J. David Robertson

Speciation of elements in NIST particulate matter SRMs 1648 and 1650

X-ray absorption fine structure (XAFS) spectra for S, Cl, V, Cr, Mn, Cu, Zn, As, Br, Cd and Pb and Mossbauer spectra for Fe have been obtained for two National Institute of Standards and Technology (NIST) particulate matter (PM) standard reference materials (SRMs): urban PM (SRM 1648) and diesel PM (SRM 1650). The spectral data, complemented by information on elemental concentrations from proton-induced X-ray-emission (PIXE) spectroscopy, were used to interpret the speciation of these elements in these complex materials. It appears that all the metallic elements investigated occur in oxidized forms, principally as sulfates in the diesel PM SRM and as sulfates, oxides, and possibly other forms (e.g. clays?) in the urban PM. A minor fraction of the sulfur and major fractions of the halogens, Cl and Br, occur as organosulfide (thiophene) and organohalide occurrences, respectively, that must be associated with the abundant carbonaceous matter that constitutes the major component of the two PM SRMs. Most of the sulfur, however, occurs as sulfate in the urban PM and as bisulfate in the diesel PM. In addition, elemental oxidation states have been determined directly by the spectroscopic techniques. Such information is often the key parameter in determining the toxicity and solubility of specific elements in PM, both of which are important in understanding the threat that such elements may pose to human health. For the two HAP elements, Cr and As, for which the toxicity depends greatly on oxidation state, the XAFS data showed that both elements are present in both SRMs predominantly in the less toxic oxidation states, Cr(III) and As(V). The potential of the XAFS spectra for use as source apportionment signatures is illustrated by reference to chromium, which exists in these two PM SRMs in very different forms.

Characterization of fly ash from Kentucky power plants

Abstract Fly ashes from 21 Kentucky power plants were grouped according to the sulfur content of the feed coal. The highest-carbon fly ashes tended to be from the lowest-sulfur feed coals, partly because many of those plants were smaller and older than the higher-sulfur units. Iron oxide content increased at the expense of aluminium and silicon oxides in the higher-sulfur feed ashes. An increase in calcium and magnesium oxides towards the higher-sulfur feed ashes was due to the greater abundance of carbonate minerals in the higher-sulfur Illinois Basin coals. The highest arsenic values were among electrostatic precipitator ashes from medium-sulfur sources. The arsenic and lead contents of low- and medium-sulfur central Appalachian coals could be higher than those of high-sulfur Illinois Basin coals. Where direct comparison of fly ash and bottom ash was possible, the bottom ash was enriched in Fe 2 O 3 relative to the fly ash and most minor elements were depleted in the bottom ash relative to the fly ash. TCLP testing of selected fly ashes indicated that all of the leachates would pass the established RCRA limits. Some of the higher As and Cr levels were from fly ashes in the highest-sulfur category. For As, though, there is no significant correlation between fly ash As and leachate As.

XAFS spectroscopic characterization of elements in combustion ash and fine particulate matter

X-ray absorption fine structure (XAFS) spectroscopy is a powerful non-destructive, direct technique for determining the speciation of environmentally important elements in products derived from combustion of fossil fuels. Such information is potentially important (i) for assessing the threat to human health posed by specific forms and oxidation states of such elements in combustion products (ash) or in combustion-derived airborne particulate matter (PM), and (ii) for possible source identification and apportionment in PM investigations. The specific examples discussed include the speciation of various elements classified as hazardous air pollutants (HAPs) in ash products from combustion of coal (As and Cr), residual oil (Ni and Cr), and biomass (Cd and Zn) and in airborne PM collected on a PM10 filter (S, Cl, Cr and As). Chromium and arsenic, which could exist in these materials in different oxidation states, were typically found predominantly in less toxic oxidation states, Cr(III) and As(V). All metal species (Cr, Ni, Cd, Zn, As) were shown to be present in the combustion ashes in predominantly oxidic environments (i.e., oxides, sulfates, arsenates, etc.). Most of the sulfur in the PM10 filter sample was present as sulfate, but minor organosulfur forms (thiophene) were also identified. For comparison with the data obtained for elements on the PM10 filter, XAFS data are also presented for the corresponding elements in two National Institute of Standards and Technology (NIST) particulate matter Standard Reference Materials (SRMs): Urban PM (SRM 1648), and Diesel PM (SRM 1650).

