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C.A. Palmer

Publications and source records attributed to C.A. Palmer.

10 recordsLinked to original sources

Direct comparison of XAFS spectroscopy and sequential extraction for arsenic speciation in coal

The speciation of arsenic in an Ohio bituminous coal and a North Dakota lignite has been examined by the complementary methods of arsenic XAFS spectroscopy and sequential extraction by aqueous solutions of ammonium acetate, HCl, HF, and HNO3. In order to facilitate a more direct comparison of the two methods, the arsenic XAFS spectra were obtained from aliquots of the coal prepared after each stage of the leaching procedure. For the aliquots, approximately linear correlations (r2 > 0.98 for the Ohio coal, > 0.90 for the ND lignite) were observed between the height of the edge-step in the XAFS analysis and the concentration of arsenic measured by instrumental neutron activation analysis. Results from the leaching sequence indicate that there are two major arsenic forms present in both coals; one is removed by leaching with HCl and the other by HNO3. Whereas the XAFS spectral signatures of the arsenic leached by HCl are compatible with arsenate for both coals, the arsenic leached by HNO3 is identified as arsenic associated with pyrite for the Ohio coal and as an As3+ species for the North Dakota lignite. Minor arsenate forms persist in both coals after the final leaching with nitric acid. The arsenate forms extracted in HCl are believed to be oxidation products derived from the other major arsenic forms upon exposure of the pulverized coals to air.

ACS Division of Fuel Chemistry, Preprints

The geology of selected peat-forming environments in temperate and tropical latitudes

We studied peat in several geologic and climatic settings: (1) a glaciated terrain in cold-temperate Maine and Minnesota, U.S.A.; (2) an island in a temperate maritime climate in the Atlantic Ocean off the coast of Maine, U.S.A., where sea level is rising rapidly and changing the environment of peat accumulation; (3) swamps along the warm-temperate U.S. Atlantic and Gulf Coastal Plains, where sea level has changed often, thus creating sites for accumulation; and (4) in a tropical climate along the coast of Sarawak, Malaysia, and the delta of the Batang Hari River, Sumatra, Indonesia (Figs. 1 and 2). With the exception of the deposits on the Atlantic and Gulf Coastal Plains, most of the deposits described are domed bogs in which peat accumulation continued above the surface of the surrounding soil. The bogs of the U.S. Atlantic and Gulf Coastal Plains have almost level surfaces. All domed bogs are not entirely ombrotrophic (watered only from precipitation); multidomed bogs that rise from irregular or hilly surfaces may be crossed by streams that supply water to the bogs. The geologic processes or organic sedimentation, namely terrestrialization and paludification, are similar in all peat deposits considered here. Differences in geomorphology affecting the quantity and that quality of peat that has ash contents of less than 25%, which are desirable for commercial purposes, depend chiefly on: (1) high humidity, which is favorable to luxuriant growth of peat-forming vegetation; (2) a depositional setting that permits extensive accumulation relatively free from inorganic contamination from sea water and streams and from dust and volcanic ash; and (3) a stable regional water table that controls the rate of decomposition under aerobic conditions and protects the deposit against the ravages of fire. Differences in peat textures are due to the type of vegetation and to the degree of decomposition. The rate of decomposition is largely the result of the amount of oxidation and aerobic microbial activity. Stratigraphic distribution of various textures and amounts of inorganic components within a peat deposit is largely determined by the vertical positions occupied by peat-forming environments, such as pond, marsh, swamp and heath where vegetation accumulated, and the depth to zones of unoxygenated water. Peat also differs in the rate of accumulation. On the basis of carbon-14 dating, an estimated 8 m of peat in the tropical Batang Hari River deposit in Sumatra has been accumulating at the rate of about 1.5 m/1,000 yr, whereas peat in the cold-temperate deposit in Maine has been accumulating at the rate of 0.66 m/1,000 yr. Accumulation rates in domed deposits such as these are affected not only by factors controlling volume of biomass and aerobic decay but also by stream erosion and fires that remove peat. Such disconformities (see Fig. 2) within the deposit may be recognized by sudden vertical changes in degree of decomposition and/or the presence of charcoal. The trace-element content of peat deposits is affected by the environments of their settings. Samples of peat that have an ash content of less than 25% dry weight and that are from small, almost level swamp deposits along the Atlantic Coastal Plain of North Carolina were compared with similar samples from small domed bogs in Maine, a glaciated area. Samples from Nort Carolina, which are from deposits in thick fluvial and nearshore marine sediments far from the bedrock source, are generally higher in Ti, Cr and Pb. The Maine samples from deposits in glacial drift close to the bedrock source contain more Zn, Mn, P, Ca, Na and Fe. The kind and amount of trace elements within the deposits appear to relate largely to depositional setting, to kinds of bedrock source, and to the modes of transportation from source to peat swamp. Trace-element concentrations in the extensive Sumatra peat deposit, which represents a potentially commercial coal bed, are similar to those found in Appalachian coals except for As and Au, which are higher in the former. This similarity most likely implies that geochemical controls on mineral matter controlled the concentrations in both. Most peat deposits found in the world today are not precursors of economic coal beds because they are too local in extent, lack beds of commercial-quality peat greater than 6 m thick, and/or are too far from sea level to be rapidly by marine or marginal marine sediments before destruction by erosion and decomposition. However, the two domed deposits in Sarawak and Sumatra described above are parts of extensive, thick, low-sulfur, fuel-quality peat deposits, which have bases below the levels of rivers on coastal deltas. These are likely to be preserved in their lower part and to become precursors of tropical coal seams of potential economic importance. The lenticular and tabular peat deposits of the Atlantic and Gulf Coastal Plains, which have little chance of survival, have features resembling those in Tertiary peat deposits in alluvial settings of western North America. The quality, shape, and extent of modern and ancient peat deposits are controlled by the same factors - humidity, vegetation type, ground- and surface-water regimes, and physiographic and geologic setting. Thus, a study of modern peat deposits may help in studies of the areal distribution and the thickness and quality of ancient coal beds.

