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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↗

Downhole measurements and fluid chemistry of a castle rock steam well, the Geysers, Lake County, California

Wellbore and reservoir processes in a steam well in the Castle Rock field of The Geysers have been studied by means of down-hole pressure and temperature measurements and analyses of ejected water and steam produced under bleed and full flow. Down-hole measurements show that below a vapor zone there is liquid water in the well in pressure equilibrium with reservoir steam at a depth of 2290 m. The progressive decreases, from 1973 to 1977, of pressure and temperature in the vapor zone indicate that wellbore heat loss is high enough to condense a large fraction of the steam inflow. The chemical composition of water ejected from the well is consistent with an origin from wellbore condensation of steam. Calculations using the differences in gas and isotopic compositions between bleed and full-flow steam show that about half of the full-flow steam originated as liquid water in the reservoir and that about 30% of the steam entering the well under bleed was condensed in the wellbore and drained downward. Heat loss calculations are also consistent with this amount of condensation.

Geothermics↗

Correlations among hydrocarbon microseepage, soil chemistry, and uptake of micronutrients by plants, Bell Creek oil field, Montana

Chelate-extractable iron and manganese concentrations in soils over and around the Bell Creek oil field suggest that compared to low average background values, there are moderate amounts of these elements directly over the production area and higher concentrations distributed in an aureole pattern around the periphery of the field. Adsorbed and organically bound iron and manganese appear to be readily taken up by plants resulting in anomalously high levels of these elements in leaves and needles over the oil field and suggesting correlation with corresponding low concentrations in soils. Iron and manganese appear to have bypassed the soil formation process where, under normal oxidizing conditions, they would have ultimately precipitated as insoluble oxides and hydroxides.

Journal of Geochemical Exploration↗

Rock chemistry and fluid inclusion studies as exploration tools for ore deposits in the Sila batholith, southern Italy

The Sila batholith is the focus of an extensive petrogenetic research program, which includes an assessment of its potential to host granite-related ore deposits. Univariate and multivariate statistical techniques were applied to major- and minor-element rock geochemical data. The analysis indicates that the highest potential for mineralization occurs in corundum-normative, peraluminous, unfoliated, relatively late-stage plutons. The plutons are enriched in Rb, Nb, Ta and U, but depleted in Fe, Mg and Sr. The K/Rb, Ba/Rb, Rb/Sr and Rb 3 /Ba·Sr·K indices and high R -factor scores of Si-K-Rb are typical of mineralized granitic rocks. A reconnaissance fluid inclusion study indicates that the sub-solidus rock was infiltrated by solutions of widely different temperatures (50–416°C) and variable salinities (0 to ∼26 wt.% NaCl equivalent). The higher-temperature solutions probably represent granite or magmatic-related Hercynian fluids, whereas the lower-temperature fluids may be either Hercynian or Alpine in age. Fluids with characteristics typical of mineralized “porphyry” systems have not been recognized.

Journal of Geochemical Exploration↗

Effects of fluoride on screech owl reproduction: Teratological evaluation, growth, and blood chemistry in hatchlings

The effects on reproduction in screech owls ( Otus asio ) of chronic dietary sodium fluoride administration at 0, 40, and 200 ppm were examined. Fluoride at 40 ppm resulted in a significantly smaller egg volume, while 200 ppm also resulted in lower egg weights and lengths. Day-one hatchlings in the 200 ppm group weighed almost 10% less than controls and had shorter crown-rump lengths. No gross abnormalities were apparent. Skeletal clearing and staining revealed significantly shorter tibiotarsus lengths in the 40 ppm and 200 ppm groups and a shorter radius-ulna length in the 200 ppm group. By 7 days of age, body weights and lengths did not differ from controls, but the tibiotarsus in the 200 ppm group remained shorter. No significant differences were detected in hematocrit, hemoglobin, plasma calcium or alkaline phosphatase. Plasma phosphorus levels were higher in the 40 ppm group than in controls. These results, in combination with the findings of Pattee et al. [25], revealed significant impairment of overall reproduction, suggesting that sodium fluoride could cause slight to moderate reproduction disorders in owls in fluoride-polluted areas.

