strong (R 2 ≥ 0.80) positive correlations between pyritic sulfur and mercury, and between ash yield and both pyritic sulfur and mercury. Laser ablation (LA) ICP-MS analysis of individual pyrite grains in the separates confirms association of Hg and As with pyrite as indicated by bulk analysis. Other elements detected in pyrite by LA-ICP-MS include Mn, Co, Ni, Tl, and Pb. Results for the separates allow prediction of Hg, trace elements, and ash yields expected in specific South African coal products. These range from 0.06 ppm Hg and an ash yield of 11.5% ash for the export fraction to 0.47 ppm Hg and an ash yield of 60.9% for the discard (stone) fraction (dry basis). Results show pronounced differences expected between coal used for domestic power generation and coal which is exported.

International Journal of Coal Geology↗

USGS2016

Radiometric dating of marine-influenced coal using Re–Os geochronology

Coal deposits are integral to understanding the structural evolution and thermal history of sedimentary basins and correlating contemporeous estuarine and fluvial delatic strata with marine sections. While marine shales may readily lend themselves to Re–Os dating due to the dominance of hydrogenous Re and Os, the lack of a chronometer for near-shore sedimentary environments hampers basinwide correlations in absolute time. Here, we employ the Re–Os geochronometer, along with total organic carbon (TOC) and Rock–Eval data, to determine the timing and conditions of a marine incursion at the top of the Matewan coal bed, Kanawha Formation, Pottsville Group, West Virginia, USA. The observed range for hydrogen index (HI: 267–290 mg hydrocarbon/gram total organic carbon) for these coal samples suggests dominance of aliphatic hydrocarbons with low carbon (<C 19 ) chain length. Average Re ( 107.6±16.4 ng/g ) and Os ( 0.52±0.09 ng/g ) concentrations of the marine-influenced Matewan coal are higher by few orders of magnitude than published data for terrestrial coal. A Re–Os isochron for the Matewan coal provides an age of 325±14 Ma (Model 3; MSWD = 12; n=19 ; 2 σ ). This is the first Re–Os age derived from coal samples; the age overlaps a new composite Re–Os age of 317±2 Ma for the immediately overlying Betsie Shale Member. External precision for replicate Os analyses carried out for several Matewan coal samples shows a positive correlation with their HI. The HI, which is low in terrestrial organic matter, reflects the degree of marine influence. Thus, samples with the most profound marine influence also have the best analytical reproducibility. Equilibration of Os isotopes with seawater under marine conditions overwhelms variability inherited from terrestrial plant debris, decreasing scatter on the isochron. The 187 Re/ 188 Os ratios of the Matewan coal (&sim;3300–5135) are higher than most of those previously published for Phanerozoic black shale (mostly <2000). Mass balance calculations based on Re/TOC and Os/TOC ratios for the Matewan coal indicate that both Re and Os are primarily marine in origin, and their high 187 Re/ 188 Os ratios confirm efficient removal of both elements from a sulfidic water column into the coal. We show that Re–Os geochronology of marine-influenced coal can be a viable tool for constraining depositional ages.

West Virginia↗

USGS2015

Re–Os age for the Lower–Middle Pennsylvanian Boundary and comparison with associated palynoflora

The Betsie Shale Member is a relatively thick and continuous unit that serves as a marker bed across the central Appalachian basin, in part because it includes an organic-rich shale unit at its base that is observable in drill logs. Deposited during a marine transgression, the Betsie Shale Member has been correlated to units in both Wales and Germany and has been proposed to mark the boundary between the Lower and Middle Pennsylvanian Series within North America. This investigation assigns a new Re–Os date to the base of the Betsie and examines the palynoflora and maceral composition of the underlying Matewan coal bed in the context of that date. The Matewan coal bed contains abundant lycopsid tree spores along its base with assemblage diversity and inertinite content increasing upsection, as sulfur content and ash yield decrease. Taken together, these palynologic and organic petrographic results suggest a submerged paleomire that transitioned to an exposed peat surface. Notably, separating the lower and upper benches of the Matewan is a parting with very high sulfur content (28 wt.%), perhaps representing an early marine pulse prior to the full on transgression responsible for depositing the Betsie. Results from Re–Os geochronology date the base of the Betsie at 323 ± 7.8 Ma, consistent with previously determined age constraints as well as the palynoflora assemblage presented herein. The Betsie Shale Member is also highly enriched in Re (ranging from 319.7 to 1213 ng/g), with high 187 Re/ 188 Os values ranging from 3644 to 5737 likely resultant from varying redox conditions between the pore water and overlying water column during deposition and early condensing of the section.