International Journal of Coal Geology

Chemistry and origin of minor and trace elements in selected vitrinite concentrates from bituminous and anthracitic coals

Organic and inorganic affinities were determined by comparing the elemental concentrations in the vitrinite concentrates to the concentrations in the companion whole coals. The ratios of these concentrations for 33 selected elements are shown in Figure 1. Ratios greater than 1 indicate organic affinity, and ratios less than 1 indicate inorganic affinity. Br and W generally showed organic affinity in all samples in this study. In the nine samples from the eastern United States (Fig. 1A-C) less than one-fourth of the trace elements show organic affinity compared to nearly one-half for the three English and Australian samples (Fig. 1D). The elements that generally show organic affinity in the non-U.S.A. samples studied include As, Cs, Hf, and Ni, which have generally inorganic affinities in the U.S.A. samples, and Cr, Sb, Se, and U, which have mixed (both organic and inorganic) affinities, in the U.S.A. coals studied, has an inorganic affinity in the English coals studied. B shows organic affinity in the samples from the Illinois basin (Fig. 1C). For the samples studied, Ba shows organic affinity in the Appalachian basin bituminous coals (Fig. 1B), inorganic affinity in the Illinois basin coals, and overall mixed affinities. In all the samples studied, Cu, Mn, Na, Sr, Ta, V, and Zn show mixed affinities, and A1, Co, Eu, Fe, Ga, K, La, Mg, Sc, Si, Th, Ti, and Ub have generally inorganic affinity.

International Journal of Coal Geology

The geology, botany and chemistry of selected peat-forming environments from temperate and tropical latitudes

Peat has been studied in several geologic settings: (1) glaciated terrain in cold temperate Maine and Minnesota, U.S.A.; (2) an island in the Atlantic Ocean off the coast of Maine, where sea level is rising; (3) the warm temperate U.S. Atlantic and Gulf Coastal Plains, where sea level has changed often; and (4) the tropical coast of Sarawak, Malaysia, and the tropical delta of the Batang Hari River, Sumatra, Indonesia. Most of these deposits are domed (ombrotrophic or partly ombrotrophic) bogs in which peat accumulation continued above the surface of the surrounding soil. However, the bogs of the U.S. Atlantic and Gulf Coastal Plains are comparatively not as domed, and many have almost level surfaces. In some bogs, aquatic or semi-aquatic plant materials accumulated, replaced water in the depressions, and formed a surface on which marsh or swamp vegetation could subsequently live, die, and accumulate. In others, the plant materials accumulated initially on level silt or sand surfaces supporting marshes or swamps. As the peat dome formed, plants growing on it changed from luxuriant ones near the base of the dome, where nutrients were brought into the bog by surface and ground water, to stunted ones at the top of the dome, where the raised bogs are fed by nutrient-poor precipitation. The physical and chemical changes that take place in the sequence of environments from the pond stage of deposit development, through the grassy marsh stage, through the forested swamp stage, and finally through the heath dome stage can be measured in terms of acidity and ash, volatile matter, carbon, hydrogen, nitrogen, sulfur and oxygen contents, as well as in the kind and distribution of trace elements. The organic and inorganic contents of the deposits relate to geomorphology, and geomorphology relates to their settings. As models of coal formation, some domed peat deposits may help in solving problems of distribution and character of ancient coal beds. But clearly not all peat deposits are precursors of coal. Most Holocene peat deposits are subject to destruction by erosion, fire and decomposition through microbial and chemical oxidation before burial. The best environments for coal precursors have biomass accumulation, a continuously rising water table within the mass, and minimum influx of clay and silt until preservation by burial. The most suitable settings for future economic coal deposits are domed bogs that accumulate thick, widespread peat having low ash and low sulfur contents. The ombrotrophic peat deposits of tropical Sarawak and Sumatra are thick and extensive, contain low-ash and low-sulfur peat, and have high heating values. They are considered to be the best tropical coal analogs because of their extent and chances of preservation; the base of the peat is below adjacent river levels, and chemical and structural conditions are favorable for accumulation.

