Source apportionment of atmospheric trace gases and particulate matter--Comparison of log-ratio and traditional approaches
No abstract available.
Conference Paper↗
Geology topics
Allan Kolker
Publications and source records attributed to Allan Kolker.
Comparison of atmospheric mercury speciation and deposition at nine sites across central and eastern North America
This study presents >5 cumulative years of tropospheric mercury (Hg) speciation measurements, over the period of 2003–2009, for eight sites in the central and eastern United States and one site in coastal Puerto Rico. The purpose of this research was to identify local and regional processes that impact Hg speciation and deposition (wet + dry) across a large swath of North America. Sites sampled were selected to represent both a wide range of mercury exposure and environmental conditions. Seasonal mean concentrations of elemental Hg (1.27 ± 0.31 to 2.94 ± 1.57 ng m−3; x ± s), reactive gaseous mercury (RGM; 1.5 ± 1.6 to 63.3 ± 529 pg m−3), and fine particulate Hg (1.2 ± 1.4 to 37.9 ± 492 pg m−3) were greatest at sites impacted by Hg point sources. Diel bin plots of Hgo and RGM suggest control by a variety of local/regional processes including impacts from Hg point sources and boundary layer/free tropospheric interactions as well as from larger‐scale processes affecting Hg speciation (i.e., input of the global Hg pool, RGM formed from oxidation of Hgo by photochemical compounds at coastal sites, and elemental Hg depletion during periods of dew formation). Comparison of wet Hg deposition (measured), RGM and fine particulate Hg dry deposition (calculated using a multiple resistance model), and anthropogenic point source emissions varied significantly between sites. Significant correlation between emission sources and dry deposition was observed but was highly dependant upon inclusion of data from two sites with exceptionally high deposition. Findings from this study highlight the importance of environmental setting on atmospheric Hg cycling and deposition rates.
Journal of Geophysical Research↗
Health effects of energy resources
Energy resources (coal, oil, and natural gas) are among the cornerstones of modern industrial society. The exploitation of these resources, however, is not without costs. Energy materials may contain harmful chemical substances that, if mobilized into air, water, or soil, can adversely impact human health and environmental quality. In order to address the issue of human exposure to toxic substances derived from energy resources, the U.S. Geological Survey (USGS) Energy Resources Program developed a project entitled 'Impacts of Energy Resources on Human Health and Environmental Quality.' The project is intended to provide policymakers and the public with the scientific information needed to weigh the human health and environmental consequences of meeting our energy needs. This fact sheet discusses several areas where the USGS Energy Resources Program is making scientific advances in this endeavor.
Fact Sheet↗
Emissions from coal fires and their impact on the environment
Self-ignited, naturally occurring coal fires and fires resulting from human activities persist for decades in underground coal mines, coal waste piles, and unmined coal beds. These uncontrolled coal fires occur in all coal-bearing parts of the world (Stracher, 2007) and pose multiple threats to the global environment because they emit greenhouse gases - carbon dioxide (CO 2 ), and methane (CH 4 ) - as well as mercury (Hg), carbon monoxide (CO), and other toxic substances (fig. 1). The contribution of coal fires to the global pool of atmospheric CO 2 is little known but potentially significant. For China, the world's largest coal producer, it is estimated that anywhere between 10 million and 200 million metric tons (Mt) of coal reserves (about 0.5 to 10 percent of production) is consumed annually by coal fires or made inaccessible owing to fires that hinder mining operations (Rosema and others, 1999; Voigt and others, 2004). At this proportion of production, coal amounts lost to coal fires worldwide would be two to three times that for China. Assuming this coal has mercury concentrations similar to those in U.S. coals, a preliminary estimate of annual Hg emissions from coal fires worldwide is comparable in magnitude to the 48 tons of annual Hg emissions from all U.S. coal-fired power-generating stations combined (U.S. Environmental Protection Agency, 2002). In the United States, the combined cost of coal-fire remediation projects, completed, budgeted, or projected by the U.S. Department of the Interior's Office of Surface Mining Reclamation and Enforcement (OSM), exceeds $1 billion, with about 90% of that in two States - Pennsylvania and West Virginia (Office of Surface Mining Enforcement and Reclamation, 2008; fig. 2). Altogether, 15 States have combined cumulative OSM coal-fire project costs exceeding $1 million, with the greatest overall expense occurring in States where underground coal fires are predominant over surface fires, reflecting the greater cost of extinguishing underground fires (fig. 2) (see 'Controlling Coal Fires'). In this fact sheet we review how coal fires occur, how they can be detected by airborne and remote surveys, and, most importantly, the impact coal-fire emissions may have on the environment and human health. In addition, we describe recent efforts by the U.S. Geological Survey (USGS) and collaborators to measure fluxes of CO 2 , CO, CH 4 , and Hg, using groundbased portable detectors, and combining these approaches with airborne thermal imaging and CO 2 measurements. The goal of this research is to develop approaches that can be extrapolated to large fires and to extrapolate results for individual fires in order to estimate the contribution of coal fires as a category of global emissions.