Toxicology Letters↗

Precipitation-chemistry measurements from the California Acid Deposition Monitoring Program, 1985-1990

The configuration of the California Acid Deposition Monitoring Program (CADMP) precipitation network is described and quality assurance results summarized. Comparison of CADMP and the National Acid Deposition Program/National Trends Network (NADP/NTN) data at four parallel sites indicated that mean depth-weighted differences were less than 3 μeq ℓ −1 for all ions, being statistically significant for ammonium, sulfate and hydrogen ion. These apparently small differences were 15–30% of the mean concentrations of ammonium, sulfate and hydrogen ion. Mean depth-weighted concentrations and mass deposition rates for the period 1985–1990 are summarized; the latter were highest either where concentrations or precipitation depths were relatively high.

Atmospheric Environment↗

Use of spatial statistics and isotopic tracers to measure the influence of arsenical pesticide use on stream sediment chemistry in New England, USA

Arsenical pesticides and herbicides, principally Pb arsenate, Ca arsenate, and Na arsenate with lesser use of other metal-As pesticides, were widely applied on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Agricultural census data for this time period is used to define an agricultural index that identifies areas that are inferred to have used arsenical pesticides extensively. Factor analysis on metal concentrations in 1597 stream sediment samples collected throughout New England, grouped by agricultural-index categories, indicate a positive association of areas with stream sediment sample populations that contain higher As and Pb concentrations than samples from the region as a whole with sample site settings having high agricultural-index values. Population statistics for As and Pb concentrations and factor scores for an As-Pb factor all increase systematically and significantly with increasing agricultural-index intensity in the region, as tested by Kruskal-Wallis analysis. Lead isotope compositions for 16 stream sediments from a range of agricultural-index settings generally overlap the observed variation in rock sulfides and their weathering products; however, sediments collected from high agricultural-index settings have slightly more radiogenic Pb compositions, consistent with an industrial Pb contribution to these samples. Although weathering products from rocks are likely to be the dominant source of As and metals to most of the stream sediment samples collected in the region, the widespread use of arsenical pesticides and herbicides in New England during the early 1900-1960s appears to be a significant anthropogenic source of As and metals to many sediments in agricultural areas in the region and has raised background levels of As in some regions. Elevated concentrations of As in stream sediments are of concern for two reasons. Stream sediments with elevated As concentrations delineate areas with elevated background concentrations of As from both natural rock and anthropogenic sources that may contribute As to groundwater systems used for drinking water supplies. Conversion of agricultural land contaminated with arsenical pesticide residues to residential development may increase the likelihood that humans will be exposed to As. In addition, many stream sediment sites have As concentrations that exceed sediment quality guidelines established for freshwater ecosystems. Thirteen percent of the New England sediment sample sites exceed 9.79 mg/kg As, the threshold effects concentration (TEC), below which harmful effects are unlikely to be observed. Arsenic concentrations exceed 33 mg/kg, the probable effects concentration (PEC), above which harmful effects on sediment-dwelling organisms are expected to occur frequently, at 1.25% of the sediment sample sites. The sample sites that exceed the PEC value occur predominately in agricultural areas that used arsenical pesticides.