West Virginia↗

USGS2014

Atmospheric particulate matter in proximity to mountaintop coal mines: Sources and potential environmental and human health impacts

Mountaintop removal mining (MTM) is a widely used approach to surface coal mining in the US Appalachian region whereby large volumes of coal overburden are excavated using explosives, removed, and transferred to nearby drainages below MTM operations. To investigate the air quality impact of MTM, the geochemical characteristics of atmospheric particulate matter (PM) from five surface mining sites in south central West Virginia, USA, and five in-state study control sites having only underground coal mining or no coal mining whatsoever were determined and compared. Epidemiologic studies show increased rates of cancer, respiratory disease, cardiovascular disease, and overall mortality in Appalachian surface mining areas compared to Appalachian non-mining areas. In the present study, 24-h coarse (>2.5 µm) and fine (≤2.5 µm) PM samples were collected from two surface mining sites in June 2011 showed pronounced enrichment in elements having a crustal affinity (Ga, Al, Ge, Rb, La, Ce) contributed by local sources, relative to controls. Follow-up sampling in August 2011 lacked this enrichment, suggesting that PM input from local sources is intermittent. Using passive samplers, dry deposition total PM elemental fluxes calculated for three surface mining sites over multi-day intervals between May and August 2012 were 5.8 ± 1.5 times higher for crustal elements than at controls. Scanning microscopy of 2,249 particles showed that primary aluminosilicate PM was prevalent at surface mining sites compared to secondary PM at controls. Additional testing is needed to establish any link between input of lithogenic PM and disease rates in the study area.

West Virginia↗

USGS2013

Shallow groundwater and soil chemistry response to 3 years of subsurface drip irrigation using coalbed-methane-produced water

Disposal of produced waters, pumped to the surface as part of coalbed methane (CBM) development, is a significant environmental issue in the Wyoming portion of the Powder River Basin, USA. High sodium adsorption ratios (SAR) of the waters could degrade agricultural land, especially if directly applied to the soil surface. One method of disposing of CBM water, while deriving beneficial use, is subsurface drip irrigation (SDI), where acidified CBM waters are applied to alfalfa fields year-round via tubing buried 0.92 m deep. Effects of the method were studied on an alluvial terrace with a relatively shallow depth to water table (∼3 m). Excess irrigation water caused the water table to rise, even temporarily reaching the depth of drip tubing. The rise corresponded to increased salinity in some monitoring wells. Three factors appeared to drive increased groundwater salinity: (1) CBM solutes, concentrated by evapotranspiration; (2) gypsum dissolution, apparently enhanced by cation exchange; and (3) dissolution of native Na–Mg–SO 4 salts more soluble than gypsum. Irrigation with high SAR (∼24) water has increased soil saturated paste SAR up to 15 near the drip tubing. Importantly though, little change in SAR has occurred at the surface.

Wyoming↗

USGS2013

Atmospheric mercury and fine particulate matter in coastal New England: implications for mercury and trace element sources in the northeastern United States