Petrology, mineralogy, and chemistry of magnetically-separated sized fly ash

A class F fly ash from a high-sulfur coal source was wet-sieved at 100, 200, 325, and 500 mesh and each of the five size fractions was then magnetically separated. Each fraction was examined for petrography by optical microscopy, mineralogy by X-ray diffraction, and major and minor element chemistry by proton-induced X-ray emission (PIXE). Spinel (magnetite) is the major magnetic mineral, with hematite being another major iron oxide phase. As expected, the magnetite is most abundant in the magnetic fractions, but, due to mixed-phase fly ash particles, is not the only component in the magnetic fractions nor is it totally excluded from the non-magnetic fractions. Other mineral phases include quartz, mullite, and calcite, the latter being a secondary phase produced in the wet-sieving procedure from lime in the original fly ash. Chromium, likely associated with the spinels, is one minor element which is significantly higher in the magnetic versus non-magnetic fractions.

Arsenic and lead concentrations in the Pond Creek and Fire Clay coal beds, eastern Kentucky coal field

Abstract The Middle Pennsylvanian Breathitt Formation (Westphalian B) Pond Creek and Fire Clay coal beds are the 2 largest producing coal beds in eastern Kentucky. Single channel samples from 22 localities in the Pond Creek coal bed were obtained from active coal mines in Pike and Martin Countries, Kentucky, and a total of 18 Fire Clay coal bed channel samples were collected from localities in the central portion of the coal field. The overall objective of this study was to investigate the concentration and distribution of potentially hazardous elements in the Fire Clay and Pond Creek coal beds, with particular emphasis on As and Pb, 2 elements that are included in the 1990 Clean Air Act Amendments as potential air toxics. The 2 coals are discussed individually as the depositional histories are distinct, the Fire Clay coal bed having more sites where relatively high-S lithologies are encountered. In an effort to characterize these coals, 40 whole channel samples, excluding 1-cm partings, were analyzed for major, minor and trace elements by X-ray fluorescence and proton-induced X-ray emission spectroscopy. Previously analyzed samples were added to provide additional geographic coverage and lithotype samples from one site were analyzed in order to provide detail of vertical elemental trends. The As and Pb levels in the Fire Clay coal bed tend to be higher than in the Pond Creek coal bed. One whole channel sample of the Fire Clay coal bed contains 1156 ppm As (ash basis), with a single lithotype containing 4000 ppm As (ash basis). Most of the As and Pb appears to be associated with pyrite, which potentially can be removed in beneficiation (particularly coarser pyrite). Disseminated finer pyrite may not be completely removable by cleaning. In the examination of pyrite conducted in this study, it does not appear that significant concentration of As or Pb occurs in the finer pyrite forms. The biggest potential problem of As- or Pb-enriched pyrite is, therefore, one of refuse disposal.

Investigation of high temperature reactions on solid substrates with Rutherford backscattering spectrometry: interaction of palladium with selenium on heated graphite surfaces

Abstract Selenium and palladium interactions on heated pyrolytically coated graphite substrates were investigated using Rutherford backscattering spectrometry. The studies were performed using selenium alone, palladium alone, and a combination of selenium and palladium deposited on the graphite substrates. The results indicate that palladium instantaneously stabilizes selenium at ambient temperatures and prevents the diffusion of selenium into the graphite. As the substrate is heated, temperature dependent diffusion of all analytes into the graphite is observed. Furthermore, it appears that the stabilization of selenium is due to the formation of a stoichiometric compound with palladium and oxygen. This compound decomposes at a temperature between 1070 and 1770 K.

Metalliferous coals of the Westphalian A Joggins Formation, Cumberland Basin, Nova Scotia, Canada: petrology, geochemistry, and palynology