Conference Paper↗

Links between climate change, water-table depth, and water chemistry in a mineralized mountain watershed

Recent studies suggest that climate change is causing rising solute concentrations in mountain lakes and streams. These changes may be more pronounced in mineralized watersheds due to the sensitivity of sulfide weathering to changes in subsurface oxygen transport. Specific causal mechanisms linking climate change and accelerated weathering rates have been proposed, but in general remain entirely hypothetical. For mineralized watersheds, a favored hypothesis is that falling water tables caused by declining recharge rates allow an increasing volume of sulfide-bearing rock to become exposed to air, thus oxygen. Here, we test the hypothesis that falling water tables are the primary cause of an increase in metals and SO4 (100-400%) observed since 1980 in the Upper Snake River (USR), Colorado. The USR drains an alpine watershed geologically and climatologically representative of many others in mineralized areas of the western U.S. Hydrologic and chemical data collected from 2005 to 2011 in a deep monitoring well (WP1) at the top of the USR watershed are utilized. During this period, both water table depths and groundwater SO4 concentrations have generally increased in the well. A numerical model was constructed using TOUGHREACT that simulates pyrite oxidation near WP1, including groundwater flow and oxygen transport in both saturated and unsaturated zones. The modeling suggests that a falling water table could produce an increase in metals and SO4 of a magnitude similar to that observed in the USR (up to 300%). Future water table declines may produce limited increases in sulfide weathering high in the watershed because of the water table dropping below the depth of oxygen penetration, but may continue to enhance sulfide weathering lower in the watershed where water tables are shallower. Advective air (oxygen) transport in the unsaturated zone caused by seasonally variable recharge and associated water table fluctuations was found to have little influence on pyrite oxidation rates near WP1. However, this mechanism could be important in the case of a shallow dynamic water table and more abundant/reactive sulfides in the shallow subsurface. Data from WP1 and numerical modeling results are thus consistent with the falling water table hypothesis, and illustrate fundamental processes linking climate and sulfide weathering in mineralized watersheds.

Applied Geochemistry↗

Modeling and management of pit lake water chemistry 2: Case studies

Pit lakes, a common product of open pit mining techniques, may become long-term, post-mining environmental risks or long-term, post-mining water resources depending upon management decisions. This study reviews two published pit lake modeling studies and one pit lake monitoring program in order to increase the transparency of approaches used in pit lake prediction and management. The first model is a two-year limnological simulation of the existing Dexter pit lake, Nevada, USA that accurately modeled temperature profiles, salinity profiles, and turnover events observed between 1999 and 2000. The second model is a 55-year prediction of a future pit lake in the Martha Mine, New Zealand that identified the need for additional mitigation and evaluated potential effects of cost-effective mitigation options. The final study reviews eight years of monitoring data collected from the Berkeley pit lake, Montana, USA, from 2004 to 2012. This study identifies changes in the physical limnology and water quality of the pit lake that resulted from metal recovery operations, and highlights the value of monitoring programs in general. Whereas these pit lakes are different in many ways, the management tools discussed herein maximized the value and understanding of the post-mining resources.

Applied Geochemistry↗

Interspecies and interregional comparisons of the chemistry of PAHs and trace elements in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from Poland and Alaska

Comparative biogeochemical studies performed on the same plant species in remote areas enable pinpointing interspecies and interregional differences of chemical composition. This report presents baseline concentrations of PAHs and trace elements in moss species Hylocomium splendens and Pleurozium schreberi from the Holy Cross Mountains (south-central Poland) (HCM) and Wrangell-Saint Elias National Park and Preserve (Alaska) and Denali National Park and Preserve (Alaska). Total PAH concentrations in the mosses of HCM were in the range of 473-2970 ??g kg-1 (dry weight basis; DW), whereas those in the same species of Alaska were 80-3390 ??g kg-1 DW. Nearly all the moss samples displayed the similar ring sequence: 3 > 4 > 5 > 6 for the PAHs. The 3 + 4 ring/total PAH ratios show statistically significant differences between HCM (0.73) and Alaska (0.91). The elevated concentrations of PAHs observed in some sampling locations of the Alaskan parks were linked to local combustion of wood, with a component of vehicle particle- and vapor-phase emissions. In HCM, the principal source of PAH emissions has been linked to residential and industrial combustion of coal and vehicle traffic. In contrast to HCM, the Alaskan mosses were distinctly elevated in most of the trace elements, bearing a signature of??the underlying geology. H.??splendens and P. schreberi showed diverse bioaccumulative capabilities of PAHs in all three study areas. ?? 2008 Elsevier Ltd.