Fact Sheet↗
Summary of mercury and trace element results in precipitation from the Culpeper, Virginia, Mercury Deposition Network Site (VA-08), 2002-2006
The VA-08 Mercury Deposition Network (MDN) site, southwest of Culpeper, Virginia, was established in autumn of 2002. This site, along with nearby VA-28 (~31 km west) at Big Meadows in Shenandoah National Park, fills a spatial gap in the Mid-Atlantic region of the MDN network and provides Hg deposition data immediately west of the Washington, D.C., metropolitan area. Results for the Culpeper site from autumn of 2002 to the end of 2006 suggest that the highest mercury (Hg) deposition (up to 5.0 µg/m 2 per quarter of the 6.5-12.6 µg/m 2 annual Hg deposition) is measured during the second and third quarters of the year (April-September). This is a result of both elevated Hg precipitation concentrations (up to 27 ng/L) and greater precipitation during these months. The data also exhibit a general statistically significant (p<0.05) negative correlation between weekly total precipitation and Hg concentrations, suggesting a dilution effect during larger precipitation events, especially during winter and spring. Comparison of results between the Culpeper and Big Meadows sites indicates that although quarterly Hg deposition was not significantly different (p<0.05) between sites, quarterly volume-averaged Hg precipitation concentrations were statistically larger (p<0.05) and precipitation was significantly lower (p<0.05) at VA-08. Lower Hg concentrations at the VA-28 site relative to VA-08 are likely a result of greater total precipitation and thus additional dilution of Hg in precipitation. Results from concomitant trace elements in precipitation collected from July, 2005, to December, 2006, were used to better identify possible sources of Hg at the Culpeper MDN site. Principal component analysis of the Hg and trace metal data identified 3 primary source categories, each with large loadings of characteristic elements: 1) Ca, Al, Mg, Sr, La, and Ce (crustal sources); 2) V, Na, and Ni (local wintertime heating oil); and 3) Zn, Cd, Mn, and Hg (regional anthropogenic emission sources). HYSPLIT air mass trajectory modeling and enrichment factor calculations are consistent with this interpretation. A preliminary source attribution model suggests that ~51% of the Hg in wet deposition is due to regional anthropogenic sources, while crustal sources and local oil combustion account for 9.5% and <1%, respectively. This calculation implies that the global Hg burden accounts for ~40% of the Hg in wet deposition.
Virginia↗
Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and 57 Fe Mössbauer spectroscopic study
Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O 2 atmosphere; (3) room atmosphere (relative humidity ∼20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and 57 Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. 57 Fe Mössbauer spectroscopy also shows a much greater proportion of Fe 3+ forms (jarosite, Fe 3+ sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.
Applied Geochemistry↗
Investigating atmospheric mercury with the U.S. Geological Survey Mobile Mercury Laboratory
Atmospheric mercury is thought to be an important source of mercury present in fish, resulting in numerous local, statewide, tribal, and province-wide fish consumption advisories in the United States and Canada (U.S. Environmental Protection Agency, 2007a). To understand how mercury occurs in the atmosphere and its potential to be transferred from the atmosphere to the biosphere, the U.S. Geological Survey (USGS) has been investigating sources and forms of atmospheric mercury, especially in locations where the amount of mercury deposited from precipitation is above average.