International Journal of Coal Geology

Chemistry and origin of minor and trace elements in vitrinite concentrates from a rank series from the eastern United States, England, and Australia

A rank series consisting of twelve vitrinite concentrates and companion whole-coal samples from mined coal beds in the eastern United States, England, and Australia were analyzed for C, H, N, O, ash, and 47 trace and minor elements by standard elemental, instrumental neutron activation analysis (INAA), and direct-current-arc spectrographic (DCAS) techniques. The reflectance of vitrinite, atomic H:C and O:C, and ash-free carbon data were used to determine ranks that range from high-volatile C bituminous coal to meta-anthracite. A van Krevelen (atomic H:C vs. O:C) diagram of the vitrinite concentrates shows a smooth curve having its lowest point at H:C = 0.18 and O:C = 0.01. This improves the van Krevelen diagram by the addition of our vitrinite concentrate from meta-anthracite from the Narragansett basin of New England. Boron content (400–450 ppm) in two Illinois basin vitrinite concentrates was about an order of magnitude higher than B contents in other concentrates analyzed. We attribute this to marine origin or hydrothermal activity. The alkaline-earth elements Ca, Mg and Ba (DCAS) have higher concentrations in our vitrinite concentrates from bituminous coals of the Appalachian basin, than they do in vitrinite concentrates from the marine-roofed bituminous coals of the Illinois basin; therefore, a nonmarine origin for these alkaline-earth elements is postulated for the Appalachian basin coals. An ion-exchange mechanism due to high concentrations of these elements as ions in diagenetic water, but probably not recent ground water, may be responsible for the relatively high values of these elements in Appalachian concentrates. Higher concentrations of Ni and Cr in one of the English vitrinite concentrates and of Zr in the Australian concentrate probably indicate organic association and detrital influence, respectively.

International Journal of Coal Geology

Using laser micro mass spectrometry with the LAMMA-1000 instrument for monitoring relative elemental concentrations in vitrinite

The variation in relative elemental concentrations among a series of coal macerals belonging to the vitrinite maceral group was determined using laser micro mass spectrometry (LAMMS). Variations in Ba, Cr, Ga, Sr, Ti, and V concentrations among the coals were determined using the LAMM A-1000 instrument. LAMMS analysis is not limited to these elements; their selection illustrates the application of the technique. Ba, Cr, Ga, Sr, Ti, and V have minimal site-to-site variance in the vitrinite macerals of the studied coals as measured by LAMMS. The LAMMS data were compared with bulk elemental data obtained by instrumental neutron activation analysis (INAA) and D. C. arc optical emission spectroscopy (DCAS) in order to determine the reliability of the LAMMS data. The complex nature of the ionization phenomena in LAMMS and the lack of standards characterized on a microscale makes obtaining quantitative elemental data within the ionization microvolume difficult; however, we demonstrate that the relative variation of an element among vitrinites from different coal beds in the eastern United States can be observed using LAMMS in a "bulk" mode by accumulating signal intensities over several microareas of each vitrinite. Our studies indicate gross changes (greater than a factor of 2 to 5 depending on the element) can be monitored when the elemental concentration is significantly above the detection limit. "Bulk" mode analysis was conducted to evaluate the accuracy of future elemental LAMMS microanalyses. The primary advantage of LAMMS is the inherent spatial resolution, ~ 20 ??m for coal. Two different vitrite bands in the Lower Bakerstown coal bed (CLB-1) were analyzed. The analysis did not establish any certain concentration differences in Ba, Cr, Ga, Sr, Ti, and V between the two bands. ?? 1988 Springer-Verlag.

Mikrochimica Acta

DISTRIBUTION OF TRACE ELEMENTS IN COAL MINERALS OF SELECTED EASTERN UNITED STATES COALS.

The association of 34 elements with minerals found in coal was determined by a combination of analytical techniques on size and density fractions of low-temperature ash (LTA). Instrumental neutron activation analysis was used to determine the concentrations of the elements, and X-ray diffraction analysis, scanning electron microscopy, and scanning transmission electron microscopy were used to identify the minerals present in the LTA. The distribution of elemental and mineral concentrations in different size fractions was also determined. Between 35 and 60 weight percent of the LTA was composed of particles smaller than 2 mu m.

Conference Paper

Distribution of trace elements in coal from the Powhatan No. 6 mine, Ohio

Size and density separates of low-temperature-ashed coal from the Powhatan No. 6 mine, Ohio, have been used to determine the mode of occurrence of 28 minor and trace elements in coal. The size distribution of the major minerals has been determined, and correlations of trace elements with major minerals have been made. The role of minor minerals in the mode of occurrence of trace elements is also discussed. Instrumental-neutron-activation analysis was used to determine elemental concentrations, and X-ray diffraction and scanning electron microscopy were used for mineral identification.

Ohio