Atmospheric Environment↗

A modern vs. Permian black shale - the hydrography, primary productivity, and water-column chemistry of deposition

The sediment currently accumulating in the Cariaco Basin, on the continental shelf of Venezuela, has an elevated organic-carbon content of approximately 5%; is accumulating under O2-depleted bottom-water conditions (SO42- reduction); is composed dominantly of foraminiferal calcite, diatomaceous silica, clay, and silt; and is dark greenish gray in color. Upon lithification, it will become a black shale. Recent studies have established the hydrography of the basin and the level of primary productivity and bottom-water redox conditions. These properties are used to model accumulation rates of Cd, Cr, Cu, Mo, Ni, V, and Zn on the seafloor. The model rates agree closely with measured rates for the uppermost surface sediment.The model is applied to the Meade Peak Phosphatic Shale Member of the Phosphoria Formation, a phosphate deposit of Permian age in the northwest United States. It too has all of the requisite properties of a black shale. Although the deposit is a world-class phosphorite, it is composed mostly of phosphatic mudstone and siltstone, chert, limestone, and dolomite. It has organic-carbon concentrations of up to 15%, is strongly enriched in several trace elements above a terrigenous contribution and is black. The trace-element accumulation defines a mean primary productivity in the photic zone of the Phosphoria Basin as moderate, at 500 g m-2 year-1 organic carbon, comparable to primary productivity in the Cariaco Basin. The source of nutrient-enriched water that was imported into the Phosphoria Basin, upwelled into the photic zone, and supported primary productivity was an O2 minimum zone of the open ocean. The depth range over which the water was imported would have been between approximately 100 and 600 m. The mean residence time of bottom water in the basin was approximately 4 years vs. 100 years in the Cariaco Basin. The bottom water was O2 depleted, but it was denitrifying, or NO3- reducing, rather than SO42- reducing. Published by Elsevier B.V.

Chemical Geology↗

Characterization of gas chemistry and noble-gas isotope ratios of inclusion fluids in magmatic-hydrothermal and magmatic-steam alunite

Chemical and isotope data were obtained for the active gas and noble gas of inclusion fluids in coarse-grained samples of magmatic-hydrothermal and magmatic-steam alunite from well-studied deposits (Marysvale, Utah; Tambo, Chile; Tapajo??s, Brazil; Cactus, California; Pierina, Peru), most of which are discussed in this Volume. Primary fluid inclusions in the alunite typically are less than 0.2 ??m but range up to several micrometers. Analyses of the active-gas composition of these alunite-hosted inclusion fluids released in vacuo by both crushing and heating indicate consistent differences in the compositions of magmatic-hydrothermal and magmatic-steam fluids. The compositions of fluids released by crushing were influenced by contributions from significant populations of secondary inclusions that trapped largely postdepositional hydrothermal fluids. Thermally released fluids gave the best representation of the fluids that formed primary alunite. The data are consistent with current models for the evolution of magmatic-hydrothermal and magmatic-steam fluids. Magmatic-steam fluids are vapor-dominant, average about 49 mol% H2O, and contain N2, H2, CH4, CO, Ar, He, HF, and HCl, with SO2 the dominant sulfur gas (average SO2/ H2S=202). In contrast, magmatic-hydrothermal fluids are liquid-dominant, average about 88 mol% H2O, and N2, H2, CO2, and HF, with H2S about as abundant as SO2 (average SO2/H2 S=0.7). The low SO2/H2S and N2/Ar ratios, and the near-absence of He in magmatic-hydrothermal fluids, are consistent with their derivation from degassed condensed magmatic fluids whose evolution from reduced-to-oxidized aqueous sulfur species was governed first by rock and then by fluid buffers. The high SO2/H2S and N2/Ar with significant concentrations of He in magmatic-steam fluids are consistent with derivation directly from a magma. None of the data supports the entrainment of atmospheric gases or mixing of air-saturated gases in meteoric water in either magmatic-hydrothermal or magmatic-steam fluids. Thus, the oxidation of SO2 to aqueous sulfate in the magmatic-steam fluids did not result from mixing with atmospheric oxygen. Both of the fluid types are characterized by high H2 contents that range from 0.2 mol% to the extraordinarily large amounts (66 mol%) observed in some magmatic-steam fluids. Modeling of gas speciation using SOLVGAS requires most of the gas species to have been in disequilibrium at the time of their trapping in the fluid inclusions. The origin of such extreme H2 concentrations, although problematic, is thought to be largely related to accumulation of H2 from the reaction of water with ferrous iron during the rise of magma and probably even after exsolution of fluid from a magma. The large contents of reduced gases in the inclusion fluids are far in excess of those observed in volcanic emanations, and are thought to reflect the close "sampling position" of the host alunite relative to the location of the magma. Isotope ratios of He and Ne indicate largely crustal sources for these gases in the alunite parental fluids derived from Tertiary magmas, but a greater mantle component for the gases in alunite parental fluids derived from Proterozoic magmas.