Intensive sampling of ambient atmospheric fine particulate matter was conducted at Woods Hole, Massachusetts over a four-month period from 3 April to 29 July, 2008, in conjunction with year-long deployment of the USGS Mobile Mercury Lab. Results were obtained for trace elements in fine particulate matter concurrently with determination of ambient atmospheric mercury speciation and concentrations of ancillary gasses (SO 2 , NO x , and O 3 ). For particulate matter, trace element enrichment factors greater than 10 relative to crustal background values were found for As, Bi, Cd, Cu, Hg, Pb, Sb, V, and Zn, indicating contribution of these elements by anthropogenic sources. For other elements, enrichments are consistent with natural marine (Na, Ca, Mg, Sr) or crustal (Ba, Ce, Co, Cs, Fe, Ga, La, Rb, Sc, Th, Ti, U, Y) sources, respectively. Positive matrix factorization was used together with concentration weighted air-mass back trajectories to better define element sources and their locations. Our analysis, based on events exhibiting the 10% highest PM 2.5 contributions for each source category, identifies coal-fired power stations concentrated in the U.S. Ohio Valley, metal smelting in eastern Canada, and marine and crustal sources showing surprisingly similar back trajectories, at times each sampling Atlantic coastal airsheds. This pattern is consistent with contribution of Saharan dust by a summer maximum at the latitude of Florida and northward transport up the Atlantic Coast by clockwise circulation of the summer Bermuda High. Results for mercury speciation show diurnal production of RGM by photochemical oxidation of Hg° in a marine environment, and periodic traverse of the study area by correlated RGM-SO 2 (NO x ) plumes, indicative of coal combustion sources.

Massachusetts↗

USGS2013

Direct estimation of diffuse gaseous emissions from coal fires: current methods and future directions

Coal fires occur in nature spontaneously, contribute to increases in greenhouse gases, and emit atmospheric toxicants. Increasing interest in quantifying coal fire emissions has resulted in the adaptation and development of specialized approaches and adoption of numerical modeling techniques. Overview of these methods for direct estimation of diffuse gas emissions from coal fires is presented in this paper. Here we take advantage of stochastic Gaussian simulation to interpolate CO 2 fluxes measured using a dynamic closed chamber at the Ruth Mullins coal fire in Perry County, Kentucky. This approach allows for preparing a map of diffuse gas emissions, one of the two primary ways that gases emanate from coal fires, and establishing the reliability of the study both locally and for the entire fire. Future research directions include continuous and automated sampling to improve quantification of gaseous coal fire emissions.

International Journal of Coal Geology↗

USGS2013

Using simulated maps to interpret the geochemistry, formation and quality of the Blue Gem Coal Bed, Kentucky, USA

This study presents geostatistical simulations of coal-quality parameters, major oxides and trace metals for an area covering roughly 812 km 2 of the Blue Gem coal bed in southeastern Kentucky, USA. The Blue Gem, characterized by low ash yield and low sulfur content, is an important economic resource. Past studies have characterized the Blue Gem's geochemistry, palynology and petrography and inferred a depositional setting of a planar peat deposit that transitioned to slightly domed later in its development. These studies have focused primarily on vertical geochemical trends within the coal bed. Simulated maps of chemical elements derived from 45 measured sample locations across the study area provide an opportunity to observe changes in the horizontal direction within the coal bed. As the Blue Gem coal bed shows significant vertical chemical trends, care was taken in this study to try to select samples from a single, middle portion of the coal. By revealing spatial distribution patterns of elements across the middle of the bed, associations between different components of the coal can be seen. The maps therefore help to provide a picture of the coal-forming peat bog at an instant in geologic time and allow interpretation of a depositional setting in the horizontal direction. Results from this middle portion of the coal suggest an association of SiO 2 with both K 2 O and TiO 2 in different parts of the study area. Further, a pocket in the southeast of the study area shows elevated concentrations of elements attributable to observed carbonate-phase minerals (MgO, CaO, Ba and Sr) as well as elements commonly associated with sulfide-phase minerals (Cu, Mo and Ni). Areas of relatively high ash yield are observed in the north and south of the mapped area, in contrast to the low ash yields seen towards the east. Additionally, we present joint probability maps where multiple coal-quality parameters are plotted simultaneously on one figure. This application allows researchers to investigate associations of more than two components in a straight-forward manner useful in guiding resource exploration.