Abstract Five coals of Westphalian A (early Middle Pennsylvanian) age were sampled from the Joggins Formation section exposed along Chignecto Bay at Joggins, Nova Scotia. Coal beds along the bay were mined beginning in the early 17th century, yet there have been few detailed published investigation of the coal beds of this classic section. The lowermost coal, the Upper Coal 28 (Upper Fundy), is a high-vitrinite coal with a spore assemblage dominated by arboreous lycopsid spores with tree ferns subdominant. The upper portions of the coal bed have the highest ratio of well-preserved to poorly-preserved telinite of any of the coals investigated. Coal 19 (“clam coal”) has 88% total vitrinite but, unlike the Fundy coal bed, the telinite has a poor preservation ratio and half the total vitrinite population comprises gelocollinite and vitrodetrinite. The latter coal bed is directly overlain by a basin-wide limestone bed. The Lower Kimberly coal shows good preservation of vitrinite with relatively abundant telinite among the total vitrinite. The Middle Kimberly coal, which underlies the tetrapod-bearing lycopsid trees found by Lyell and Dawson in 1852, exhibits an upward decrease in arboreous lycopod spores and an upward increase in the tree fern spore Punctatisporites minutus . Telinite preservation increases upwards in the Middle Kimberly but overall is well below the preservation ratio of the Upper Fundy coal bed. The coals all have high sulfur contents, yielding up to 13.7% total sulfur for the lower lithotype of the Upper Fundy coal bed. The Kimberly coals are not only high in total and pyritic sulfur, but also have high concentrations of chalcophile elements. Zinc, ranging up to 15,000 ppm (ash basis), is present as sphalerite in fusain lumens. Arsenic and lead each exceed 6000 ppm (ash basis) in separate lithotypes of the Kimberly coals. Together these data are consistent with elevated pH in planar mires. The source of the elemental enrichment in this presumed continental section is enigmatic.

Influence of flue-gas desulfurization systems on coal combustion by-product quality at kentucky power stations burning high-sulfur coal

Two Kentucky power plants burning similar blends of high-sulfur western Kentucky and southern Indiana coal provide a unique opportunity to examine the variations in coal combustion by-products due to differences in the method of wet flue-gas desulfurization (FGD). One plant employed carbide lime-based scrubbing for two units and a dual-alkali process for the third unit. The second plant employed a Mississippian limestone from Kentucky for all four units. This study provides an example of optical and SEM petrographic techniques, supplemented by chemical analyses, applied to the study of, at least from the geologic perspective, non-traditional materials. The coal sources comprise a blend of high volatile C and B bituminous, high vitrinite (85–90%, mmf), high-sulfur (> 3%, dry) coals. The fly ash is dominated by glassy phases (70–80%) with about 5–10% spinel (predominately magnetite), 3–10% quartz, and 4–10% isotropic coke comprising the remaining portion of the ash. SEM observations indicate that the glassy particles exhibit a bimodal size distribution with sub-micron glass spheres and a population of larger (several 10s of microns) spheres. The bottom ash has higher proportions of spinels and mullite, with negligible carbon forms, compared to the fly ash from the same units. Fly ashes were observed to be lower in Fe and higher in Al, Si, and S compared to the bottom ashes. Carbide lime, a by-product of acetylene manufacture, soda ash, and limestone were the reagents used in the flue-gas desulfurization processes. The primary FGD by-product is a calcium sulfite slurry which is vacuum filtered and mixed with fly ash and, usually, lime, to form a stable product for disposal. The FGD by-products have some potential, as yet unrealized, for utilization.

Investigation of high temperature reactions on graphite with Rutherford backscattering spectrometry: interaction of cadmium, lead and silver with a phosphate modifier

The depth-dependent concentration profiles of nitrate salts of Pb, Cd and Ag were observed with and without the addition of (NH4)H2PO4 chemical modifier using Rutherford backscattering spectrometry (RBS). The RBS results demonstrate that the analytes, in all the systems investigated, readily migrate (≥3 µm) into the pyrolytic graphite coated graphite substrate at room temperature. The stabilization of Cd and Pb with the phosphate modifier is proposed to be due to the formation of a phosphate glass. Silver did not extensively interact with the phosphate modifier and was, as a result, not stabilized.

Petrography and Chemistry of High-Carbon Fly Ash from the Shawnee Power Station, Kentucky

Abstract The Shawnee power station in western Kentucky consists of ten 150-MW units, eight of which bum low-sulfur ( 1 wt %) coal in an atmospheric fluidized-bed combustion unit and in a research unit. The eight low-sulfur coal units were sampled in a 1992 survey of Kentucky utilities. Little between-unit variation is seen in the ash-basis major oxide and minor element chemistry. The carbon content of the fly ashes varies from 5 to 25 wt %. Similarly, the isotropic and anisotropic coke in the fly ash varies from 6% to 42% (volume basis). Much of the anisotropic coke is a thin-walled macroporous variety, but there is a portion that is a thick-walled variety similar to a petroleum coke.