Chemical Geology↗

Inorganic chemistry, petrography and palaeobotany of Permian coals in the Prince Charles Mountains, East Antarctica

Sampled outcrops of Permian coal seams of the Bainmedart Coal Measures in the Lambert Graben, eastern Antarctica, have been analysed for their proximates, ultimates, ash constituents and trace elements. A similar series of samples has been analysed for their principle maceral and microlithotype components and vitrinite reflectance. The coals are sub-bituminous to high volatile bituminous in rank; maturity increases markedly in southern exposures around Radok Lake where the oldest part of the succession is exposed and some strata have been intruded by mafic dykes and ultramafic sills. The coal ash is mostly silica and aluminium oxides, indicating that the mineral ash component is mostly quartz and various clay minerals. The ratio of silica to aluminium oxides appears to increase in an upward stratigraphic direction. The coal macerals include a relatively high liptinite content (mainly sporinite) that is significantly higher than for typical Gondwana coals. Greater degrees of weathering within the floodbasin/peat mire environments associated with climatic drying towards the end of the Permian might account for both preferential sporopollenin preservation and increased silica:aluminium oxide ratios up-section. Correlation of the coal maceral components to adjacent peninsula India coals indicates the closest comparative coals of similar age and rank occur within the Godavari Basin, rather then the Mahanadi Basin, which is traditionally interpreted to have been contiguous with the Lambert Graben before Gondwanan breakup. The petrological characteristics suggest that either previous interpretations of Palaeozoic basin alignments between Antarctica and India are incorrect, or that environmental settings and post-Permian burial histories of these basins were strongly independent of their tectonic juxtaposition. A permineralized peat bed within the succession reveals that the coals predominantly comprise wood- and leaf-rich debris derived from low-diversity forest-mire communities dominated by glossopterid and noeggerathiopsid gymnosperms. ?? 2005 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

Trace element geochemistry and surface water chemistry of the Bon Air coal, Franklin County, Cumberland Plateau, southeast Tennessee