Kentucky↗

USGS2013

Whole-coal versus ash basis in coal geochemistry: a mathematical approach to consistent interpretations

Several standard methods require coal to be ashed prior to geochemical analysis. Researchers, however, are commonly interested in the compositional nature of the whole-coal, not its ash. Coal geochemical data for any given sample can, therefore, be reported in the ash basis on which it is analyzed or the whole-coal basis to which the ash basis data are back calculated. Basic univariate (mean, variance, distribution, etc.) and bivariate (correlation coefficients, etc.) measures of the same suite of samples can be very different depending which reporting basis the researcher uses. These differences are not real, but an artifact resulting from the compositional nature of most geochemical data. The technical term for this artifact is subcompositional incoherence. Since compositional data are forced to a constant sum, such as 100% or 1,000,000 ppm, they possess curvilinear properties which make the Euclidean principles on which most statistical tests rely inappropriate, leading to erroneous results. Applying the isometric logratio (ilr) transformation to compositional data allows them to be represented in Euclidean space and evaluated using traditional tests without fear of producing mathematically inconsistent results. When applied to coal geochemical data, the issues related to differences between the two reporting bases are resolved as demonstrated in this paper using major oxide and trace metal data from the Pennsylvanian-age Pond Creek coal of eastern Kentucky, USA. Following ilr transformation, univariate statistics, such as mean and variance, still differ between the ash basis and whole-coal basis, but in predictable and calculated manners. Further, the stability between two different components, a bivariate measure, is identical, regardless of the reporting basis. The application of ilr transformations addresses both the erroneous results of Euclidean-based measurements on compositional data as well as the inconsistencies observed on coal geochemical data reported on different bases.

International Journal of Coal Geology↗

USGS2011

Summary of inorganic compositional data for groundwater, soil-water, and surface-water samples collected at the Headgate Draw subsurface drip irrigation site, Johnson County, Wyoming

As part of a 5-year project on the impact of subsurface drip irrigation (SDI) application of coalbed-methane (CBM) produced waters, water samples were collected from the Headgate Draw SDI site in the Powder River Basin, Wyoming, USA. This research is part of a larger study to understand short- and long-term impacts on both soil and water quality from the beneficial use of CBM waters to grow forage crops through use of SDI. This document provides a summary of the context, sampling methodology, and quality assurance and quality control documentation of samples collected prior to and over the first year of SDI operation at the site (May 2008-October 2009). This report contains an associated database containing inorganic compositional data, water-quality criteria parameters, and calculated geochemical parameters for samples of groundwater, soil water, surface water, treated CBM waters, and as-received CBM waters collected at the Headgate Draw SDI site.

Montana, Wyoming↗

USGS2011

Quality assurance and quality control of geochemical data—A primer for the research scientist

Geochemistry is a constantly expanding science. More and more, scientists are employing geochemical tools to help answer questions about the Earth and earth system processes. Scientists may assume that the responsibility of examining and assessing the quality of the geochemical data they generate is not theirs but rather that of the analytical laboratories to which their samples have been submitted. This assumption may be partially based on knowledge about internal and external quality assurance and quality control (QA/QC) programs in which analytical laboratories typically participate. Or there may be a perceived lack of time or resources to adequately examine data quality. Regardless of the reason, the lack of QA/QC protocols can lead to the generation and publication of erroneous data. Because the interpretations drawn from the data are primary products to U.S. Geological Survey (USGS) stakeholders, the consequences of publishing erroneous results can be significant. The principal investigator of a scientific study ultimately is responsible for the quality and interpretation of the project's findings, and thus must also play a role in the understanding, implementation, and presentation of QA/QC information about the data. Although occasionally ignored, QA/QC protocols apply not only to procedures in the laboratory but also in the initial planning of a research study and throughout the life of the project. Many of the tenets of developing a sound QA/QC program or protocols also parallel the core concepts of developing a good study: What is the main objective of the study? Will the methods selected provide data of enough resolution to answer the hypothesis? How should samples be collected? Are there known or unknown artifacts or contamination sources in the sampling and analysis methods? Assessing data quality requires communication between the scientists responsible for designing the study and those collecting samples, analyzing samples, treating data, and interpreting results. This primer has been developed to provide basic information and guidance about developing QA/QC protocols for geochemical studies. It is not intended to be a comprehensive guide but rather an introduction to key concepts tied to a list of relevant references for further reading. The guidelines are presented in stepwise order beginning with presampling considerations and continuing through final data interpretation. The goal of this primer is to outline basic QA/QC practices that scientists can use before, during, and after chemical analysis to ensure the validity of the data they collect with the goal of providing defendable results and conclusions.

Open-File Report↗