Fact Sheet↗
Mercury in coal and the impact of coal quality on mercury emissions from combustion systems
The proportion of Hg in coal feedstock that is emitted by stack gases of utility power stations is a complex function of coal chemistry and properties, combustion conditions, and the positioning and type of air pollution control devices employed. Mercury in bituminous coal is found primarily within Fe-sulfides, whereas lower rank coal tends to have a greater proportion of organic-bound Hg. Preparation of bituminous coal to reduce S generally reduces input Hg relative to in-ground concentrations, but the amount of this reduction varies according to the fraction of Hg in sulfides and the efficiency of sulfide removal. The mode of occurrence of Hg in coal does not directly affect the speciation of Hg in the combustion flue gas. However, other constituents in the coal, notably Cl and S, and the combustion characteristics of the coal, influence the species of Hg that are formed in the flue gas and enter air pollution control devices. The formation of gaseous oxidized Hg or particulate-bound Hg occurs post-combustion; these forms of Hg can be in part captured in the air pollution control devices that exist on coal-fired boilers, without modification. For a given coal type, the capture efficiency of Hg by pollution control systems varies according to type of device and the conditions of its deployment. For bituminous coal, on average, more than 60% of Hg in flue gas is captured by fabric filter (FF) and flue-gas desulfurization (FGD) systems. Key variables affecting performance for Hg control include Cl and S content of the coal, the positioning (hot side vs. cold side) of the system, and the amount of unburned C in coal ash. Knowledge of coal quality parameters and their effect on the performance of air pollution control devices allows optimization of Hg capture co-benefit.
Applied Geochemistry↗
Expanding the mercury deposition network in Virginia and the U.S. mid-Atlantic region
No abstract available.
Fact Sheet↗
Arsenic in southeastern Michigan
Arsenic levels exceeding 10 μg/L are present in hundreds of private supply wells distributed over ten counties in eastern and southeastern Michigan. Most of these wells are completed in the Mississippian Marshall Sandstone, the principal bedrock aquifer in the region, or in Pleistocene glacial or Pennsylvanian bedrock aquifers. About 70% of ground water samples taken from more than 100 wells, have arsenic contents ≥10 μg/L with a maximum value of 220 μg/L . Water samples and continuous cores were taken from two test wells. Arsenic content of core samples ranges from <5 to more than 300 ppm, with the highest values found for pyritic black shales. Authigenic cements in the Marshall Sandstone include patchy authigenic pyrite that locally contains arsenic-rich (up to 8.5 wt. % As) domains. Bulk arsenic contents of pyrite-bearing intervals, sampled in well cuttings, are a high as 1020 ppm. Arsenic-rich pyrite is likely the ultimate source of arsenic in eastern and southeastern Michigan ground water, but evidence for pyrite oxidation at depth in bedrock aquifers is generally lacking. Pyrite oxidation may occur or have occurred in tills derived from the Marshall Sandstone and Coldwater Shale, which were found to contain arsenic-rich (up to at least 0.7 wt. % As) iron oxyhydroxides. Plausible mechanisms for widespread arsenic mobilization in eastern and southeastern Michigan ground water include weathering of pyrite in tills, reductive dissolution of iron oxyhydroxides in tills, and potentially, pyrite oxidation in bedrock aquifers, due to drawdown in wells or lowering of water-table levels in response to Pleistocene glaciation.
Michigan↗
Arsenic in stream sediments of northern Alabama
OVERVIEW OF ARSENIC IN STREAM SEDIMENTS The overall range of arsenic in the NURE stream sediments was from 0.3 to 44 mg/kg sediment (ppm) As in the sample data set. The mean value was 4.3 ppm with a standard deviation of 4.1 ppm. For comparison, the crustal abundance of arsenic is 1.8 ppm (Taylor, 1964). Shale is higher, with average values of 15 ppm. Coal samples from the entire USGS National Coal Resource Data System coal database (Finkelman, 1994) average 24 ppm arsenic. A study of stream sediments from throughout the U.S. by the USGS NAWQA program reported that the 75th percentile for arsenic in 541 stream sediments was 9.5 ppm (Rice, 1999). Given the relatively low crustal abundance of arsenic, a number of stream-sediment samples in this study may be considered geochemically anomalous in this element.