Mean contents of trace elements and ash in channel, bench-column, and dump samples of the abandoned Bon Air coal (Lower Pennsylvanian) in Franklin County, Tennessee are similar to Appalachian COALQUAL mean values, but are slightly lower for As, Fe, Hg, Mn, Na, Th, and U, and slightly higher for ash, Be, Cd, Co, Cr, REEs, Sr, and V, at the 95% confidence level. Compared to channel samples, dump sample means are slightly lower in chalcophile elements (As, Cu, Fe, Ni, Pb, S, Sb, and V) and slightly higher in clay or heavy-mineral elements (Al, K, Mn, REEs, Th, Ti, U, and Y), but at the 95% confidence level, only As and Fe are different. Consistent abundances of clay or heavy-mineral elements in low-Br, high-S, high-ash benches that are relatively enriched in quartz and mire-to-levee species like Paralycopodites suggest trace elements are largely fluvial in origin. Factor analysis loadings and correlation coefficients between elements suggest that clays host most Al, Cr, K, Ti, and Th, significant Mn and V, and some Sc, U, Ba, and Ni. Heavy accessory minerals likely house most REEs and Y, lesser Sc, U, and Th, and minor Cr, Ni, and Ti. Pyrite appears to host As, some V and Ni, and perhaps some Cu, but Cu probably exists largely as chalcopyrite. Data suggest that organic debris houses most Be and some Ni and U, and that Pb and Sb occur as Pb-Sb sulfosalt(s) within organic matrix. Most Hg, and some Mn and Y, appear to be hosted by calcite, suggesting potential Hg remobilization from original pyrite, and Hg sorption by calcite, which may be important processes in abandoned coals. Most Co, Zn, Mo, and Cd, significant V and Ni, and some Mn probably occur in non-pyritic sulfides; Ba, Sr, and P are largely in crandallite-group phosphates. Selenium does not show organic or "clausthalite" affinities, but Se occurrence is otherwise unclear. Barium, Mn, Ni, Sc, U, and V, with strongly divided statistical affinities, likely occur subequally in multiple modes. For study area surface waters, highest levels of most trace elements occur in mine-adit or mine-dump drainage. Effluent flow rates strongly affect both acidity and trace element levels. Adit drainages where flow is only a trickle have the most acidic waters (pH 3.78-4.80) and highest trace element levels (up to two orders of magnitude higher than in non-mine site waters). Nonetheless, nearly all surface waters have low absolute concentrations of trace elements of environmental concern, and all waters sampled meet U.S. EPA primary drinking water standards and aquatic life criteria for all elements analyzed. Secondary drinking water standards are also met for all parameters except Al, pH, Fe, and Mn, but even in extreme cases (mine waters with pH as low as 3.78 and up to 1243 ppb Al, 6280 ppb Fe, and 721 ppb Mn, and non-mine dam-outflow waters with up to 18,400 ppb Fe and 1540 ppb Mn) downslope attenuation is apparently rapid, as down-drainage plateau-base streams show background levels for all these parameters. ?? 2005 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

Petrology and chemistry of Permian coals from the Paraná Basin: 1. Santa Terezinha, Leão-Butiá and Candiota Coalfields, Rio Grande do Sul, Brazil

The current paper presents results on petrological and geochemical coal seam characterization in Permian coal-bearing strata from the Paraná Basin, southern Brazil. Sequence stratigraphic analysis shows that peat accumulation in Permian time was closely linked to transgressive/regressive cycles, with peat accumulation occurring in a predominantly back barrier/lagoonal setting. Coal petrographic analysis indicates subbituminous coals at Candiota and Leão-Butiá and high volatile bituminous coals at Santa Terezinha, where locally the coal seams are thermally altered by volcanic intrusions. Petrographic composition is highly variable, with seams at Candiota and Santa Terezinha frequently enriched in inertinite. Chemical analyses indicate that all coals are mineral matter-rich (mean 49.09 wt.%), with SiO 2 and Al 2 O 3 dominating as determined by ICP-AES. Quartz is also the predominant mineral detected by X-ray diffraction, where it is associated with feldspar, kaolinite and hematite and iron-rich carbonates. The results from Scanning Electron Microscopy are broadly consistent with the bulk chemical and mineralogical analysis. Quartz and clays are common in all samples analyzed. Other minerals observed were, amongst others, carbonates (calcite, siderite, ankerite), pyrite, monazite, kaolinite, barite, sphalerite, rutile and quartz of volcanic origin. The distribution of trace elements is well within the range typical for coal basins of other areas despite the fact that the Paraná Basin coals are very high in ash yields. The average concentrations for elements of environmental concern (As, B, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Tl, U, V, Zn) are similar to or less than the mean values for U.S. coal. However, considered on an equal energy basis, Paraná Basin coals will produce in combustion 5 to 10 times the amount of most elements compared to an equal weight US coal. Concentrations of major and trace elements, such as Fe, B and S, appear to be controlled by depositional setting, with increasing values in coal seams overlain by brackish/marine strata. Hierarchical cluster analysis identified three groups of major minerals and seven groups of trace elements based on similarity levels. On a regional scale, the coalfields can be separated by the differences in rank (Candiota and Leão-Butiá versus Santa Terezinha) and by applying discriminant analysis based on 4 trace elements (Li, As, Sr, Sb). Highest Rb and Sr values occur at Candiota and are linked to syngenetic volcanism of the area, whereas high Y and Sr values at Santa Terezinha can be related to the frequent diabase intrusions in that area.

International Journal of Coal Geology↗

Chemistry of thermally altered high volatile bituminous coals from southern Indiana

The optical properties and chemical characteristics of two thermally altered Pennsylvanian high volatile bituminous coals, the non-coking Danville Coal Member (Ro = 0.55%) and the coking Lower Block Coal Member (Ro = 0.56%) were investigated with the purpose of understanding differences in their coking behavior. Samples of the coals were heated to temperatures of 275????C, 325????C, 375????C and 425????C, with heating times of up to one hour. Vitrinite reflectance (Ro%) rises with temperature in both coals, with the Lower Block coal exhibiting higher reflectance at 375????C and 425????C compared to the Danville coal. Petrographic changes include the concomitant disappearance of liptinites and development of vesicles in vitrinites in both coals, although neither coal developed anisotropic coke texture. At 375????C, the Lower Block coal exhibits a higher aromatic ratio, higher reflectance, higher carbon content, and lower oxygen content, all of which indicate a greater degree of aromatization at this temperature. The Lower Block coal maintains a higher CH2/CH3 ratio than the Danville coal throughout the heating experiment, indicating that the long-chain unbranched aliphatics contained in Lower Block coal liptinites are more resistant to decomposition. As the Lower Block coal contains significant amounts of liptinite (23.6%), the contribution of aliphatics from these liptinites appears to be the primary cause of its large plastic range and high fluidity. ?? 2006 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

Depositional setting, petrology and chemistry of Permian coals from the Paraná Basin: 2. South Santa Catarina Coalfield, Brazil

In Brazil economically important coal deposits occur in the southern part of the Paraná Basin, where coal seams occur in the Permian Rio Bonito Formation, with major coal development in the states of Rio Grande de Sul and Santa Catarina. The current paper presents results on sequence stratigraphic interpretation of the coal-bearing strata , and petrological and geochemical coal seam characterization from the South Santa Catarina Coalfield, Paraná Basin. In terms of sequence stratigraphic interpretation the precursor mires of the Santa Catarina coal seams formed in an estuarine-barrier shoreface depositional environment , with major peat accumulation in a high stand systems tract (Pre-Bonito and Bonito seams), a lowstand systems tract (Ponta Alta seam, seam A, seam B) and a transgressive systems tract (Irapuá, Barro Branco and Treviso seams). Seam thicknesses range from 1.70 to 2.39 m, but high proportions of impure coal (coaly shale and shaley coal), carbonaceous shale and partings reduce the net coal thickness significantly. Coal lithoypes are variable, with banded coal predominant in the Barro Branco seam, and banded dull and dull coal predominantly in Bonito and Irapuá seams, respectively. Results from petrographic analyses indicate a vitrinite reflectance range from 0.76 to 1.63 %Rrandom (HVB A to LVB coal). Maceral group distribution varies significantly, with the Barro Branco seam having the highest vitrinite content (mean 67.5 vol%), whereas the Irapuá seam has the highest inertinite content (33.8 vol%). Liptinite mean values range from 7.8 vol% (Barro Branco seam) to 22.5 vol% (Irapuá seam). Results from proximate analyses indicate for the three seams high ash yields (50.2 – 64.2 wt.%). Considering the International Classification of in-Seam Coals, all samples are in fact classified as carbonaceous rocks (> 50 wt.% ash). Sulfur contents range from 3.4 to 7.7 wt.%, of which the major part occurs as pyritic sulfur. Results of X-ray diffraction indicate the predominance of quartz and kaolinite (also pyrite). Gypsum , gibbsite , jarosite and calcite were also identified in some samples. Feldspar was noted but is rare. The major element distribution in the three seams (coal basis) is dominated by SiO 2 (31.3 wt.%, mean value), Al 2 O 3 (14.5 wt.%, mean value) and Fe 2 O 3 (6.9 wt.%, mean value). Considering the concentrations of trace elements that are of potential environmental hazards the Barro Branco, Bonito and Irapuá seams (coal base) are significantly enriched in Co (15.7 ppm), Cr (54.5 ppm), Li (59.3 ppm), Mn (150.4 ppm), Pb (58.0 ppm) and V (99.6 ppm), when compared to average trace elements contents reported for U. S. coals. Hierarchical cluster analysis identified, based on similarity levels, three groups of major elements and seven groups of trace elements. Applying discriminant analyses using trace and major element distribution, it could be demonstrated that the three seams from Santa Catarina show distinct populations in the discriminant analyses plots, and also differ from the coals of Rio Grande do Sul analyzed in a previous study.