Alabama↗
Chemical analysis and modes of occurrence of selected trace elements in a Powder River basin coal and its corresponding simulated cleaned coal
This report provides semi-quantitative data on modes of occurrence of 19 elements in as-mined Powder River Basin coal and its corresponding simulated cleaned coal. The data are in support of the project "Prediction of Trace Element Removal from Coal" --a Cooperative Research and Development Agreement (CRADA) with CQ Inc. The purpose of this CRADA is to apply modes of occurrence information to coal cleaning procedures. Techniques used in this study include sequential selective leaching procedures, scanning electron microscopy, X-ray diffraction analysis, and electron microprobe analysis. Selective leaching results indicate that greater than 40 percent of the elements Co, U, Be, Ca, Fe, Mn, Ba, Zn, Cd, Pb are associated with HCIsoluble carbonates, iron oxides, or monosulfides, greater than 40 percent of the Al, Cr and Mo are associated with HF-soluble silicates, greater than 40 percent of the Ni, Cu, As and Sb are associated with acid-insoluble phases and/or organic matter, and greater than 50 percent of the Hg is associated with HMDs-soluble pyrite. Thirty percent of the Th was leached by HCI and 30 percent of this element was leached by HF. Scanning electron microscopy indicates that quartz, kaolinite, illite and iron oxide, possibly hematite, are the major minerals present. X-ray diffraction analysis confirmed that quartz, kaolinite and hematite are present, but did not determine illite, indicating that illite in these coals is of low abundance or is poorly crystalline. Electron microprobe data indicate that concentrations of the chalcophile elements As, Se, Cu, Ni, Zn, and Cd in most pyrite grains are at or below the detection limit of about 100-200 ppm in both the as-mined coal and its corresponding simulated cleaned coal product. The results of this project should aid in the development of models for predicting the response of potentially toxic trace elements in commercial coal cleaning procedures.
Open-File Report↗
Semi-quantitative determination of the modes of occurrence of elements in coal: Results from an international round robin project
No abstract available.
Open-File Report↗
Characterization of fly ash from low-sulfur and high-sulfur coal sources: Partitioning of carbon and trace elements with particle size
Fly ash samples were collected in November and December of 1994, from generating units at a Kentucky power station using high- and low-sulfur feed coals. The samples are part of a two-year study of the coal and coal combustion byproducts from the power station. The ashes were wet screened at 100, 200, 325, and 500 mesh (150, 75, 42, and 25 mu m, respectively). The size fractions were then dried, weighed, split for petrographic and chemical analysis, and analyzed for ash yield and carbon content. The low-sulfur ''heavy side'' and ''light side'' ashes each have a similar size distribution in the November samples. In contrast, the December fly ashes showed the trend observed in later months, the light-side ash being finer (over 20 % more ash in the 500 mesh [25 mu m] fraction) than the heavy-side ash. Carbon tended to be concentrated in the coarse fractions in the December samples. The dominance of the 325 mesh (42 mum) fractions in the overall size analysis implies, though, that carbon in the fine sizes may be an important consideration in the utilization of the fly ash. Element partitioning follows several patterns. Volatile elements, such as Zn and As, are enriched in the finer sizes, particularly in fly ashes collected at cooler, light-side electrostatic precipitator (ESP) temperatures. The latter trend is a function of precipitation at the cooler-ESP temperatures and of increasing concentration with the increased surface area of the finest fraction. Mercury concentrations are higher in high-carbon fly ashes, suggesting Hg adsorption on the fly ash carbon. Ni and Cr are associated, in part, with the spinel minerals in the fly ash.
Energy Sources↗
Preliminary report on the International Energy Agency mode of occurrence inter-laboratory comparison; Phase I, USGS results
No abstract available.
Open-File Report↗