Santa Catarina↗

The estuarine chemistry and isotope systematics of 234,238U in the Amazon and Fly Rivers

Natural concentrations of 238U and ??234U values were determined in estuarine surface waters and pore waters of the Amazon and Fly (Papua New Guinea) Rivers to investigate U transport phenomena across river-dominated land-sea margins. Discharge from large, tropical rivers is a major source of dissolved and solid materials transported to the oceans, and are important in defining not only oceanic mass budgets, but also terrestrial weathering rates. On the Amazon shelf, salinity-property plots of dissolved organic carbon, pH and total suspended matter revealed two vastly contrasting water masses that were energetically mixed. In this mixing zone, the distribution of uranium was highly non-conservative and exhibited extensive removal from the water column. Uranium removal was most pronounced within a salinity range of 0-16.6, and likely the result of scavenging and flocculation reactions with inorganic (i.e., Fe/Mn oxides) and organic colloids/particles. Removal of uranium may also be closely coupled to exchange and resuspension processes at the sediment/water interface. An inner-shelf pore water profile indicated the following diagenetic processes: extensive (???1 m) zones of Fe(III) - and, to a lesser degree, Mn(IV) - reduction in the absence of significant S(II) concentrations appeared to facilitate the formation of various authigenic minerals (e.g., siderite, rhodocrosite and uraninite). The pore water dissolved 238U profile co-varied closely with Mn(II). Isotopic variations as evidenced in ??234U pore waters values from this site revealed information on the origin and history of particulate uranium. Only after a depth of about 1 m did the ??234U value approach unity (secular equilibrium), denoting a residual lattice bound uranium complex that is likely an upper-drainage basin weathering product. This suggests that the enriched ??234U values represent a riverine surface complexation product that is actively involved in Mn-Fe diagenetic cycles and surface complexation reactions. In the Fly River estuary, 238U appears to exhibit a reasonably conservative distribution as a function of salinity. The absence of observed U removal does not necessarily imply non-reactivity, but instead may record an integration of concurrent U removal and release processes. There is not a linear correlation between ??234U vs. 1/ 238U that would imply simple two component mixing. It is likely that resuspension of bottom sediments, prolonged residence times in the lower reaches of the Fly River, and energetic particle-colloid interactions contribute to the observed estuarine U distribution. The supply of uranium discharged from humid, tropical river systems to the sea appears to be foremost influenced by particle/water interactions that are ultimately governed by the particular physiographic and hydrologic characteristics of an estuary. ?? 2004 Elsevier Ltd. All rights reserved.

Continental Shelf Research↗